WO2020059382A1 - Light-shielding film, method for manufacturing light-shielding film, optical element, solid-state imaging element, and headlight unit - Google Patents

Light-shielding film, method for manufacturing light-shielding film, optical element, solid-state imaging element, and headlight unit Download PDF

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Publication number
WO2020059382A1
WO2020059382A1 PCT/JP2019/032377 JP2019032377W WO2020059382A1 WO 2020059382 A1 WO2020059382 A1 WO 2020059382A1 JP 2019032377 W JP2019032377 W JP 2019032377W WO 2020059382 A1 WO2020059382 A1 WO 2020059382A1
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Prior art keywords
light
group
black
shielding film
layer
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PCT/JP2019/032377
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French (fr)
Japanese (ja)
Inventor
貴洋 大谷
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富士フイルム株式会社
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Priority to CN201980050527.6A priority Critical patent/CN112513692A/en
Priority to JP2020548151A priority patent/JP7245843B2/en
Priority to KR1020217001039A priority patent/KR102660236B1/en
Publication of WO2020059382A1 publication Critical patent/WO2020059382A1/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S41/00—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps
    • F21S41/40—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps characterised by screens, non-reflecting members, light-shielding members or fixed shades
    • F21S41/43—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps characterised by screens, non-reflecting members, light-shielding members or fixed shades characterised by the shape thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S45/00—Arrangements within vehicle lighting devices specially adapted for vehicle exteriors, for purposes other than emission or distribution of light
    • F21S45/10—Protection of lighting devices
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14601—Structural or functional details thereof
    • H01L27/1462—Coatings
    • H01L27/14623—Optical shielding

Definitions

  • the present invention relates to a light-shielding film, a method for manufacturing the light-shielding film, an optical element, a solid-state imaging device, and a headlight unit.
  • a color filter used in a liquid crystal display device is provided with a light-shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast.
  • a solid-state imaging device such as a charge coupled device (CCD) image sensor and a complementary metal-oxide semiconductor (CMOS) image sensor is provided with a light shielding film for the purpose of preventing noise generation and improving image quality.
  • CCD charge coupled device
  • CMOS complementary metal-oxide semiconductor
  • a technique of providing an oxygen blocking layer on a light shielding film and a colored pixel is known.
  • a black matrix, a color filter layer, an oxygen blocking layer that covers the black matrix and the color filter layer and contains at least an oxygen blocking compound, and a color filter layer and an oxygen blocking layer is disclosed.
  • a color filter including a mixed layer containing a dye and an oxygen-blocking compound therebetween.
  • the present inventors have examined the black matrix including the oxygen barrier layer described in Patent Document 1, and found that the black matrix (light-shielding film) may not be able to sufficiently satisfy the light resistance and the moisture resistance. did.
  • the black color material contains at least one metal oxynitride selected from the group consisting of titanium, vanadium, zirconium, and niobium.
  • the black color material contains carbon black, a benzofuranone compound or a perylene compound.
  • [4] The light-shielding film according to any one of [1] to [3], wherein the content of the black colorant is 20 to 80% by mass based on the total mass of the black layer.
  • [5] The light-shielding film according to any one of [1] to [4], wherein the oxygen barrier layer contains silicon oxide.
  • [6] The light-shielding film according to any one of [1] to [5], wherein a ratio of a thickness of the black layer to a thickness of the oxygen barrier layer is 2 to 100.
  • [7] The light-shielding film according to any one of [1] to [6], wherein the oxygen barrier layer has an oxygen permeability of 10 ml / (m 2 ⁇ day ⁇ atm) or less.
  • the method for producing a light-shielding film according to [9], wherein the step of forming the oxygen barrier layer includes a step of depositing an inorganic material.
  • Method for manufacturing a light-shielding film [12] The method for producing a light-shielding film according to any one of [9] to [11], wherein the light-shielding composition contains at least two kinds of polymerizable compounds.
  • a headlight unit for a vehicular lamp comprising: a light source; and a light shielding unit that shields at least a part of light emitted from the light source, wherein the light shielding unit is any one of [1] to [8].
  • a headlight unit comprising the light-shielding film according to item 1.
  • a light-shielding film having excellent light resistance and moisture resistance can be provided. Further, the present invention can provide a method for manufacturing a light-shielding film, an optical element, a solid-state imaging device, and a headlight unit.
  • FIG. 3 is a schematic sectional view illustrating a configuration example of a solid-state imaging device.
  • FIG. 2 is a schematic cross-sectional view showing, on an enlarged scale, an imaging unit provided in the solid-state imaging device shown in FIG. 1.
  • FIG. 3 is a schematic sectional view illustrating a configuration example of an infrared sensor. It is a schematic diagram which shows the example of a structure of a headlight unit.
  • FIG. 3 is a schematic perspective view illustrating a configuration example of a light shielding unit of the headlight unit. It is a schematic diagram which shows an example of the light distribution pattern by a headlight unit. It is a schematic diagram which shows the other example of the light distribution pattern by a headlight unit.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
  • the notation of not indicating substituted or unsubstituted includes a group having a substituent as well as a group having no substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • actinic rays or “radiation” means, for example, far ultraviolet rays, extreme ultraviolet (EUV), X-rays, electron beams, and the like.
  • light means actinic rays and radiation.
  • exposure in this specification includes not only exposure with far ultraviolet rays, X-rays, EUV light, and the like, but also drawing with particle beams such as electron beams and ion beams.
  • (meth) acrylate represents acrylate and methacrylate.
  • (meth) acryl represents acryl and methacryl.
  • (meth) acryloyl represents acryloyl and methacryloyl.
  • (meth) acrylamide represents acrylamide and methacrylamide.
  • “monomer” and “monomer” have the same meaning.
  • ppm means “parts-per-million (10 ⁇ 6 )
  • ppb means “parts-per-billion (10 ⁇ 9 )
  • ppt is “ppt”. parts-per-trillion (10 -12 ) ".
  • the weight average molecular weight (Mw) is a value in terms of polystyrene measured by a GPC (Gel Permeation Chromatography) method.
  • the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), and uses TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) as a column and THF (tetrahydrofuran) as an eluent. ).
  • the light-shielding film of the present invention includes a black layer containing a black coloring material, and an oxygen blocking layer provided on the black layer.
  • the oxygen barrier layer is a single layer made of an inorganic material.
  • the thickness of the oxygen barrier layer is 10 to 500 nm.
  • the light-shielding film of the present invention on a support, a black colorant, a resin, a polymerizable compound, and a light-shielding composition containing a polymerization initiator is applied, and the obtained coating film is cured, It can be manufactured by a manufacturing method including a step of forming a black layer and a step of forming an oxygen barrier layer on the black layer.
  • the black layer contained in the light-shielding film of the present invention contains a black color material.
  • the black layer is not limited by the manufacturing method, and is, for example, a black layer (including a patterned black layer) obtained by curing a coating film formed using the light-shielding composition.
  • the light-shielding composition used for forming the black layer (hereinafter, simply referred to as “composition”) will be described.
  • the light-shielding composition contains at least a black coloring material, a resin, a polymerizable compound, and a polymerization initiator.
  • the light-shielding composition contains a black coloring material.
  • a black coloring material at least one selected from the group consisting of black pigments and black dyes can be used.
  • One type of black color material may be used alone, or two or more types may be used.
  • the content of the black color material in the black layer is not particularly limited, and may be, for example, 20 to 80% by mass based on the total mass of the black layer.
  • the content of the black colorant is preferably more than 20% by mass, more preferably 30% by mass or more, even more preferably 50% by mass or more based on the total mass of the black layer, from the viewpoint that the heat resistance of the light-shielding film is more excellent.
  • the content of the black colorant is preferably less than 80% by mass, more preferably 70% by mass or less, and more preferably 65% by mass or less based on the total mass of the black layer, from the viewpoint that the moisture resistance of the light-shielding film is more excellent. More preferred.
  • the content of the black colorant in the light-shielding composition may be, for example, 20 to 80% by mass based on the total solid content of the light-shielding composition, and from the viewpoint that the heat resistance of the light-shielding film is more excellent, It is preferably more than 20% by mass, more preferably 30% by mass or more, even more preferably 50% by mass or more based on the total solid content of the light-shielding composition. Further, the content of the black colorant in the light-shielding composition is preferably less than 80% by mass, and more preferably 70% by mass or less based on the total solid content of the light-shielding composition, from the viewpoint that the moisture resistance of the light-shielding film is more excellent.
  • the “total solid content” of the composition means a component that forms a layer or a film by curing or the like, and when the composition contains a solvent (organic solvent, water, or the like), the solvent is used. Means all components except. Liquid components are also considered as solids as long as they form a film. That is, by adjusting the content of the black coloring material with respect to the total solid content of the light-shielding composition, the content of the black coloring material in the black layer can be adjusted to a desired value.
  • a plurality of colorants that cannot be used alone as a black color material may be combined and adjusted so as to be black as a whole to be used as a black color material.
  • a single pigment may be used as a black pigment by combining a plurality of pigments having colors other than black.
  • a black dye may be used alone as a black dye by combining a plurality of dyes having colors other than black, and a pigment having a color other than black alone and a dye having a color other than black alone may be used. You may use as.
  • a black colorant means a colorant that absorbs over the entire wavelength range of 400 to 700 nm. More specifically, for example, a black color material that meets the evaluation criteria Z described below is preferable.
  • a composition containing a coloring material, a transparent resin matrix (such as an acrylic resin), and a solvent, and having a coloring material content of 60% by mass based on the total solid content is prepared.
  • the obtained composition is applied on a glass substrate so that the thickness of the coating film after drying becomes 1 ⁇ m to form a coating film.
  • the light-shielding properties of the dried coating film are evaluated using a spectrophotometer (UV-3600 manufactured by Hitachi, Ltd.). If the maximum value of the transmittance of the coating film after drying at a wavelength of 400 to 700 nm is less than 10%, it can be determined that the coloring material is a black coloring material that meets the evaluation criterion Z.
  • Black pigment Various known black pigments can be used as the black pigment.
  • the black pigment may be an inorganic pigment or an organic pigment.
  • a black pigment is preferable because the light resistance of the black layer is more excellent.
  • the black pigment a pigment that independently expresses black is preferable, and a pigment that independently expresses black and absorbs infrared light is more preferable.
  • the black pigment that absorbs infrared rays has, for example, absorption in a wavelength region of an infrared region (preferably, a wavelength of 650 to 1300 nm).
  • a black pigment having a maximum absorption wavelength in a wavelength range of 675 to 900 nm is also preferable.
  • the particle size of the black pigment is not particularly limited, but is preferably 5 to 100 nm, more preferably 5 to 50 nm, since the balance between the handleability and the stability over time of the composition (the black pigment does not settle out) is more excellent. 5 to 30 nm is more preferred.
  • particle diameter means the average primary particle diameter of the particle measured by the following method.
  • the average primary particle diameter can be measured using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • a transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
  • the maximum length of a particle image obtained using a transmission electron microscope (Dmax: the maximum length at two points on the contour of the particle image), and the maximum vertical length (DV-max: two straight lines parallel to the maximum length)
  • Dmax the maximum length at two points on the contour of the particle image
  • DV-max maximum vertical length
  • the geometric mean value (Dmax ⁇ DV-max) 1/2 was defined as the particle diameter.
  • the particle diameter of 100 particles was measured by this method, and the arithmetic average value was defined as the average primary particle diameter of the particles.
  • the inorganic pigment is not particularly limited as long as it has a light-shielding property and is a particle containing an inorganic compound, and a known inorganic pigment can be used.
  • a known inorganic pigment can be used.
  • an inorganic pigment is preferable because the black layer has more excellent low reflectivity and light blocking properties.
  • inorganic pigments include Group 4 metal elements such as titanium (Ti) and zirconium (Zr), Group 5 metal elements such as vanadium (V) and niobium (Nb), cobalt (Co), and chromium (Cr). , Copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and one or more selected from the group consisting of silver (Ag) Metal oxides, metal nitrides, metal oxynitrides, and the like containing the above metal element.
  • the metal oxide, metal nitride, and metal oxynitride particles in which other atoms are mixed may be used.
  • metal nitride-containing particles further containing an atom (preferably an oxygen atom and / or a sulfur atom) selected from the elements of Groups 13 to 17 of the periodic table can be used.
  • the method for producing the above-described metal nitride, metal oxide or metal oxynitride is not particularly limited as long as a black pigment having desired physical properties can be obtained. You can use any method. Examples of the gas phase reaction method include an electric furnace method and a thermal plasma method, and a thermal plasma method is preferable in that impurities are less mixed, particle diameters are easily formed, and productivity is high.
  • the above-mentioned metal nitride, metal oxide or metal oxynitride may be subjected to a surface modification treatment.
  • the surface modification treatment may be performed with a surface treatment agent having both a silicone group and an alkyl group. Examples of such inorganic particles include the “KTP-09” series (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • a nitride or oxynitride of at least one metal selected from the group consisting of titanium, vanadium, zirconium and niobium is more preferable, since generation of an undercut when forming a black layer can be suppressed.
  • the black color material further contains at least one metal oxynitride selected from the group consisting of titanium, vanadium, zirconium and niobium, in that the light resistance and the moisture resistance of the light-shielding film are more excellent. It is particularly preferable to contain a titanium oxynitride (titanium black).
  • Titanium black is black particles containing titanium oxynitride.
  • the surface of titanium black can be modified as needed for the purpose of improving dispersibility, suppressing cohesion, and the like. Titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and a water-repellent substance as disclosed in JP-A-2007-302636. Processing is also possible.
  • a method for producing titanium black a method in which a mixture of titanium dioxide and metallic titanium is reduced by heating in a reducing atmosphere (Japanese Patent Application Laid-Open No. 49-5432), an ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride.
  • a method of reducing titanium in a hydrogen-containing reducing atmosphere Japanese Patent Application Laid-Open No. 57-205322
  • a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia Japanese Patent Application Laid-Open No. 60-65069
  • the particle size of titanium black is not particularly limited, but is preferably from 10 to 45 nm, more preferably from 12 to 20 nm.
  • the specific surface area of titanium black is not particularly limited, but the value measured by the BET (Brunauer, Emmett, Teller) method is 5 to 5 because the water repellency after surface treatment with a water repellent has a predetermined performance. It is preferably 150 m 2 / g, more preferably 20 to 100 m 2 / g.
  • titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name, manufactured by Mitsubishi Materials Corporation), Tilac D (Trade name, manufactured by Ako Kasei Co., Ltd.) and MT-150A (trade name, manufactured by Teika Co., Ltd.).
  • the light-shielding composition also preferably contains titanium black as a dispersion containing titanium black and Si atoms.
  • titanium black is contained in the composition as a dispersion.
  • the content ratio of Si atoms to Ti atoms (Si / Ti) in the dispersion is preferably 0.05 to 0.5 in terms of mass, more preferably 0.07 to 0.4.
  • the above-mentioned dispersion target includes both those in which titanium black is in the state of primary particles and those in the form of aggregates (secondary particles).
  • the Si / Ti of the dispersion is too small, a residue tends to remain in the removed portion when the coating film using the dispersion is patterned by photolithography or the like, and the Si / Ti of the dispersion is large. If too much, the light-shielding ability tends to decrease.
  • the following means can be used.
  • a dispersion is obtained by dispersing titanium oxide particles and silicon oxide particles using a dispersing machine, and the mixture is subjected to a reduction treatment at a high temperature (for example, 850 to 1000 ° C.), whereby titanium black particles are reduced.
  • a dispersed object containing Si and Ti as a main component can be obtained.
  • Titanium black with adjusted Si / Ti can be produced, for example, by the method described in paragraphs 0005 and 0016 to 0021 of paragraph number publication of JP-A-2008-266045.
  • the content ratio of Si atoms to Ti atoms (Si / Ti) in the dispersion is determined, for example, by the method (2-1) or the method (2-3) described in paragraphs 0054 to 0056 of WO2011 / 049090. ) Can be measured.
  • the above-mentioned titanium black can be used.
  • a black pigment composed of iron oxide, carbon black, aniline black, or the like may be used alone or in combination of two or more as a dispersion. In this case, it is preferable that 50% by mass or more of the entirety of the dispersion is occupied by the dispersion composed of titanium black.
  • the light-shielding composition also preferably contains zirconium nitride or zirconium oxynitride.
  • Zirconium nitride or zirconium oxynitride is preferably coated with an inorganic compound.
  • the photocatalytic activity of the light-shielding pigment is suppressed without deteriorating the light-shielding properties of the pigment (light-shielding pigment), and the deterioration of the light-shielding composition is prevented. It will be easier.
  • Preferred specific examples of the inorganic compound include titanium dioxide, zirconia, silica, and alumina, and examples thereof include silica and alumina. It is also preferable to use a combination of titanium black and zirconium nitride, titanium black and zirconium oxynitride, titanium black and zirconium nitride coated with silica, and titanium black and zirconium nitride coated with alumina.
  • the inorganic pigment examples include carbon black.
  • the black coloring material preferably contains carbon black from the viewpoint of excellent light-shielding light resistance and more excellent suppression of fluctuations in optical characteristics after a light resistance test.
  • Examples of the carbon black include furnace black, channel black, thermal black, acetylene black, and lamp black.
  • a carbon black produced by a known method such as an oil furnace method may be used, or a commercially available product may be used.
  • Specific examples of commercially available carbon black include C.I. I. An organic pigment such as CI Pigment Black 1; I. Pigment Black 7 and the like.
  • the carbon black surface-treated carbon black is preferable.
  • the surface treatment By the surface treatment, the particle surface state of the carbon black can be modified, and the dispersion stability in the composition can be improved.
  • the surface treatment include a coating treatment with a resin, a surface treatment for introducing an acidic group, and a surface treatment with a silane coupling agent.
  • the carbon black carbon black coated with a resin is preferable.
  • the coating resin include epoxy resin, polyamide, polyamideimide, novolak resin, phenol resin, urea resin, melamine resin, polyurethane, diallyl phthalate resin, alkylbenzene resin, polystyrene, polycarbonate, polybutylene terephthalate, and modified polyphenylene oxide.
  • the content of the coating resin is preferably from 0.1 to 40% by mass, more preferably from 0.5 to 30% by mass, based on the total of the carbon black and the coating resin, from the viewpoint that the black layer has more excellent light-shielding properties and insulating properties. More preferred.
  • Organic pigment is not particularly limited as long as it has a light-shielding property and contains an organic compound, and a known organic pigment can be used.
  • Specific examples of the organic pigment include a benzofuranone compound, an azomethine compound, a perylene compound, and an azo compound.
  • the black coloring material preferably contains a benzofuranone compound or a perylene compound from the viewpoint that the moisture resistance of the light-shielding film is more excellent.
  • the benzofuranone compound is a compound having a benzofuran-2 (3H) -one structure or a benzofuran-3 (2H) -one structure in a molecule and which is colored black by absorbing light having a visible light wavelength.
  • benzofuranone compound examples include compounds described in JP-T-2010-534726, JP-T-2012-515233, and JP-T-2012-515234. Further, as the benzofuranone compound, a compound represented by any of the general formulas (63) to (68) is preferable.
  • R 206 , R 207 , R 212 , R 213 , R 218 and R 219 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or Represents an alkyl group having 1 to 20 carbon atoms and having 1 to 20 fluorine atoms.
  • a plurality of R 208 , R 209 , R 214 , R 215 , R 220 or R 221 may form a ring by a direct bond or an oxygen atom bridge, a sulfur atom bridge, an NH bridge or an NR 251 bridge.
  • R 210 , R 211 , R 216 , R 217 , R 222 and R 223 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.
  • a, b, c, d, e and f each independently represent an integer of 0 to 4.
  • R 206 , R 207 , R 212 , R 213 , R 218 and R 219 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or An alkyl group having 1 to 6 carbon atoms and having 1 to 12 fluorine atoms is preferable.
  • R 251 and R 252 each independently represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a cycloalkenyl having 4 to 7 carbon atoms.
  • R 210 , R 211 , R 216 , R 217 , R 222 and R 223 are each independently preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • the above-mentioned alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group and aryl group may have a hetero atom, and may be unsubstituted or substituted.
  • R 253 , R 254 , R 259 , R 260 , R 265 and R 266 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or Represents an alkyl group having 1 to 20 carbon atoms and having 1 to 20 fluorine atoms.
  • a plurality of R 255 , R 256 , R 261 , R 262 , R 267 or R 268 may form a direct bond or a ring with an oxygen atom bridge, a sulfur atom bridge, an NH bridge or an NR 271 bridge.
  • R 257 , R 258 , R 263 , R 264 , R 269 and R 270 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.
  • a, b, c, d, e and f each independently represent an integer of 0 to 4.
  • R 253 , R 254 , R 259 , R 260 , R 265 and R 266 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or An alkyl group having 1 to 6 carbon atoms and having 1 to 12 fluorine atoms is preferable.
  • R 271 and R 272 each independently represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a cycloalkenyl having 4 to 7 carbon atoms.
  • R 257 , R 258 , R 263 , R 264 , R 269 and R 270 are each independently preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • the above-mentioned alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group and aryl group may have a hetero atom, and may be unsubstituted or substituted.
  • the benzofuranone compound is available, for example, as Irgaphor Black S0100CF (trade name, manufactured by BASF).
  • a perylene compound is a compound that has a perylene structure in the molecule and is colored black by absorbing light having a wavelength of visible light.
  • Examples of the perylene compound include compounds described in JP-A-62-1753 and JP-B-63-26784. Further, as the perylene compound, a perylene compound represented by any of the general formulas (69) to (71) is preferable.
  • X 92 , X 93 , X 94 and X 95 each independently represent an alkylene group having 1 to 10 carbon atoms.
  • R 224 and R 225 each independently represent hydrogen, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms.
  • R 273 and R 274 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • a and b each independently represent an integer of 0 to 5.
  • X 92 , X 93 , X 94 and X 95 are each independently preferably an alkylene group having 1 to 6 carbon atoms.
  • R 224 and R 225 are each independently preferably a hydrogen atom, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, or an acyl group having 2 to 4 carbon atoms.
  • Each of R 273 and R 274 is preferably independently hydrogen or an alkyl group having 1 to 6 carbon atoms.
  • the above-mentioned alkylene group, alkoxy group, acyl group and alkyl group may have a hetero atom and may be either unsubstituted or substituted.
  • Perylene compounds are described, for example, in C.I. I. Pigment Black 21, 30, 31, 32, 33, and 34, and Paliogen Black S0084, K0084, L0086, K0086, EH0788, and FK4281 (all of which are brand names, all manufactured by BASF). .
  • Black dye a dye that expresses black alone can be used, for example, a pyrazole azo compound, a pyrromethene compound, an anilino azo compound, a triphenylmethane compound, an anthraquinone compound, a benzylidene compound, an oxonol compound, a pyrazolotriazole azo compound, and a pyridone azo compound.
  • black dyes examples include JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-T-2592207, and US Pat. No. 4,808,501. Specification, US Pat. No. 5,679,920, US Pat. No. 505,950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, and JP-A-6-194828. Reference can be made to compounds described in gazettes and the like, the contents of which are incorporated herein.
  • these black dyes include dyes defined by the color index (CI) of Solvent Black 27 to 47, and C.I. of Solvent Black 27, 29 or 34. I. Are preferred.
  • commercially available products of these black dyes include Spiron Black MH, Black BH (all manufactured by Hodogaya Chemical Industry Co., Ltd.), VALIFAST Black 3804, 3810, 3820, 3830 (all manufactured by Orient Chemical Industry Co., Ltd.), Dyes such as Savinyl Black RLSN (all manufactured by Clariant), KAYASET Black KR and K-BL (all manufactured by Nippon Kayaku Co., Ltd.).
  • a dye multimer may be used as the black dye.
  • the dye multimer include compounds described in JP-A-2011-213925 and JP-A-2013-041097.
  • a polymerizable dye having polymerizability in the molecule may be used, and examples of commercially available products include RDW series manufactured by Wako Pure Chemical Industries.
  • a single dye having a color other than black may be used alone as a black dye. Examples of such coloring dyes include chromatic dyes (chromatic dyes) such as R (red), G (green), and B (blue), as well as paragraphs 0027 to 264 of JP-A-2014-42375. No. 0200 can also be used.
  • the black coloring material contains a nitride or oxynitride of at least one metal selected from the group consisting of titanium, vanadium, zirconium and niobium from the viewpoint of suppressing the occurrence of undercut when forming the black layer. More preferably, from the viewpoint that the light resistance and moisture resistance of the light-shielding film are more excellent, it is further preferable that the light-shielding film contains at least one metal oxynitride selected from the group consisting of titanium, vanadium, zirconium and niobium. It is particularly preferable to contain titanium oxynitride (titanium black). Further, the black coloring material preferably contains carbon black, a benzofuranone compound or a perylene compound.
  • the light-shielding composition may contain a coloring agent other than the black coloring material.
  • the light-shielding characteristics of the black layer (light-shielding film) can be adjusted by using both the black colorant and one or more colorants. Further, for example, when a black layer is used as a light attenuating film, it is easy to uniformly attenuate each wavelength with respect to light containing a wide wavelength component.
  • the coloring agent include pigments and dyes other than the above-described black coloring material.
  • the total content of the black colorant and the colorant is preferably from 10 to 90% by mass, more preferably from 30 to 70% by mass, based on the total mass of the solid content of the composition.
  • the total content of the black coloring material and the coloring agent is preferably smaller than the above preferred range.
  • the mass ratio of the content of the coloring agent to the content of the black coloring material is preferably 0.1 to 9.0.
  • the composition may further contain an infrared absorber.
  • the infrared absorbing agent means a compound having absorption in a wavelength region of an infrared region (preferably, a wavelength of 650 to 1300 nm).
  • a compound having a maximum absorption wavelength in a wavelength range of 675 to 900 nm is preferable.
  • colorants having such spectral characteristics include, for example, pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterylene Compounds, dithiol metal complex-based compounds, croconium compounds, and the like.
  • phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound and croconium compound the compounds disclosed in paragraphs 0010 to 0081 of JP-A-2010-11110 may be used. Will be incorporated into the book.
  • the cyanine compound can be referred to, for example, “Functional Dye, Shin Ogawara / Sen Matsuoka / Teijiro Kitao / Tsunaki Hirashima, Kodansha Scientific”, the contents of which are incorporated herein.
  • Examples of the colorant having the above-mentioned spectral characteristics include compounds disclosed in paragraphs 0004 to 0016 of JP-A-07-164729 and / or compounds disclosed in paragraphs 0027 to 0062 of JP-A-2002-146254.
  • Near-infrared absorbing particles comprising a crystallite of an oxide containing Cu and / or P disclosed in Paragraphs 0034 to 0067 of JP-A No. 003-0067 and having a number average agglomerated particle size of 5 to 200 nm can also be used.
  • the compound having a maximum absorption wavelength in a wavelength range of 675 to 900 nm at least one selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound is preferable.
  • the infrared absorbent is preferably a compound that dissolves in water at 25 ° C in an amount of 1% by mass or more, and more preferably a compound that dissolves in water at 25 ° C in an amount of 10% by mass or more. By using such a compound, the solvent resistance is improved.
  • paragraphs 0049 to 0062 of JP-A-2010-222557 can be referred to, and the contents thereof are incorporated herein.
  • the cyanine compound and the squarylium compound are described in paragraphs 0022 to 0063 of WO 2014/088063, paragraphs 0053 to 0118 of WO 2014/030628, paragraphs 0028 to 0074 of JP-A-2014-59550, and WO 2012/2012.
  • paragraphs 0029 to 0085 of JP-A-2015-40895 paragraphs 0022 to 0036 of JP-A-2014-126642, paragraphs 0011 to 0017 of JP-A-2014-148567, and JP-A-2015-157893.
  • Paragraphs 0010 to 0025, paragraphs 0013 to 0026 of JP-A-2014-095007, paragraphs 0013 to 0047 of JP-A-2014-80487, and paragraphs 0007 to 0028 of JP-A-2013-227403 can be referred to. This content is incorporated herein.
  • the light-shielding composition contains a resin.
  • the resin include a dispersion resin and an alkali-soluble resin.
  • the content of the resin in the composition is not particularly limited, but is preferably 3 to 60% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 35% by mass based on the total solid content of the composition. .
  • One type of resin may be used alone, or two or more types may be used in combination.
  • a dispersion resin described below and an alkali-soluble resin described later may be used in combination as the resin.
  • the total content is preferably within the above range.
  • the resin is a component dissolved in the composition and means a component having a molecular weight of more than 2000. When the molecular weight of the resin is polydisperse, the weight average molecular weight of the resin is more than 2,000.
  • the light-shielding composition preferably contains a dispersion resin.
  • a dispersion resin means a compound different from an alkali-soluble resin described below.
  • the content of the dispersing resin in the composition is not particularly limited, but is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 20% by mass based on the total solid content of the composition. .
  • the dispersion resin one type may be used alone, or two or more types may be used in combination. When two or more dispersing resins are used in combination, the total content is preferably within the above range.
  • the mass ratio of the content of the dispersing resin (preferably the graft polymer) to the content of the black coloring material (content of the dispersing resin / content of the black coloring material) is from 0.05 to 0.05. 1.00 is preferred, 0.05 to 0.35 is more preferred, and 0.20 to 0.35 is even more preferred.
  • the dispersing resin for example, a known dispersing agent can be appropriately selected and used. Among them, a polymer compound is preferable.
  • the dispersing resin include polymer dispersants (eg, polyamidoamine and its salts, polycarboxylic acids and its salts, high-molecular unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic-based resins). Copolymer, naphthalenesulfonic acid formalin condensate), polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, and pigment derivatives.
  • the polymer compound can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer based on its structure.
  • ⁇ Polymer compound The high molecular compound is adsorbed on the surface of a dispersion target such as a black pigment and other pigments used in combination as required (hereinafter, the black pigment and the other pigments are collectively referred to simply as “pigment”) and the like, Acts to prevent re-aggregation of Therefore, a terminal-modified polymer, a graft-type (containing a polymer chain) polymer, or a block-type polymer containing an anchor site to the pigment surface is preferable.
  • the polymer compound may have a curable group.
  • the curable group include a group containing an ethylenically unsaturated bond (hereinafter, also referred to as an “ethylenically unsaturated group”) (eg, a (meth) acryloyl group, a vinyl group, and a styryl group), And a cyclic ether group (for example, an epoxy group, an oxetanyl group, and the like) and the like, but are not limited thereto.
  • the ethylenically unsaturated group is preferable as the curable group, and a (meth) acryloyl group is more preferable, since polymerization can be controlled by a radical reaction.
  • the light-shielding composition preferably contains a dispersion resin having a curable group (more preferably, an ethylenically unsaturated group) from the viewpoint that the light-shielding film has more excellent light resistance, moisture resistance, and heat resistance.
  • the dispersion resin containing a curable group include a polymer compound having a structural unit having a curable group (more preferably, an ethylenically unsaturated group such as a (meth) acryloyl group).
  • structural unit is synonymous with “repeating unit”.
  • a curable group may be introduced at a terminal of a graft chain of a structural unit containing the following graft chain.
  • a curable group (preferably, an ethylenically unsaturated group such as a (meth) acryloyl group) may be introduced.
  • the content of the structural unit having a curable group is preferably from 2 to 90% by mass, more preferably from 5 to 30% by mass, based on the total mass of the polymer compound in terms of mass.
  • the resin containing a curable group preferably contains at least one selected from the group consisting of a polyester structure and a polyether structure.
  • the main chain may contain a polyester structure and / or a polyether structure.
  • the polymer may be used.
  • the chains may have a polyester structure and / or a polyether structure.
  • the polymer chain it is more preferable that the polymer chain has a polyester structure.
  • the polymer compound preferably contains a structural unit containing a graft chain.
  • structural unit is synonymous with “repeating unit”. Since the polymer compound containing a structural unit containing such a graft chain has an affinity for a solvent due to the graft chain, the dispersibility of a pigment or the like and the dispersion stability after aging (stability with time) Excellent.
  • the polymer compound containing the structural unit containing the graft chain has an affinity for a polymerizable compound or another resin that can be used in combination. As a result, residues are less likely to be generated in alkali development.
  • the number of atoms in the graft chain excluding hydrogen atoms is preferably from 40 to 10,000, more preferably from 50 to 2000 except for hydrogen atoms, and the number of atoms excluding hydrogen atoms is more preferably 50 to 2000. More preferably, it is 60 to 500.
  • the term “graft chain” refers to the range from the base of the main chain of the copolymer (the atom bonded to the main chain in the group branched from the main chain) to the terminal of the group branched from the main chain.
  • the graft chain preferably contains a polymer structure.
  • a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acryl structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide.
  • a polyether structure preferably is selected from the group consisting of a polyester structure, a polyether structure, and a poly (meth) acrylate structure in order to improve the interaction between the graft chain and the solvent and thereby enhance the dispersibility of the pigment or the like. Further, it is preferable that the graft chain contains at least one kind, and it is more preferable that the graft chain contains at least one of a polyester structure and a polyether structure.
  • the macromonomer containing such a graft chain (a monomer having a polymer structure and binding to the main chain of the copolymer to form a graft chain) is not particularly limited, but contains an ethylenically unsaturated group. Macromonomers can be suitably used.
  • the polymer compound preferably contains a curable group, and contains an ethylenically unsaturated group such as a (meth) acryloyl group, from the viewpoint of more excellent light resistance, moisture resistance, and heat resistance of the light-shielding film. Is more preferable.
  • AA-6, AA-10, AB-6, AS-6, AN-6, AW-6, AA-714, AY-707, AY-714, AK-5, AK-30, and AK-32 all trade names, manufactured by Toagosei Co., Ltd.
  • Blemmer PP- 100, Blemmer PP-500, Blemmer PP-800, Blemmer PP-1000, Blemmer 55-PET-800, Blemmer PME-4000, Blemmer PSE-400, Blemmer PSE-1300, and Blemmer 43PAPE-600B all trade names
  • AA-6, AA-10, AB-6, AS-6, AN-6 or Blemmer PME-4000 are preferred.
  • the dispersion resin preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and a cyclic or linear polyester, and includes polymethyl acrylate and polymethacrylic acid.
  • Methyl and more preferably contain at least one structure selected from the group consisting of linear polyesters, polymethyl acrylate structure, polymethyl methacrylate structure, polycaprolactone structure, and polyvalerolactone structure More preferably, it contains at least one structure selected from the group consisting of
  • the dispersed resin may contain the above structure alone in one resin, or may contain a plurality of these structures in one resin.
  • the polycaprolactone structure refers to a structure containing a ring-opened structure of ⁇ -caprolactone as a repeating unit.
  • the polyvalerolactone structure refers to a structure containing a ring-opened structure of ⁇ -valerolactone as a repeating unit.
  • Specific examples of the dispersed resin having a polycaprolactone structure include resins in which j and k in the following formulas (1) and (2) are 5: Further, specific examples of the dispersion resin having a polyvalerolactone structure include resins in which j and k in the following formulas (1) and (2) are 4.
  • dispersed resin having a polymethyl acrylate structure examples include a resin in which X 5 in the following formula (4) is a hydrogen atom and R 4 is a methyl group.
  • dispersion resin having a polymethyl methacrylate structure examples include a resin in which X 5 in the following formula (4) is a methyl group, and R 4 is a methyl group.
  • the polymer compound preferably contains a structural unit represented by any one of the following formulas (1) to (4) as a structural unit containing a graft chain, and includes the following formulas (1A) and (2A) ), The following formula (3A), the following formula (3B), and more preferably a structural unit represented by any of the following (4).
  • W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH.
  • W 1 , W 2 , W 3 and W 4 are preferably oxygen atoms.
  • X 1 , X 2 , X 3 , X 4 and X 5 each independently represent a hydrogen atom or a monovalent organic group.
  • X 1 , X 2 , X 3 , X 4 and X 5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (number of carbon atoms) from the viewpoint of synthesis restrictions. Independently, a hydrogen atom or a methyl group is more preferred, and a methyl group is even more preferred.
  • Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure.
  • Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following linking groups (Y-1) to (Y-21).
  • a and B mean the binding sites to the left terminal group and right terminal group in formulas (1) to (4), respectively.
  • (Y-2) or (Y-13) is more preferable from the viewpoint of convenience of synthesis.
  • Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a monovalent organic group.
  • the structure of the organic group is not particularly limited, specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group And the like.
  • a group having a steric repulsion effect is particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 carbon atoms.
  • alkyl group or an alkoxy group having up to 24 carbon atoms is more preferable, and among them, a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable. More preferred.
  • the alkyl group contained in the alkoxy group may be linear, branched, or cyclic.
  • n, m, p, and q are each independently an integer of 1 to 500.
  • j and k each independently represent an integer of 2 to 8.
  • j and k are preferably integers of 4 to 6, and more preferably 5 from the viewpoint of the stability over time and the developability of the composition.
  • n and m are preferably integers of 10 or more, and more preferably integers of 20 or more.
  • the number of repetitions of the polycaprolactone structure and the sum of the number of repetitions of the polyvalerolactone are preferably integers of 10 or more, and 20 or more. Integers are more preferred.
  • R 3 represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different.
  • R 4 represents a hydrogen atom or a monovalent organic group, and the structure of the monovalent organic group is not particularly limited. As R 4 , a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group is preferable, and a hydrogen atom or an alkyl group is more preferable.
  • R 4 is an alkyl group
  • examples of the alkyl group include a linear alkyl group having 1 to 20 carbon atoms, a branched chain alkyl group having 3 to 20 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms.
  • a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is further preferable.
  • q is 2 to 500
  • a plurality of X 5 and R 4 present in the graft copolymer may be the same or different.
  • the polymer compound may contain a graft chain-containing structural unit having two or more different structures. That is, in the molecule of the polymer compound, structural units represented by formulas (1) to (4) having different structures may be included, and in the formulas (1) to (4), n, m, p , And q each represent an integer of 2 or more, in formulas (1) and (2), j and k may include different structures in the side chain, and formulas (3) and (4) )), A plurality of R 3 , R 4 and X 5 present in the molecule may be the same or different.
  • the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of stability over time and developability of the composition.
  • the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of stability over time and developability of the composition.
  • the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or (3B) from the viewpoint of stability over time and developability of the composition. .
  • the polymer compound contains a structural unit represented by the formula (1A) as a structural unit containing a graft chain.
  • the content of the structural unit containing the graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is calculated in terms of mass with respect to the total mass of the polymer compound. It is preferably from 2 to 90% by mass, more preferably from 5 to 30% by mass.
  • the structural unit containing a graft chain is contained within this range, the dispersibility of the pigment is high and the developability when forming a black layer is good.
  • the polymer compound preferably contains a hydrophobic structural unit different from the structural unit containing the graft chain (that is, does not correspond to the structural unit containing the graft chain).
  • the hydrophobic structural unit is a structural unit having no acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, and the like).
  • the hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, and is a structural unit derived from a compound having a ClogP value of 1.2 to 8. Is more preferable. Thereby, the effect of the present invention can be more reliably achieved.
  • ClogP values are measured using Daylight Chemical Information System, Inc. This is a value calculated by the program “CLOGP” available from. This program provides the value of "calculated log P" calculated by the Hansch, Leo fragment approach (see literature below). The fragment approach is based on the chemical structure of a compound, dividing the chemical structure into substructures (fragments) and summing the logP contributions assigned to the fragments to estimate the logP value of the compound. The details are described in the following documents. In this specification, a ClogP value calculated by the program CLOGP v4.82 is used. A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P .; G. FIG. Sammmens, J .; B. Taylor and C.I.
  • logP means a common logarithm of a partition coefficient P (Partition Coefficient), and quantitatively describes how an organic compound is distributed in an equilibrium of a two-phase system of an oil (generally, 1-octanol) and water. It is a physical property value expressed as a simple numerical value, and is represented by the following equation.
  • logP log (Coil / Cwater)
  • Coil represents the molar concentration of the compound in the oil phase
  • Cwater represents the molar concentration of the compound in the aqueous phase.
  • the polymer compound preferably contains, as a hydrophobic structural unit, at least one structural unit selected from structural units derived from monomers represented by the following formulas (i) to (iii).
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or Represents an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, and a propyl group).
  • R 1 , R 2 , and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.
  • R 2 and R 3 are more preferably a hydrogen atom.
  • X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • L is a single bond or a divalent linking group.
  • the divalent linking group include a divalent aliphatic group (eg, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group) and a divalent aromatic group (eg, an arylene group) , Substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 Represents an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), and a combination thereof.
  • a divalent aliphatic group eg, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the carbon number of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10.
  • the aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group.
  • the carbon number of the divalent aromatic group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10.
  • the aromatic group may have a substituent.
  • substituents include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably contains a 5- or 6-membered ring as a heterocyclic ring.
  • Another heterocycle, aliphatic ring, or aromatic ring may be condensed to the heterocycle.
  • L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L may include a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • As the polyoxyalkylene structure a polyoxyethylene structure or a polyoxypropylene structure is preferable.
  • the polyoxyethylene structure is represented by-(OCH 2 CH 2 ) n-, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z represents an aliphatic group (eg, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (eg, an aryl group, a substituted aryl group, an arylene group, a substituted arylene group) , A heterocyclic group, and a combination thereof.
  • These groups include an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR 31 —, where R 31 is an aliphatic group or an aromatic group. Group or heterocyclic group) or a carbonyl group (—CO—).
  • the aliphatic group may have a cyclic structure or a branched structure.
  • the carbon number of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10.
  • the aliphatic group further includes a ring-assembled hydrocarbon group and a cross-linked cyclic hydrocarbon group. Examples of the ring-assembled hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -A cyclohexylphenyl group and the like.
  • bridged cyclic hydrocarbon ring examples include, for example, pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring and the like) and the like.
  • Tricyclic hydrocarbon rings such as a cyclic hydrocarbon ring, homobredan, adamantane, tricyclo [5.2.1.0 2,6 ] decane, and tricyclo [4.3.1.1 2,5 ] undecane ring , And tetracyclo [4.4.0.1 2,5 .
  • the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring, for example, perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings such as a perhydrophenalene ring is also included.
  • perhydronaphthalene decalin
  • perhydroanthracene perhydrophenanthrene
  • perhydroacenaphthene perhydrofluorene
  • perhydroindene perhydroindene
  • a condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings such as a perhydrophenalene ring is also included.
  • the aliphatic group a saturated aliphatic group is more preferable than an unsaturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
  • the number of carbon atoms in the aromatic group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.
  • R 4 , R 5 , and R 6 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), and a C 1-6 carbon atom.
  • a halogen atom eg, a fluorine atom, a chlorine atom, a bromine atom, etc.
  • C 1-6 carbon atom Represents an alkyl group (eg, a methyl group, an ethyl group, and a propyl group), Z, or LZ.
  • L and Z have the same meaning as the above groups.
  • R 4 , R 5 and R 6 a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.
  • R 1 , R 2 , and R 3 are a hydrogen atom or a methyl group, and L contains a single bond or an alkylene group or an oxyalkylene structure.
  • Compounds that are divalent linking groups, wherein X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group are preferred.
  • R 1 is a hydrogen atom or a methyl group
  • L is an alkylene group
  • Z is an aliphatic group, a heterocyclic group, or an aromatic group.
  • Compounds that are groups are preferred.
  • R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Compounds that are groups are preferred.
  • Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylates, methacrylates, styrenes, and the like.
  • Examples of typical compounds represented by formulas (i) to (iii) compounds described in paragraphs 0089 to 0093 of JP-A-2013-249417 can be referred to, and the contents thereof are described in the present specification. Incorporated in
  • the content of the hydrophobic structural unit in terms of mass is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, based on the total mass of the polymer compound. When the content is in the above range, a sufficient pattern formation can be obtained.
  • the polymer compound can introduce a functional group capable of forming an interaction with a pigment or the like (for example, a black pigment).
  • the polymer compound preferably further contains a structural unit having a functional group capable of forming an interaction with a pigment or the like.
  • the functional group capable of forming an interaction with the pigment or the like include an acid group, a basic group, a coordinating group, and a reactive functional group.
  • the polymer compound contains an acid group, a basic group, a coordinating group, or a reactive functional group
  • the structural unit containing an acid group the structural unit containing a basic group
  • the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, developability for pattern formation by alkali development can be imparted to the polymer compound. That is, if an alkali-soluble group is introduced into the polymer compound, the above-mentioned composition contains a polymer compound as a dispersing resin that contributes to dispersion of pigments and the like, which is alkali-soluble.
  • the composition containing such a polymer compound is excellent in the light-shielding property of a black layer formed by exposure, and the alkali developability of an unexposed portion is improved. Further, when the polymer compound contains a structural unit containing an acid group, the polymer compound is easily compatible with a solvent, and the coating property tends to be improved. This is because the acid group in the structural unit containing an acid group easily interacts with the pigment and the like, and the polymer compound stably disperses the pigment and the like, and the viscosity of the polymer compound that disperses the pigment and the like becomes low. This is presumed to be because the polymer compound itself is easily dispersed stably.
  • the structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the above-described structural unit containing a graft chain, or may be a different structural unit.
  • the structural unit containing a soluble group is a structural unit different from the above-mentioned hydrophobic structural unit (that is, does not correspond to the above-mentioned hydrophobic structural unit).
  • the acid group which is a functional group capable of forming an interaction with a pigment
  • examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. And at least one phosphoric acid group is preferable, and a carboxylic acid group is more preferable.
  • Carboxylic acid groups have good adsorptivity to pigments and the like and have high dispersibility. That is, the polymer compound preferably further contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
  • the polymer compound may have one or more structural units containing an acid group.
  • the polymer compound may or may not contain a structural unit containing an acid group, but if it does, the content of the structural unit containing an acid group is 5% based on the total mass of the polymer compound.
  • the amount is preferably from 80 to 80% by mass, and more preferably from 10 to 60% by mass, from the viewpoint of suppressing damage to image strength due to alkali development.
  • Examples of the basic group which is a functional group capable of forming an interaction with a pigment or the like include a primary amino group, a secondary amino group, a tertiary amino group, a hetero ring containing an N atom, and an amide.
  • Preferred basic groups are tertiary amino groups because they have good adsorptivity to pigments and the like and have high dispersibility.
  • the polymer compound can contain one or more of these basic groups.
  • the polymer compound may or may not contain a structural unit containing a basic group, but when it is contained, the content of the structural unit containing a basic group is calculated based on the total amount of the polymer compound in terms of mass. The amount is preferably 0.01 to 50% by mass, and more preferably 0.01 to 30% by mass, from the viewpoint of suppressing the inhibition of developing property.
  • Examples of the coordinating group which is a functional group capable of forming an interaction with a pigment
  • the reactive functional group include, for example, acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, and acid chloride Objects and the like.
  • a preferred functional group is an acetylacetoxy group in that it has good adsorptivity to pigments and the like and high dispersibility of the pigments and the like.
  • the polymer compound may have one or more of these groups.
  • the polymer compound may or may not contain a structural unit containing a coordinating group, or a structural unit containing a reactive functional group, but if it contains, the content of these structural units Is preferably from 10 to 80% by mass, and more preferably from 20 to 60% by mass, in terms of suppression of development property inhibition, based on the total mass of the polymer compound.
  • the polymer compound other than the graft chain, contains a functional group capable of forming an interaction with a pigment or the like, it is sufficient that the polymer compound contains a functional group capable of forming an interaction with the various pigments described above,
  • the manner in which these functional groups are introduced is not particularly limited, and the polymer compound may be one selected from structural units derived from monomers represented by the following formulas (iv) to (vi). It is preferable to contain the above structural units.
  • R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or the like) or a carbon atom.
  • a halogen atom for example, a fluorine atom, a chlorine atom, a bromine atom, or the like
  • R 11 , R 12 , and R 13 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.
  • R 12 and R 13 are more preferably hydrogen atoms.
  • X 1 in the formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • Y in the formula (v) represents a methine group or a nitrogen atom.
  • L 1 in the formulas (iv) to (v) represents a single bond or a divalent linking group.
  • the definition of the divalent linking group is the same as the definition of the divalent linking group represented by L in the formula (i).
  • L 1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L 1 may include a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • a polyoxyethylene structure or a polyoxypropylene structure is preferable.
  • the polyoxyethylene structure is represented by-(OCH 2 CH 2 ) n-, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z 1 represents a functional group capable of forming an interaction with a pigment or the like other than the graft chain, and is preferably a carboxylic acid group or a tertiary amino group, and is preferably a carboxylic acid group. More preferred.
  • R 14 , R 15 , and R 16 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms. group (e.g., methyl group, ethyl group, and propyl group), - Z 1, or an L 1 -Z 1.
  • L 1 and Z 1 have the same meanings as L 1 and Z 1 described above, and preferred examples are also the same.
  • R 14 , R 15 , and R 16 a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.
  • R 11 , R 12 , and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is a divalent group containing an alkylene group or an oxyalkylene structure. Preferred are compounds in which X 1 is an oxygen atom or an imino group and Z 1 is a carboxylic acid group. Further, as the monomer represented by the formula (v), R 11 is a hydrogen atom or a methyl group, L 1 is an alkylene group, Z 1 is a carboxylic acid group, and Y is a methine group. Are preferred.
  • R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group
  • L 1 is a single bond or an alkylene group
  • Z Compounds in which 1 is a carboxylic acid group are preferred.
  • Examples of the monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction of a compound containing an addition-polymerizable double bond and a hydroxyl group in a molecule (eg, 2-hydroxyethyl methacrylate) with succinic anhydride.
  • the content of the structural unit containing a functional group capable of forming an interaction with a pigment or the like is, in terms of the interaction with the pigment or the like, the stability over time, and the permeability into a developer, the amount of the polymer compound in terms of mass. Is preferably from 0.05 to 90% by mass, more preferably from 1.0 to 80% by mass, and still more preferably from 10 to 70% by mass, based on the total mass.
  • the polymer compound interacts with a graft chain-containing structural unit, a hydrophobic structural unit, and a pigment, for the purpose of improving various performances such as image strength, as long as the effects of the present invention are not impaired.
  • It further has another structural unit having various functions different from the structural unit containing a functional group that can be formed (for example, a structural unit containing a functional group having an affinity for a solvent described below). Is also good.
  • Such other structural units include, for example, structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
  • the polymer compound may use one or more of these other structural units, and its content is preferably from 0 to 80% by mass, and preferably from 10 to 80% by mass, based on the total mass of the polymer compound. 60 mass% is more preferable. When the content is in the above range, sufficient pattern formability is maintained.
  • the acid value of the polymer compound is preferably from 0 to 250 mgKOH / g, more preferably from 10 to 200 mgKOH / g, still more preferably from 30 to 180 mgKOH / g, particularly preferably from 70 to 120 mgKOH / g.
  • the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development in forming a black layer can be more effectively suppressed.
  • the acid value of the polymer compound is 10 mgKOH / g or more, the alkali developability becomes better.
  • the acid value of the polymer compound is 20 mgKOH / g or more, sedimentation of pigments and the like can be further suppressed, the number of coarse particles can be reduced, and the stability over time of the composition can be further improved.
  • the acid value can be calculated, for example, from the average content of acid groups in the compound.
  • a resin having a desired acid value can be obtained by changing the content of the structural unit containing an acid group, which is a constituent component of the resin.
  • the weight average molecular weight of the polymer compound is preferably from 4,000 to 300,000, more preferably from 5,000 to 200,000, still more preferably from 6,000 to 100,000, particularly preferably from 10,000 to 50,000. preferable.
  • the polymer compound can be synthesized based on a known method.
  • polymer compound examples include “DA-7301” manufactured by Kusumoto Kasei, “Disperbyk-101 (polyamideamine phosphate)” manufactured by BYK Chemie, 107 (carboxylate), and 110 (copolymer containing an acid group).
  • MYS-IEX polyoxyethylene monostearate
  • Hinoact T-8000E manufactured by Kawaken Fine Chemical, Shin-Etsu Chemical Co., Ltd.
  • organosiloxane polymer KP-341 Yu "W001: cationic surfactant"
  • polyoxyethylene lauryl ether polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol dilaurate
  • Nonionic surfactants such as stearates and sorbitan fatty acid esters
  • anionic surfactants such as "W004, W005, W017”;"EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA” manufactured by Morishita Sangyo Polymer 400, EFKA polymer 401, EFKA polymer
  • amphoteric resin containing an acid group and a basic group.
  • the amphoteric resin is preferably a resin having an acid value of 5 mgKOH / g or more and an amine value of 5 mgKOH / g or more.
  • Commercially available amphoteric resins include, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, and DISPERBY manufactured by BYK Chemie.
  • One of these polymer compounds may be used alone, or two or more thereof may be used in combination.
  • polymer compound As specific examples of the polymer compound, reference can be made to the polymer compounds described in paragraphs 0127 to 0129 of JP-A-2013-249417, the contents of which are incorporated herein.
  • the dispersing resin besides the above-mentioned polymer compounds, graft copolymers described in paragraphs 0037 to 0115 of JP-A-2010-106268 (corresponding to columns 0075 to 0133 of US2011 / 0124824) can be used. Is incorporated herein by reference. Further, in addition to the above, it contains a side chain structure in which an acidic group described in paragraphs 0028 to 0084 of JP-A-2011-153283 (corresponding to columns 2011 to 0133 of US2011 / 0279759) is bonded via a linking group. High molecular compounds containing the following constituents can be used, the contents of which are incorporated herein by reference.
  • dispersing resin resins described in paragraphs 0033 to 0049 of JP-A-2016-109763 can also be used, and the contents thereof are incorporated herein.
  • the composition preferably contains an alkali-soluble resin.
  • the alkali-soluble resin means a resin containing a group that promotes alkali solubility (an alkali-soluble group, for example, an acid group such as a carboxylic acid group), and a resin different from the dispersion resin described above. I do.
  • the content of the alkali-soluble resin in the composition is not particularly limited, but is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and more preferably 5 to 15% by mass based on the total solid content of the composition. More preferred.
  • One alkali-soluble resin may be used alone, or two or more alkali-soluble resins may be used in combination. When two or more alkali-soluble resins are used in combination, the total content is preferably within the above range.
  • alkali-soluble resin examples include resins containing at least one alkali-soluble group in a molecule, such as polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide resin, and (meth) acrylic resin.
  • An acryl / (meth) acrylamide copolymer resin, an epoxy resin, a polyimide resin, and the like can be given.
  • the alkali-soluble resin include a copolymer resin of an unsaturated carboxylic acid and an ethylenically unsaturated compound.
  • the unsaturated carboxylic acid is not particularly limited, but monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and vinyl acetic acid; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, or acid anhydrides thereof
  • polyvalent carboxylic acid monoesters such as mono (2- (meth) acryloyloxyethyl) phthalate; and the like.
  • Examples of the copolymerizable ethylenically unsaturated compound include methyl (meth) acrylate. Further, the compounds described in paragraph 0027 of JP-A-2010-97210 and paragraphs 0036 to 0037 of JP-A-2015-68893 can also be used, and the above description is incorporated in the present specification.
  • a copolymerizable ethylenically unsaturated compound having a side chain containing an ethylenically unsaturated group may be used in combination.
  • a (meth) acrylic acid group is preferable.
  • the acrylic resin containing an ethylenically unsaturated group in the side chain is, for example, an addition reaction of an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to a carboxylic acid group of an acrylic resin containing a carboxylic acid group. Obtained.
  • an alkali-soluble resin containing a curable group is also preferable.
  • the curable group include curable groups that may be contained in the above-mentioned polymer compound, and the preferable range is also the same.
  • the alkali-soluble resin containing a curable group an alkali-soluble resin having a curable group in a side chain is preferable.
  • the alkali-soluble resin containing a curable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polythane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264, and KS resist 106 (KS).
  • alkali-soluble resin examples include, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, and JP-A-54-92723.
  • polyvinyl alcohol-based binder resin containing an alkali-soluble group described in JP-A-2001-318463; polyvinylpyrrolidone; polyethylene oxide; alcohol-soluble nylon and 2,2-bis- (4 -Hydroxyphenyl) -propane and epichlorohydrin
  • polyimide resin described in WO 2008/123097 pamphlet; and the like can be used polyethers such as that.
  • alkali-soluble resin for example, the compounds described in paragraphs 0225 to 0245 of JP-A-2016-75845 can also be used, and the above description is incorporated herein.
  • a polyimide precursor can also be used as the alkali-soluble resin.
  • the polyimide precursor means a resin obtained by subjecting a compound containing an acid anhydride group and a diamine compound to an addition polymerization reaction at 40 to 100 ° C.
  • the polyimide precursor include a resin containing a repeating unit represented by the formula (1).
  • the structure of the polyimide precursor include, for example, an amic acid structure represented by the following formula (2), the following formula (3) in which the amic acid structure is partially imide-closed, and the following formula (4) in which all imides are closed.
  • the polyimide precursor containing an imide structure represented by the formula (1) In this specification, a polyimide precursor having an amic acid structure may be referred to as a polyamic acid.
  • R 1 represents a tetravalent organic group having 2 to 22 carbon atoms
  • R 2 represents a divalent organic group having 1 to 22 carbon atoms
  • n is 1 or 2 Represents
  • polyimide precursor examples include, for example, the compounds described in paragraphs 0011 to 0031 of JP-A-2008-106250, the compounds described in paragraphs 0022 to 0039 of JP-A-2016-122101, and Compounds described in paragraphs 0061 to 0092 of 2016-68401 can be mentioned, and the above description is incorporated herein.
  • the alkali-soluble resin is also preferable to contain at least one selected from the group consisting of a polyimide resin and a polyimide precursor, in that the pattern shape of the patterned black layer obtained using the composition is more excellent. .
  • the polyimide resin containing an alkali-soluble group is not particularly limited, and a known polyimide resin containing an alkali-soluble group can be used.
  • Examples of the polyimide resin include a resin described in paragraph 0050 of JP-A-2014-137523, a resin described in paragraph 0058 of JP-A-2015-187676, and a resin described in JP-A-2014-106326. Examples include the resins described in paragraphs 0012 to 0013, and the contents described above are incorporated herein.
  • a polybenzoxazole precursor can also be used as the alkali-soluble resin.
  • the polybenzoxazole precursor is a resin synthesized from a hydroxyl group-containing diamine and a dicarboxylic acid derivative.
  • the hydroxyl group-containing diamine include aromatic diamines having a phenolic hydroxyl group, such as bisaminophenol compounds.
  • Specific examples of the hydroxyl group-containing diamine include 3,3-dihydroxybenzidine and 3,3′-dihydroxy-4,4′-diaminodiphenyl ether.
  • dicarboxylic acid derivatives examples include dicarboxylic acid derivatives such as dicarboxylic acid chloride and dicarboxylic acid ester, and aromatic dicarboxylic acid derivatives are preferable.
  • dicarboxylic acid derivative examples include isophthalic acid dichloride and terephthalic acid dichloride.
  • polybenzoxazole precursor examples include polyhydroxyamide, polyaminoamide, polyamide, and polyamideimide.
  • polybenzoxazole precursor examples include, for example, the compounds described in paragraphs 0049 to 0062 of JP-A-2003-121997, the compounds described in paragraphs 0050 to 0057 of WO2017 / 057281 and international publications
  • the compounds described in paragraphs 0015 to 0043 of JP-A-2016 / 043203 are exemplified, and the above description is incorporated herein.
  • the copolymer of the polyimide precursor and the polybenzoxazole precursor is a copolymer having a polyamic acid ester structural unit and a hydroxypolyamide structural unit, for example, an alternating copolymer structure of a polyamic acid ester structural unit and a hydroxypolyamide structural unit And a copolymer having the formula:
  • the alkali-soluble resin at least one selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a copolymer thereof is preferable because the light resistance and the heat resistance of the light-shielding film are more excellent. Is more preferred.
  • alkali-soluble resin examples include [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer, and [allyl (meth) acrylate / (meth) acrylic acid]. / If necessary, other addition-polymerizable vinyl monomers] copolymers are suitable because they have an excellent balance of film strength, sensitivity, and developability. The above-mentioned other addition-polymerizable vinyl monomers may be used alone or in combination of two or more.
  • the above-mentioned copolymer preferably has a curable group, and more preferably contains an ethylenically unsaturated group such as a (meth) acryloyl group, in that the moisture resistance of the black layer is more excellent.
  • a curable group may be introduced into the copolymer using a monomer having a curable group as the above-mentioned other addition-polymerizable vinyl monomer.
  • a curable group (preferably ((A) or (B)) may be added to a part or all of one or more of units derived from (meth) acrylic acid and / or units derived from the other addition-polymerizable vinyl monomers in the copolymer.
  • a (meth) acryloyl group or other ethylenically unsaturated group examples include methyl (meth) acrylate, styrene-based monomers (such as hydroxystyrene), and ether dimers.
  • the ether dimer examples include a compound represented by the following general formula (ED1) and a compound represented by the following general formula (ED2).
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • the description in JP-A-2010-168538 can be referred to.
  • ether dimer for example, paragraph 0317 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated herein.
  • the ether dimer may be only one kind or two or more kinds.
  • the acid value of the alkali-soluble resin is not particularly limited, but is generally preferably from 30 to 500 mgKOH / g, and more preferably from 50 to 200 mgKOH / g.
  • the light-shielding composition contains a polymerizable compound.
  • the polymerizable compound means a compound which is polymerized by the action of a polymerization initiator described later, and means a component different from the above-described dispersion resin and alkali-soluble resin.
  • the content of the polymerizable compound in the composition is not particularly limited, but is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, and preferably 15 to 25% by mass based on the total solid content of the composition. More preferred.
  • the polymerizable compound one type may be used alone, or two or more types may be used in combination. When two or more polymerizable compounds are used in combination, the total content is preferably within the above range.
  • the molecular weight (or weight average molecular weight) of the polymerizable compound is not particularly limited, but is preferably 2000 or less.
  • the light-shielding composition preferably contains a low-molecular compound containing an ethylenically unsaturated group as a polymerizable compound.
  • a compound containing one or more ethylenically unsaturated bonds is preferable, a compound containing two or more ethylenically unsaturated bonds is more preferable, a compound containing three or more ethylenically unsaturated bonds is more preferable, and a compound containing five or more ethylenically unsaturated bonds is particularly preferable.
  • the upper limit is, for example, 15 or less.
  • Examples of the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • the polymerizable compound for example, the compounds described in paragraph 0050 of JP-A-2008-260927 and paragraph 0040 of JP-A-2015-68893 can be used, and the contents described above are incorporated herein. It is.
  • the polymerizable compound may be in any of chemical forms such as, for example, monomers, prepolymers, oligomers, and mixtures thereof, and multimers thereof.
  • the polymerizable compound is preferably a 3-15 functional (meth) acrylate compound, more preferably a 3-6 functional (meth) acrylate compound.
  • a compound containing at least one ethylenically unsaturated group and having a boiling point of 100 ° C. or more under normal pressure is also preferable.
  • the compounds described in paragraphs 0227 of JP-A-2013-29760 and paragraphs 0254 to 0257 of JP-A-2008-292970 can be referred to, and the contents thereof are incorporated herein.
  • Polymerizable compounds include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available product KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acryloyl groups are mediated by an ethylene glycol residue or a propylene glycol residue (for example, commercially available from Sartomer, SR454 , SR499)
  • oligomer types can also be used.
  • NK ester A-TMMT penentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • KAYARAD RP-1040 KAYARAD DPEA-12LT, KAYARAD DPHA LT, KAYARAD RP-3060, and KAYARAD DPEA-12 (all products) Name, manufactured by Nippon Kayaku Co., Ltd.
  • Preferred embodiments of the polymerizable compound are shown below.
  • the light-shielding composition preferably contains at least two kinds of polymerizable compounds. Among them, from the viewpoint of more excellent heat resistance and moisture resistance of the light-shielding film, it has a similar structure, contains two or more polymerizable compounds having different numbers of ethylenically unsaturated groups, and has an ethylenically unsaturated group. Is preferably a compound containing at least one or more hydroxyl groups. By using such two or more polymerizable compounds, the reason why the heat resistance and moisture resistance of the light-shielding film are improved is not clear, but by using a polymerizable compound having a hydroxyl group, an alkali-soluble resin can be obtained.
  • Examples of such a mixture of two or more compounds having similar structures and different numbers of ethylenically unsaturated groups include, for example, formulas (Z-1), (Z-4), and ( Z-5), a mixture of compounds having different numbers of terminal ethylenically unsaturated groups (preferably (meth) acryloyl groups), wherein the compound having a smaller number of ethylenically unsaturated groups is at least Mixtures that are compounds containing one or more hydroxyl groups are included.
  • the polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
  • an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to form an acid.
  • a polymerizable compound having a group is more preferable, and in this ester, a compound in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol is further preferable.
  • Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.
  • the acid value of the polymerizable compound having an acid group is preferably from 0.1 to 40 mgKOH / g, more preferably from 5 to 30 mgKOH / g.
  • the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the developing dissolution property is good, and when the acid value is 40 mgKOH / g or less, it is advantageous in production and / or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.
  • the polymerizable compound is a compound having a caprolactone structure.
  • the compound having a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule.
  • a compound having a caprolactone structure represented by the following formula (Z-1) is preferable.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents the number of 1 or 2
  • “*” represents a bond.
  • R 1 represents a hydrogen atom or a methyl group, and “*” represents a bond.
  • Commercially available polymerizable compounds having a caprolactone structure include M-350 (trade name) (trimethylolpropane triacrylate) manufactured by Toagosei Co., Ltd.
  • a compound represented by the following formula (Z-4) or (Z-5) can also be used.
  • E represents — ((CH 2 ) y CH 2 O) — or ((CH 2 ) y CH (CH 3 ) O) —, and y is , 0 to 10, and X represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
  • the total number of the (meth) acryloyl groups is 3 or 4
  • m represents an integer of 0 to 10
  • the total of each m is an integer of 0 to 40.
  • the total number of the (meth) acryloyl groups is 5 or 6, and n represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.
  • m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and further preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, more preferably 0 to 4. Further, the sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and further preferably an integer of 6 to 12.
  • -((CH 2 ) y CH 2 O)-or ((CH 2 ) y CH (CH 3 ) O)- A form in which the terminal is bonded to X is preferred.
  • the compound represented by the formula (Z-4) or (Z-5) may be used alone or in combination of two or more.
  • a form in which all six Xs are acryloyl groups in Formula (Z-5), a compound in which all six Xs are acryloyl groups,
  • a preferred embodiment is a mixture with a compound in which at least one is a hydrogen atom.
  • the total content of the compound represented by the formula (Z-4) or the formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
  • a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
  • the polymerizable compound may contain a cardo skeleton.
  • a polymerizable compound having a 9,9-bisarylfluorene skeleton is preferable.
  • examples of the polymerizable compound having a cardo skeleton include, but are not limited to, Oncoat EX series (manufactured by Nagase & Co., Ltd.) and Ogusol (manufactured by Osaka Gas Chemical Company).
  • a compound containing an isocyanuric acid skeleton as a central nucleus is also preferable.
  • Examples of such a polymerizable compound include, for example, NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • the content of the ethylenically unsaturated group in the polymerizable compound (meaning the value obtained by dividing the number of ethylenically unsaturated groups in the polymerizable compound by the molecular weight (g / mol) of the polymerizable compound) is 5.0 mmol / g or more is preferable.
  • the upper limit is not particularly limited, but is generally 20.0 mmol / g or less.
  • the light-shielding composition preferably contains a polymerization initiator.
  • the polymerization initiator is not particularly limited, and a known polymerization initiator can be used. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, and a photopolymerization initiator is preferable. In addition, what is called a radical polymerization initiator is preferable as a polymerization initiator.
  • the content of the polymerization initiator in the composition is not particularly limited, but is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, and more preferably 1.5 to 10% by mass based on the total solid content of the composition. -8% by mass is more preferred.
  • One type of polymerization initiator may be used alone, or two or more types may be used in combination. When two or more polymerization initiators are used in combination, the total content is preferably within the above range.
  • thermal polymerization initiator examples include 2,2′-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalenonitrile, and dimethyl- (2,2 ′)-azobis (2 -Methylpropionate) [V-601], and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
  • AIBN 2,2′-azobisisobutyronitrile
  • 3-carboxypropionitrile 3-carboxypropionitrile
  • azobismalenonitrile examples
  • organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
  • organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
  • the composition preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited as long as the polymerization of the polymerizable compound can be started, and a known photopolymerization initiator can be used.
  • a photopolymerization initiator for example, a photopolymerization initiator having photosensitivity from an ultraviolet region to a visible light region is preferable.
  • an activator that generates an active radical by causing some action with the photoexcited sensitizer may be used, or an initiator that starts cationic polymerization depending on the type of the polymerizable compound may be used.
  • the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least 50 in the range of 300 to 800 nm (more preferably 330 to 500 nm).
  • the content of the photopolymerization initiator in the composition is not particularly limited, but is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, based on the total solid content of the composition. More preferably, it is from 0.5 to 8% by mass.
  • One photopolymerization initiator may be used alone, or two or more photopolymerization initiators may be used in combination. When two or more photopolymerization initiators are used in combination, the total content is preferably within the above range.
  • Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, Examples include oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenone.
  • paragraphs 0265 to 0268 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated herein.
  • the photopolymerization initiator for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used.
  • the hydroxyacetophenone compound for example, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF) can be used.
  • the aminoacetophenone compound for example, commercially available products IRGACURE-907, IRGACURE-369 and IRGACURE-379EG (trade names, all manufactured by BASF) can be used.
  • aminoacetophenone compound a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long-wavelength light source having a wavelength of 365 nm or 405 nm can also be used.
  • acylphosphine compound commercially available products IRGACURE-819 and IRGACURE-TPO (trade names, both manufactured by BASF) can be used.
  • an oxime ester-based polymerization initiator (oxime compound) is more preferable.
  • oxime compounds are preferable because they have high sensitivity and high polymerization efficiency, and the content of the coloring material in the composition is easy to design.
  • compounds described in JP-A-2001-233842 compounds described in JP-A-2000-80068, and compounds described in JP-A-2006-342166 can be used.
  • Examples of the oxime compound include 3-benzoyloximinobtan-2-one, 3-acetoxyimiminobtan-2-one, 3-propionyloxyimiminobtan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxy Carbonyloxyimino-1-phenylpropan-1-one and the like.
  • J.I. C. S. Perkin II (1979) pp. 1653-1660 C. S. Perkin II (1979) pp.
  • IRGACURE-OXE01 manufactured by BASF
  • IRGACURE-OXE02 manufactured by BASF
  • IRGACURE-OXE03 manufactured by BASF
  • IRGACURE-OXE04 manufactured by BASF
  • TR-PBG-304 manufactured by Changzhou Strong Electronics New Materials Co., Ltd.
  • Adeka Aquel's NCI-831 Adeka Aquel's NCI-930
  • N-1919 a carbazole / oxime ester skeleton-containing light Initiators
  • oxime compounds other than those described above include compounds described in JP-T-2009-519904 in which an oxime is linked to the carbazole N-position; compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety; Compounds described in JP-A-2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into a dye site; ketoxime compounds described in WO 2009-131189; and a triazine skeleton A compound described in US Pat. No.
  • R and B each independently represent a monovalent substituent
  • A represents a divalent organic group
  • Ar represents an aryl group.
  • the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
  • the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Further, these groups may have one or more substituents. Further, the above-mentioned substituent may be further substituted with another substituent.
  • substituents examples include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
  • an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group is preferable, and an aryl group or a heterocyclic group is preferable. preferable.
  • These groups may have one or more substituents. Examples of the substituent include the substituents described above.
  • the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the substituents described above.
  • Oxime compounds containing a fluorine atom can also be used as the photopolymerization initiator.
  • fluorine-containing oxime compounds include compounds described in JP-A-2010-262028; compounds 24, 36 to 40 described in JP-A-2014-500852; and JP-A-2013-164471.
  • photopolymerization initiator compounds represented by the following general formulas (1) to (4) can also be used.
  • R 1 and R 2 each independently represent an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or When R 1 and R 2 are a phenyl group, the phenyl groups may combine with each other to form a fluorene group, and R 3 and R 4 each independently represent a fluorene group.
  • X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms; Represents a group.
  • R 1, R 2, R 3 and, R 4 is, R 1, R 2, R 3 in the formula (1), and has the same meaning as R 4,
  • R 5 are, -R 6 , -OR 6 , -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6 , -COSR 6 , -CSOR 6 , —CN represents a halogen atom or a hydroxyl group
  • R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a C 4 to C 4 20 represents a heterocyclic group
  • X represents a direct bond or a carbonyl group
  • a represents an integer of 0 to 4.
  • R 1 represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms.
  • R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, Represents a heterocyclic group represented by Formulas 4 to 20, and X represents a direct bond or a carbonyl group.
  • R 1, R 3 and, R 4 is, R 1, R 3 in the formula (3), and has the same meaning as R 4,
  • R 5 are, -R 6, -OR 6, -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6 , -COSR 6 , -COR 6 , -CN, halogen atom, Or a hydroxyl group
  • R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms.
  • X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.
  • R 1 and R 2 are preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group.
  • R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xylyl group.
  • R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a naphthyl group.
  • R 1 is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group.
  • R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xylyl group.
  • R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a naphthyl group.
  • X is preferably a direct bond.
  • Specific examples of the compounds represented by the formulas (1) and (2) include the compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated herein.
  • oxime compound preferably used in the above composition
  • the oxime compound represented by the formula (C-13) is more preferable.
  • the oxime compound the compound described in Table 1 of International Publication No. 2015-036910 Pamphlet can also be used, and the above description is incorporated herein.
  • the oxime compound preferably has a maximum absorption wavelength in a wavelength region of 350 to 500 nm, more preferably has a maximum absorption wavelength in a wavelength region of 360 to 480 nm, and further preferably has high absorbance at wavelengths of 365 nm and 405 nm. .
  • the molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, and still more preferably from 5,000 to 200,000, from the viewpoint of sensitivity.
  • the molar extinction coefficient of the compound can be measured by a known method.
  • the molar extinction coefficient is measured at a concentration of 0.01 g / L using ethyl acetate with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian). Is preferred. Photopolymerization initiators may be used in combination of two or more as necessary.
  • photopolymerization initiator examples include compounds described in paragraph 0052 of JP-A-2008-260927, paragraphs 0033 to 0037 of JP-A-2010-97210, and paragraph 0044 of JP-A-2015-68893. Can also be used, and the above is incorporated herein.
  • the composition may contain a polymerization inhibitor.
  • the polymerization inhibitor is not particularly limited, and a known polymerization inhibitor can be used.
  • the polymerization inhibitor include phenol-based polymerization inhibitors (eg, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-ditert-butyl-4-methylphenol, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4-methoxynaphthol and the like; hydroquinone-based polymerization inhibitors (for example, Quinone-based polymerization inhibitors (eg, benzoquinone); free-radical polymerization inhibitors (eg, 2,2,6,6-tetramethylpiperidine 1-).
  • phenol-based polymerization inhibitors eg, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-diter
  • Nitrobenzene-based polymerization inhibitor e.g., nitrobenzene, 4-nitrotoluene, etc.
  • phenothiazine-based polymerization inhibitor e.g., phenothiazine, 2-methoxy phenothiazine, etc.
  • a phenol-based polymerization inhibitor or a free radical-based polymerization inhibitor is preferable in that the composition has a more excellent effect.
  • the effect of the polymerization inhibitor is remarkable when it is used together with a resin containing a curable group.
  • the content of the polymerization inhibitor in the composition is not particularly limited, but is preferably 0.0001 to 0.5% by mass, more preferably 0.001 to 0.2% by mass, based on the total solid content of the composition. It is more preferably 0.008 to 0.05% by mass.
  • the polymerization inhibitor one type may be used alone, or two or more types may be used in combination. When two or more polymerization inhibitors are used in combination, the total content is preferably within the above range.
  • the ratio of the content of the polymerization inhibitor to the content of the polymerizable compound in the composition is preferably more than 0.0005, 0.0006 to 0.02 is more preferable, and 0.0006 to 0.005 is still more preferable.
  • the composition may contain an ultraviolet absorber. Thereby, the shape of the pattern of the black layer can be made more excellent (fine).
  • an ultraviolet absorber salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
  • compounds described in paragraphs 0137 to 0142 of JP-A-2012-068418 corresponding to paragraphs 0251 to 0254 of US2012 / 0068292 can be used, and the contents thereof can be referred to and incorporated herein. .
  • a diethylamino-phenylsulfonyl-based ultraviolet absorber (trade name, UV-503, manufactured by Daito Chemical Co., Ltd.) and the like are also preferably used.
  • the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP-A-2012-32556.
  • the content of the ultraviolet absorbent is preferably from 0.001 to 15% by mass, more preferably from 0.01 to 10% by mass, even more preferably from 0.1 to 5% by mass, based on the total solid content of the composition.
  • the composition may contain a silane coupling agent.
  • the silane coupling agent functions as an adhesive for improving the adhesion between the substrate and the black layer when forming the black layer on the substrate.
  • the silane coupling agent is a compound containing a hydrolyzable group and other functional groups in the molecule. Note that a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
  • the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by a hydrolysis reaction and / or a condensation reaction.
  • hydrolyzable group examples include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group.
  • the hydrolyzable group contains a carbon atom, the number of carbon atoms is preferably 6 or less, more preferably 4 or less. Particularly, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
  • the silane coupling agent improves the adhesion between the substrate and the black layer, so that a fluorine atom and a silicon atom (excluding a silicon atom to which a hydrolyzable group is bonded) are used. It is preferable not to contain a fluorine atom, a silicon atom (however, a silicon atom to which a hydrolyzable group is bonded), an alkylene group substituted by a silicon atom, a linear alkyl group having 8 or more carbon atoms, and It is desirable not to include a branched alkyl group having 3 or more carbon atoms.
  • the silane coupling agent may contain an ethylenically unsaturated group such as a (meth) acryloyl group.
  • an ethylenically unsaturated group When an ethylenically unsaturated group is contained, the number is preferably 1 to 10, more preferably 4 to 8.
  • a silane coupling agent containing an ethylenically unsaturated group (for example, a compound containing a hydrolyzable group and an ethylenically unsaturated group and having a molecular weight of 2000 or less) does not correspond to the above-described polymerizable compound.
  • the content of the silane coupling agent in the composition is preferably from 0.1 to 10% by mass, more preferably from 0.5 to 8% by mass, and more preferably from 1.0 to 10% by mass, based on the total solids in the composition. 6% by mass is more preferred.
  • the composition may contain one kind of the silane coupling agent alone, or may contain two or more kinds. When the composition contains two or more silane coupling agents, the total may be within the above range.
  • silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, Vinyl trimethoxy silane, vinyl triethoxy silane and the like can be mentioned.
  • the composition may contain a surfactant.
  • the surfactant contributes to improving the coatability of the composition.
  • the content of the surfactant is preferably from 0.001 to 2.0% by mass, and more preferably from 0.005 to 0. 5 mass% is more preferable, and 0.01 to 0.1 mass% is further preferable.
  • One type of surfactant may be used alone, or two or more types may be used in combination. When two or more surfactants are used in combination, the total amount is preferably within the above range.
  • surfactant examples include a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant.
  • the liquid properties (particularly, fluidity) of the composition are further improved. That is, when a film is formed using a composition containing a fluorine-based surfactant, the interfacial tension between the surface to be coated and the coating solution is reduced, the wettability to the surface to be coated is improved, and The applicability to the surface is improved. For this reason, even when a thin film having a thickness of about several ⁇ m is formed with a small amount of liquid, it is effective in that a uniform thickness film having small thickness unevenness can be more suitably formed.
  • the fluorine content in the fluorinated surfactant is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, even more preferably from 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of the thickness of the coating film and / or liquid saving properties, and has good solubility in the composition.
  • fluorine-based surfactant examples include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479.
  • F482, F554, and F780 all made by DIC Corporation
  • Florado FC430, FC431, and FC171 all made by Sumitomo 3M Limited
  • Surflon S-382, SC-101, same SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 all manufactured by Asahi Glass Co., Ltd.
  • PF636, PF656, PF6320, PF6520, and PF7002 manufactured by OMNOVA
  • a block polymer can also be used as the fluorinated surfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
  • the composition preferably contains a solvent.
  • the solvent is not particularly limited, and a known solvent can be used.
  • the content of the solvent in the composition is not particularly limited, but is preferably an amount such that the solid content of the composition is 10 to 90% by mass, more preferably 10 to 40% by mass, and more preferably 15 to 35% by mass. Is more preferred.
  • One type of solvent may be used alone, or two or more types may be used in combination. When two or more solvents are used in combination, the composition is preferably adjusted so that the total solid content of the composition falls within the above range.
  • Examples of the solvent include water and an organic solvent.
  • organic solvent examples include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and acetylacetone.
  • Cyclohexanone, cyclopentanone, diacetone alcohol ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol mono Butyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, ethyl acetate, Examples include, but are not limited to, butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, and ethyl lactate.
  • water When the composition contains water, its content is preferably from 0.001 to 5.0% by mass, more preferably from 0.01 to 3.0% by mass, based on the total mass of the composition. More preferably, the amount is from 1 to 1.0% by mass. Above all, if the content of water is 3.0% by mass or less (more preferably 1.0% by mass or less) with respect to the total mass of the composition, the viscosity over time due to hydrolysis of the components in the composition and the like. It is easy to suppress the deterioration of stability, and if it is 0.01% by mass or more (preferably 0.1% by mass or more), the sedimentation stability over time is easily improved.
  • the composition may further contain other optional components other than the components described above.
  • a sensitizer, a co-sensitizer, a cross-linking agent, a curing accelerator, a thermosetting accelerator, a filler, a plasticizer, a diluent, and a sensitizer may be used.
  • Agents and other auxiliaries eg, conductive particles, fillers, defoamers, flame retardants, leveling agents, release accelerators, antioxidants, fragrances, surface tension regulators, chain transfer agents, etc. May be added as necessary.
  • paragraphs 0183 to 0228 of JP-A-2012-003225 paragraphs 0237 to 0309 of US Patent Application Publication No. 2013/0034812
  • paragraph 0101 of JP-A-2008-250074 paragraphs 0103 to 0104, paragraphs 0107 to 0109, and paragraphs 0159 to 0184 of JP-A-2013-195480 can be referred to, and the contents thereof are incorporated in the specification of the present application.
  • the composition is preferably prepared by first producing a coloring material composition containing a black coloring material, and further mixing the obtained coloring material composition with other components.
  • the coloring material composition is preferably prepared by mixing a black coloring material, a resin (preferably, a dispersing resin), and a solvent. It is also preferable to include a polymerization inhibitor in the coloring material composition.
  • the coloring material composition can be prepared by mixing the above-mentioned components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, or a wet disperser). .
  • a known mixing method for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, or a wet disperser.
  • the components may be blended together, or the components may be dissolved or dispersed in a solvent and then blended sequentially.
  • the order of charging and the working conditions for mixing are not particularly limited.
  • the light-shielding composition is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects.
  • the filter can be used without any particular limitation as long as it is a filter conventionally used for filtration or the like.
  • a filter made of a fluorine resin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, and a polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP) can be used.
  • a filter made of a fluorine resin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, and a polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP) can be used. .
  • polypropylene (including high-density polypropylene) and nylon are preferable.
  • the pore size of the filter is preferably from 0.1 to 7.0 ⁇ m, more preferably from 0.2 to 2.5 ⁇ m, even more preferably from 0.2 to 1.5 ⁇ m, and particularly preferably from 0.3 to 0.7 ⁇ m. Within this range, fine foreign substances such as impurities and agglomerates contained in the pigment can be reliably removed while suppressing clogging of the pigment (including the black pigment) by filtration.
  • different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed two or more times. When filtering is performed two or more times by combining different filters, it is preferable that the diameters of the holes after the second filtering are the same as or larger than the diameters of the holes after the first filtering.
  • first filters having different hole diameters within the above-described range may be combined.
  • the pore diameter here can refer to the nominal value of the filter manufacturer.
  • Commercially available filters can be selected from various filters provided by, for example, Nippon Pall Co., Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (former Nippon Microlith Co., Ltd.), and Kitz Micro Filter Co., Ltd.
  • As the second filter a filter formed of the same material as the first filter described above can be used.
  • the pore size of the second filter is preferably from 0.2 to 10.0 ⁇ m, more preferably from 0.2 to 7.0 ⁇ m, even more preferably from 0.3 to 6.0 ⁇ m.
  • the composition preferably does not contain impurities such as metals, metal salts containing halogens, acids, and alkalis.
  • the content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 1 mass ppb or less, still more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and it is substantially free of ( Below the detection limit of the measuring device).
  • the impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).
  • the method for forming the black layer is not particularly limited, and the light-shielding composition of the present invention is applied on a support, and the obtained coating film is cured to form a black layer (including a patterned black layer). Is done.
  • the method for forming a black layer preferably includes the following steps. ⁇ Film formation process ⁇ Curing process ⁇ Development process Hereinafter, each step will be described.
  • a light-shielding composition is applied on a support to form a coating film (composition layer).
  • a support for example, a substrate for a solid-state imaging device in which an imaging device (light-receiving device) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (eg, a silicon substrate). It can. If necessary, an undercoat layer may be provided on the support for improving adhesion to an upper layer, preventing diffusion of a substance, and flattening the surface of the substrate.
  • an imaging device light-receiving device
  • CCD Charge Coupled Device
  • CMOS Complementary Metal-Oxide Semiconductor
  • the composition on the support As a method of applying the composition on the support, various application methods such as a slit coating method, an ink jet method, a spin coating method, a casting coating method, a roll coating method, and a screen printing method can be applied.
  • the thickness of the coating film is preferably from 0.1 to 10 ⁇ m, more preferably from 0.2 to 5 ⁇ m, even more preferably from 0.2 to 3 ⁇ m. Drying (prebaking) of the coating film applied on the support can be performed, for example, on a hot plate or an oven at a temperature of 50 to 140 ° C. for 10 to 300 seconds.
  • the coating film formed in the coating film forming step is exposed to actinic rays or radiation and exposed to cure the light-irradiated coating film.
  • the method of light irradiation is not particularly limited, but light irradiation is preferably performed through a photomask having a pattern-shaped opening. Exposure is preferably performed by irradiation with radiation.
  • radiation that can be used for exposure ultraviolet rays such as g-rays, h-rays and i-rays are particularly preferred, and a high-pressure mercury lamp is preferred as a light source.
  • the irradiation intensity is preferably 5 ⁇ 1500mJ / cm 2, more preferably 10 ⁇ 1000mJ / cm 2.
  • a composition contains a thermal-polymerization initiator
  • the heating temperature is not particularly limited, but is preferably from 80 to 250 ° C.
  • the heating time is not particularly limited, but is preferably 30 to 300 seconds.
  • the developing step is a step of developing the exposed coating film.
  • the type of the developing solution used in the developing step is not particularly limited, but an alkali developing solution that does not cause damage to the underlying image pickup device, circuits, and the like is preferable.
  • the development temperature is, for example, 20 to 30 ° C.
  • the development time is, for example, 20 to 90 seconds. In order to remove the residue better, in recent years, it may be performed for 120 to 180 seconds. Further, in order to further improve the residue removal property, the step of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
  • an alkaline aqueous solution prepared by dissolving an alkaline compound in water so as to have a concentration of 0.001 to 10% by mass (preferably 0.01 to 5% by mass) is preferable.
  • the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropyl.
  • Ammonium hydroxide tetrabutylammonium hydroxy, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like. preferable.).
  • a washing treatment with water is generally performed after development.
  • Post-bake is a heat treatment after development to complete curing.
  • the heating temperature is preferably 240 ° C. or lower, more preferably 220 ° C. or lower. There is no particular lower limit, but in consideration of efficient and effective treatment, the temperature is preferably 50 ° C or higher, more preferably 100 ° C or higher.
  • Post-baking can be performed in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater.
  • the post-baking is preferably performed in an atmosphere having a low oxygen concentration.
  • the oxygen concentration is preferably 19% by volume or less, more preferably 15% by volume or less, still more preferably 10% by volume or less, particularly preferably 7% by volume or less, and most preferably 3% by volume or less. There is no particular lower limit, but 10 ppm by volume or more is practical.
  • the curing may be completed by UV (ultraviolet) irradiation instead of the post-baking by heating.
  • the above-mentioned composition preferably further contains a UV curing agent.
  • the UV curing agent is preferably a UV curing agent that can be cured at a wavelength shorter than 365 nm, which is the exposure wavelength of the polymerization initiator added for the lithography process using ordinary i-ray exposure.
  • the UV curing agent for example, Chibile Gacure 2959 (trade name) can be mentioned.
  • the coating film is a material that cures at a wavelength of 340 nm or less.
  • the exposure amount of UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, and further preferably 800 to 3500 mJ.
  • This UV curing step is preferably performed after the curing step in order to more effectively perform low-temperature curing.
  • the exposure light source preferably uses an ozone-less mercury lamp.
  • the optical density (OD: Optical Density) per 1.0 ⁇ m in the wavelength region of 400 to 1200 nm is preferably 1.7 or more, more preferably 2.0 or more. Preferably, 2.1 or more is more preferable.
  • the upper limit is not particularly limited, but is generally preferably 10 or less.
  • the expression that the optical density per 1.0 ⁇ m thickness in the wavelength region of 400 to 1200 nm is 2.0 or more means that the optical density per 1.0 ⁇ m thickness in the entire wavelength range of 400 to 1200 nm. Is 2.0 or more.
  • the optical density of the black layer is determined by first forming a black layer (light-shielding film) on a glass substrate and using a spectrophotometer U-4100 (trade name, manufactured by Hitachi High-Technologies Corp.) It can be measured by measuring using a unit, measuring the thickness of the measurement location, and calculating the optical density per predetermined thickness.
  • the thickness of the black layer is, for example, preferably from 0.1 to 4.0 ⁇ m, more preferably from 1.0 to 2.5 ⁇ m.
  • the black layer may be thinner or thicker than this range depending on the application.
  • the light-shielding property may be adjusted by making the black layer thinner (for example, 0.1 to 0.5 ⁇ m) than the above range.
  • the optical density per 1.0 ⁇ m thickness in the wavelength region of 400 to 1200 nm is preferably 0.1 to 1.5, and more preferably 0.2 to 1.0.
  • the oxygen blocking layer is a layer formed on the black layer, and has a function of blocking oxygen passing from the surface opposite to the surface in contact with the black layer to the black layer.
  • the oxygen barrier layer include a layer having an oxygen permeability in the thickness direction (hereinafter, also simply referred to as “oxygen permeability”) of 50 ml / (m 2 ⁇ day ⁇ atm) or less, and an oxygen permeability of 10 ml. / (m 2 ⁇ day ⁇ atm ) layers preferably not more than, 1.5 ml / more preferably the layer is (m 2 ⁇ day ⁇ atm) or less, 1.0ml / (m 2 ⁇ day ⁇ atm) or less Certain layers are more preferred.
  • the lower limit of the oxygen permeability is preferably 0.001 ml / (m 2 ⁇ day ⁇ atm).
  • the oxygen transmission rate can be measured using, for example, an oxygen transmission measurement apparatus (Model 8001, manufactured by Illinois Co., Ltd.).
  • the oxygen barrier layer is a single layer made of an inorganic material.
  • single layer means a layer in which the composition of the material constituting the layer is uniform along the thickness direction and the in-plane direction.
  • a laminate of the layer A made of the inorganic material a and the layer B made of the inorganic material b having a different composition from the inorganic material a has a function of blocking oxygen in both the layer A and the layer B. If it does, it is not included in the oxygen barrier layer as defined herein.
  • “comprising an inorganic material” means that the content of carbon atoms in the material constituting the oxygen barrier layer is 5% by mass or less based on the total mass of the oxygen barrier layer.
  • the content of the carbon atoms is preferably 2.5% by mass or less based on the total mass of the oxygen barrier layer.
  • the lower limit of the content of the carbon atom is not particularly limited, and may be lower than the detection limit.
  • the content of carbon atoms in the material constituting the oxygen-blocking layer is determined by forming a smooth surface on the oxygen-blocking layer by polishing or cutting, and then forming the formed smooth surface on an electron beam microanalyzer (EPMA). (Eg, “JXA-8530F” (trade name) manufactured by JEOL Ltd.) and analyzed.
  • the thickness of the oxygen barrier layer is 10 to 500 nm.
  • a light-shielding film having a more excellent balance between light resistance and moisture resistance can be manufactured. More specifically, when the thickness of the oxygen barrier layer is 10 nm or more, the effect of suppressing the variation in the thickness of the light-shielding film and the variation in optical characteristics (transmittance and reflectance) after the light resistance test is improved.
  • the thickness of the layer is 500 nm or less, the effect of suppressing peeling of the black layer from the substrate after the moisture resistance test is improved.
  • the reason why the moisture resistance is improved when the thickness of the oxygen barrier layer is 500 nm or less is not clear, when the thickness of the oxygen barrier layer is more than 500 nm, the black layer with the oxygen barrier layer and the substrate after the moisture resistance test are performed. This is presumed to be due to the fact that the stress generated due to the difference in the shrinkage ratio between the substrate and the substrate increases, causing the black layer to peel off from the substrate.
  • the thickness of the oxygen blocking layer is 500 nm or less, the light reflected on the surface of the black layer and the light reflected on the surface of the oxygen blocking layer when a light-shielding film composed of the black layer and the oxygen blocking layer are provided on the device. Can be reduced, and a decrease in device performance can be prevented.
  • the thickness of the oxygen barrier layer is preferably more than 50 nm and less than 250 nm, more preferably 70 to 200 nm, from the viewpoint that the moisture resistance and heat resistance of the light shielding film are more excellent.
  • the ratio of the thickness of the black layer to the thickness of the oxygen blocking layer may be 2 to 100, and the moisture resistance and the heat resistance of the light-shielding film are more improved. From the viewpoint of superiority, 7 to 30 is preferable, and 10 to 25 is more preferable.
  • the inorganic material constituting the oxygen barrier layer is not particularly limited, and includes a metal oxide, a metal nitride, and a metal oxynitride.
  • the metal contained in the inorganic material include silicon, titanium, aluminum, indium, tin, niobium, zirconium, cerium, tantalum, and zinc, with silicon, titanium or aluminum being preferred, and silicon being more preferred.
  • the inorganic material constituting the oxygen barrier layer silicon oxide, silicon nitride, indium oxide, tin oxide, niobium oxide, titanium oxide, zirconium oxide, cerium oxide, tantalum oxide, aluminum oxide and zinc oxide, Silicon oxide and silicon nitride are preferred, and silicon oxide is more preferred because the light-shielding film has better light resistance and moisture resistance.
  • the oxygen barrier layer of the present invention is a single layer made of an inorganic material, and does not substantially contain an organic component.
  • the oxygen barrier layer contains an organic component
  • the organic component contained therein is decomposed by light irradiation on the oxygen barrier layer, and the oxygen barrier ability is reduced.
  • the oxygen barrier layer of the present invention which is a single layer made of an inorganic material, can prevent such a decrease in oxygen barrier ability.
  • the oxygen-barrier layer "contains substantially no organic component” means that the content of carbon atoms in the material constituting the oxygen-barrier layer is 5 mass% with respect to the total mass of the oxygen-barrier layer. % Or less.
  • the content of carbon atoms in the material constituting the oxygen barrier layer is measured by the above-described method using an electron beam microanalyzer.
  • the oxygen barrier layer does not substantially contain particles from the viewpoint of more excellent heat resistance.
  • the composition of the material constituting the layer is not uniform, and a region having different heat shrinkage is generated, so that the oxygen barrier layer is greatly distorted in a high temperature environment, and the heat resistance is reduced. This is because there are times.
  • the oxygen barrier layer contains substantially no particles from the viewpoint that the surface becomes smoother and the in-plane uniformity of the reflectance is more excellent.
  • the “particles” described above are particles of a substance having a different composition from the inorganic material forming the oxygen barrier layer, and mean particles having a particle size of 10 nm or more.
  • the content of the particles in the oxygen barrier layer can be measured by the following method using an electron beam microanalyzer (EPMA) (for example, “JXA-8530F” (trade name) manufactured by JEOL Ltd.).
  • EPMA electron beam microanalyzer
  • the oxygen barrier layer is polished or cut to form a smooth surface.
  • the distribution of the element composition on the formed smooth surface is measured using an electron beam microanalyzer to obtain a mapping image of the element composition.
  • a region where the particles exist is specified based on a difference in element composition from the continuous phase.
  • the area ratio of the particles on the observation surface is obtained by dividing the total area of the particle regions by the observation area.
  • the area ratio is converted into a volume ratio (3/2 power of the area ratio), and further converted into a mass ratio based on the elemental composition, thereby obtaining the content of the particles with respect to the total amount of the oxygen barrier layer.
  • silicon oxide particles are present in an oxygen barrier layer made of silicon oxide (SiO 2 )
  • the outline of the silicon oxide particles is displayed on a mapping image due to silanol groups (SiOH) present on the surface of the silicon oxide particles. Therefore, the presence of particles can be confirmed.
  • the content of the particles can be measured based on the difference in the composition between the continuous phase and the particles in the oxygen barrier layer.
  • the oxygen barrier layer "substantially contains no particles" means that the content of the particles in the oxygen barrier layer measured by the above method is based on the total mass of the oxygen barrier layer. 5% by mass or less, or below the detection limit.
  • the method for forming the oxygen barrier layer is not particularly limited, and a known method for forming a film of an inorganic material can be used.
  • a film forming method a sputtering method, a vacuum deposition method, an ion beam assisted deposition method, an ion plate method, a deposition method such as a plasma CVD (chemical vapor deposition) method, a spin coating method, a dip coating method, and a casting method Method, a slit coating method, and a wet method such as a spray method.
  • an oxygen barrier layer by vapor deposition because it is easier to form a thin film, it is easier to control the thickness, and the adhesion to the black layer that is the object is more excellent. It is more preferable to form an oxygen barrier layer by a sputtering method.
  • the sputtering method is not particularly limited, and may be a known method such as a pulse sputtering method, an AC sputtering method, and a digital sputtering method.
  • an oxygen barrier layer is formed by a sputtering method
  • a substrate having a black layer formed on a surface thereof is disposed in a chamber in a mixed gas atmosphere of an inert gas and a reactive gas (eg, oxygen or nitrogen),
  • a target is selected so as to have a desired composition, and an oxygen barrier layer is formed.
  • the type of the inert gas is not particularly limited, and an inert gas such as argon or helium can be used.
  • the reactive gas may be selected according to the composition of the oxygen barrier layer to be formed.
  • the pressure in the chamber by the mixed gas of the inert gas and the reactive gas is not particularly limited, and may be 1.0 Pa or less, preferably 0.5 Pa or less.
  • the lower limit of the pressure in the chamber due to the mixed gas of the inert gas and the reactive gas is not particularly limited, but is preferably, for example, 0.1 Pa or more.
  • the thickness of the oxygen barrier layer can be adjusted by adjusting the discharge power or the deposition time.
  • the method for producing the light-shielding film of the present invention is not particularly limited.
  • the light-shielding film of the present invention on a support, a black colorant, a resin, a polymerizable compound, and a light-shielding composition containing a polymerization initiator is applied, and the obtained coating film is cured to form a black layer.
  • a step of forming an oxygen barrier layer on the black layer As the "step of forming a black layer”, the method described in the above “formation of a black layer” may be applied, and as the “step of forming an oxygen barrier layer”, the "step of forming an oxygen barrier layer” May be applied.
  • the thickness of the light-shielding film is, for example, preferably from 0.1 to 6.0 ⁇ m, more preferably from 1.0 to 3.5 ⁇ m.
  • the light-shielding film may be thinner or thicker than this range depending on the application.
  • the reflectance of the light-shielding film is preferably less than 5%, more preferably less than 3%, even more preferably less than 2%.
  • the light-shielding film may be a portable device such as a personal computer, a tablet, a mobile phone, a smartphone, and a digital camera; an OA (Office Automation) device such as a multifunction printer and a scanner; a monitoring camera, a barcode reader, and cash Industrial equipment such as an automated teller machine (ATM), a high-speed camera, and a device having a personal authentication function using face image authentication or biometric authentication; a vehicle-mounted camera device; an endoscope, in a capsule Medical camera equipment such as endoscopes and catheters; and biometric sensors, biosensors, military reconnaissance cameras, stereo map cameras, weather and ocean observation cameras, land resources exploration cameras, and astronomical and deep space astronomy Space equipment such as exploration cameras for targets Light blocking member and the light-shielding film of the optical filter and module used etc., and further is suitable for anti-reflection member and the antireflection film.
  • OA Office Automation
  • ATM automated teller machine
  • the light-shielding film can also be used for applications such as a micro LED (Light Emitting Diode) and a micro OLED (Organic Light Emitting Diode).
  • the light-shielding film is suitable for a member having a light-shielding function or an anti-reflection function, in addition to an optical filter and an optical film used for a micro LED and a micro OLED.
  • Examples of the micro LED and the micro OLED include the examples described in JP-T-2015-500562 and JP-T-2014-533890.
  • the light-shielding film is also suitable as an optical filter and an optical film used for a quantum dot sensor and a quantum dot solid-state imaging device. Further, it is suitable as a member for providing a light blocking function and an anti-reflection function. Examples of the quantum dot sensor and the quantum dot solid-state imaging device include those described in U.S. Patent Application Publication No. 2012/37789 and WO 2008/131313.
  • the light-shielding film of the present invention is also preferably used for a solid-state imaging device. As described above, the light-shielding film of the present invention is excellent in light resistance and moisture resistance. Further, the light-shielding film of the present invention has excellent heat resistance.
  • the present invention also includes the invention of an optical element.
  • the optical element of the present invention is an optical element having the above-mentioned light shielding film.
  • Examples of the optical element include an optical element used for an optical device such as a camera, binoculars, a microscope, and a semiconductor exposure apparatus. Above all, as the optical element, for example, a solid-state imaging element mounted on a camera or the like is preferable.
  • a solid-state imaging device is a solid-state imaging device having the light-shielding film.
  • the form in which the solid-state imaging device includes the light-shielding film is not particularly limited. For example, a plurality of photodiodes, polysilicon, and the like, which form a light receiving area of the solid-state imaging device (CCD image sensor, CMOS image sensor, and the like) on the substrate And a light-shielding film on the side of the support on which the light-receiving element is formed (for example, a portion other than the light-receiving portion and / or the pixel for color adjustment) or on the side opposite to the formation surface.
  • the dynamic range of the solid-state imaging device can be improved.
  • the solid-state imaging device includes the solid-state imaging device.
  • FIG. 1 is a schematic sectional view showing a configuration example of a solid-state imaging device including the solid-state imaging device of the present invention.
  • the solid-state imaging device 100 includes a rectangular solid-state imaging device 101, and a transparent cover glass 103 that is held above the solid-state imaging device 101 and seals the solid-state imaging device 101. I have. Further, a lens layer 111 is provided on the cover glass 103 with a spacer 104 interposed therebetween.
  • the lens layer 111 includes a support 113 and a lens material 112.
  • the lens layer 111 may have a configuration in which the support 113 and the lens material 112 are integrally formed.
  • the peripheral area of the lens layer 111 is shielded from light by providing the light shielding film 114.
  • the light shielding film of the present invention can be used as the light shielding film 114.
  • the solid-state imaging device 101 photoelectrically converts an optical image formed by the imaging unit 102, which is a light receiving surface, and outputs an image signal.
  • the solid-state imaging device 101 includes a laminated substrate 105 in which two substrates are laminated.
  • the laminated substrate 105 includes a rectangular chip substrate 106 and a circuit substrate 107 having the same size, and the circuit substrate 107 is laminated on the back surface of the chip substrate 106.
  • the material of the substrate used as the chip substrate 106 is not particularly limited, and a known material can be used.
  • the imaging unit 102 is provided at the center of the surface of the chip substrate 106. Further, a light-shielding film 115 is provided in a peripheral area of the imaging unit 102. Since the light shielding film 115 shields the stray light incident on the peripheral region, generation of dark current (noise) from circuits in the peripheral region can be prevented. It is preferable to use the light-shielding film of the present invention as the light-shielding film 115.
  • a plurality of electrode pads 108 are provided on the surface edge of the chip substrate 106.
  • the electrode pad 108 is electrically connected to the imaging unit 102 via a signal line (not shown) (not shown) provided on the surface of the chip substrate 106.
  • External connection terminals 109 are provided on the rear surface of the circuit board 107 at positions substantially below the electrode pads 108, respectively. Each external connection terminal 109 is connected to an electrode pad 108 via a through electrode 110 vertically penetrating the laminated substrate 105. In addition, each external connection terminal 109 is connected to a control circuit that controls driving of the solid-state imaging device 101, an image processing circuit that performs image processing on an imaging signal output from the solid-state imaging device 101, and the like via wiring (not shown). Have been.
  • FIG. 2 is a schematic cross-sectional view of the imaging unit 102.
  • the imaging unit 102 includes various units provided on a substrate 204 such as a light receiving element 201, a color filter 202, and a micro lens 203.
  • the color filter 202 has a blue pixel 205b, a red pixel 205r, a green pixel 205g, and a black matrix 205bm.
  • the light shielding film of the present invention may be used as the black matrix 205bm.
  • a p-well layer 206 is formed on the surface of the substrate 204.
  • light receiving elements 201 which are made of an n-type layer and generate and accumulate signal charges by photoelectric conversion are arranged in a square lattice.
  • a vertical transfer path 208 made of an n-type layer is formed via a readout gate 207 on the surface of the p-well layer 206.
  • a vertical transfer path 208 belonging to an adjacent pixel is formed via an element isolation region 209 made of a p-type layer.
  • the read gate unit 207 is a channel region for reading signal charges accumulated in the light receiving element 201 to the vertical transfer path 208.
  • a gate insulating film 210 made of an ONO (Oxide-Nitride-Oxide) film is formed on the surface of the substrate 204.
  • a vertical transfer electrode 211 made of polysilicon or amorphous silicon is formed so as to cover the vertical transfer path 208, the read gate unit 207, and almost immediately above the element isolation region 209.
  • the vertical transfer electrode 211 functions as a drive electrode that drives the vertical transfer path 208 to transfer charges and a read electrode that drives the read gate unit 207 to read signal charges.
  • the signal charges are sequentially transferred from the vertical transfer path 208 to a horizontal transfer path (not shown) and an output unit (floating diffusion amplifier), and then output as a voltage signal.
  • a light shielding film 212 is formed so as to cover the surface thereof.
  • the light-shielding film 212 has an opening at a position immediately above the light-receiving element 201, and shields other areas from light.
  • the light shielding film of the present invention may be used as the light shielding film 212.
  • an insulating film 213 made of borophosphosilicate glass (BPSG), an insulating film (passivation film) 214 made of P-SiN, and a transparent intermediate layer made of a flattening film 215 made of a transparent resin or the like are provided. ing.
  • the color filter 202 is formed on the intermediate layer.
  • the image display device of the present invention includes the light-shielding film of the present invention.
  • Examples of the mode in which the image display device has a light-shielding film include a mode in which a color filter containing a light-shielding film as a black matrix is used in the image display device.
  • a black matrix and a color filter containing a black matrix will be described, and a liquid crystal display device containing such a color filter will be described as a specific example of an image display device.
  • the light-shielding film of the present invention is also preferably used as a black matrix.
  • the black matrix may be included in an image display device such as a color filter, a solid-state imaging device, and a liquid crystal display device.
  • As the black matrix those already described above; black edges provided on the periphery of an image display device such as a liquid crystal display device; grids between red, blue, and green pixels, and / or stripes A black portion; and a dot and / or linear black pattern for light blocking of a thin film transistor (TFT).
  • TFT thin film transistor
  • the black matrix has a high light-shielding property (at an optical density OD) in order to improve display contrast and, in the case of an active matrix drive type liquid crystal display device using a thin film transistor (TFT), to prevent deterioration in image quality due to light current leakage. 3 or more).
  • TFT thin film transistor
  • the method for producing the black matrix is not particularly limited, it can be produced by the same method as the above-mentioned method for producing the light shielding film. Specifically, by applying the composition to the substrate, forming a coating film, exposure, and, after forming a patterned black layer by developing, by forming an oxygen barrier layer on the black layer, A black matrix can be manufactured.
  • the thickness of the light shielding film used as the black matrix is preferably from 0.1 to 4.0 ⁇ m.
  • the material of the substrate is not particularly limited, but preferably has a transmittance of 80% or more with respect to visible light (wavelength: 400 to 800 nm).
  • a material include glasses such as soda lime glass, non-alkali glass, quartz glass, and borosilicate glass; and plastics such as polyester resin and polyolefin resin. In view of chemical resistance and heat resistance, alkali-free glass or quartz glass is preferred.
  • the light-shielding film of the present invention is preferably contained in a color filter.
  • the form in which the color filter contains a light-shielding film is not particularly limited, and examples thereof include a color filter including a substrate and the above-described black matrix. That is, a color filter including red, green, and blue colored pixels formed in the openings of the black matrix formed on the substrate can be exemplified.
  • a color filter containing a black matrix can be manufactured, for example, by the following method.
  • the composition for each color is not particularly limited, and a known composition can be used.However, in the composition described in this specification, a composition in which a black coloring material is replaced with a coloring agent corresponding to each pixel is used. It is preferred to use.
  • the coating film is exposed through a photomask having a pattern corresponding to the opening of the black matrix.
  • baking is performed to form colored pixels in the openings of the black matrix.
  • the light-shielding film of the present invention is preferably contained in a liquid crystal display device.
  • the mode in which the liquid crystal display device includes the light-shielding film is not particularly limited, and examples include a mode in which the color filter including the black matrix described above is included.
  • the liquid crystal display device includes, for example, a mode including a pair of substrates arranged to face each other and a liquid crystal compound sealed between the substrates.
  • the substrate is as described above for the substrate for the black matrix.
  • liquid crystal display device for example, from a user side, a polarizing plate / substrate / color filter / transparent electrode layer / alignment film / liquid crystal layer / alignment film / transparent electrode layer / TFT (Thin Film Transistor) A laminated body containing an element / substrate / polarizing plate / backlight unit in this order is exemplified.
  • the liquid crystal display device is not limited to the above.
  • display device by Junsho Ibuki, Sangyo Tosho Co., Ltd., Heisei Gen) Liquid crystal display device described in “A.
  • a liquid crystal display device described in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by the Industrial Research Institute, Inc., 1994)” may be mentioned.
  • the light-shielding film of the present invention is preferably contained in an infrared sensor.
  • the infrared sensor according to the above embodiment will be described with reference to FIG.
  • FIG. 3 is a schematic sectional view showing a configuration example of an infrared sensor having the light-shielding film of the present invention.
  • the infrared sensor 300 shown in FIG. The imaging region provided on the solid-state imaging device 310 is configured by combining an infrared absorption filter 311 and a color filter 312 according to the embodiment of the present invention.
  • the infrared absorption filter 311 transmits light in the visible light range (for example, light having a wavelength of 400 to 700 nm), and transmits light in the infrared range (for example, light having a wavelength of 800 to 1300 nm, preferably light having a wavelength of 900 to 1200 nm).
  • it is a film that blocks light having a wavelength of 900 to 1000 nm), and a cured film containing an infrared absorbing agent as a coloring agent (the form of the infrared absorbing agent is as described above) can be used.
  • the color filter 312 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible light region are formed.
  • red (R), green (G), and blue (B) pixels are formed.
  • a color filter or the like is used, and the form is as described above.
  • a resin film 314 (for example, a transparent resin film or the like) capable of transmitting light having a wavelength transmitted through the infrared transmission filter 313 is arranged.
  • the infrared transmission filter 313 is a filter that has a visible light shielding property and transmits infrared light of a specific wavelength, and is a colorant that absorbs light in a visible light region (for example, a perylene compound and / or a benzofuranone compound).
  • an infrared absorber for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, and a polymethine compound
  • the infrared transmission filter 313 preferably blocks light having a wavelength of 400 to 830 nm and transmits light having a wavelength of 900 to 1300 nm.
  • a micro lens 315 is arranged on the side of the incident light h ⁇ of the color filter 312 and the infrared transmission filter 313.
  • a flattening film 316 is formed so as to cover the microlens 315. In the embodiment shown in FIG.
  • the resin film 314 is provided, but an infrared transmission filter 313 may be formed instead of the resin film 314. That is, the infrared transmission filter 313 may be formed on the solid-state imaging device 310.
  • the thickness of the color filter 312 and the thickness of the infrared transmission filter 313 are the same, but the thicknesses of the two may be different.
  • the color filter 312 is provided on the incident light h ⁇ side of the infrared absorption filter 311, but the order of the infrared absorption filter 311 and the color filter 312 is changed, and 311 may be provided closer to the incident light h ⁇ than the color filter 312. Further, in the embodiment shown in FIG.
  • the infrared absorption filter 311 and the color filter 312 are stacked adjacent to each other, but the two filters do not necessarily have to be adjacent to each other, and another layer may be provided between them.
  • the light-shielding film of the present invention can be used as a light-shielding film at the end and / or the side surface of the surface of the infrared absorption filter 311, and when it is used on the inner wall of the device of the infrared sensor, light that does not imply internal reflection and / or light to the light-receiving unit. Can be prevented and sensitivity can be improved.
  • this infrared sensor since image information can be taken in at the same time, motion sensing or the like that recognizes a target whose motion is to be detected is possible. Further, according to this infrared sensor, since distance information can be obtained, it is possible to capture an image including 3D information. Further, this infrared sensor can be used as a biometric authentication sensor.
  • the solid-state imaging device includes a lens optical system, a solid-state imaging device, an infrared light emitting diode, and the like. Note that, regarding each configuration of the solid-state imaging device, paragraphs 0032 to 0036 of JP-A-2011-233983 can be referred to, and the contents thereof are incorporated in the specification of the present application.
  • the light-shielding film of the present invention is also preferably contained in a headlight unit of a vehicle lamp such as an automobile.
  • the light-shielding film of the present invention contained in the headlight unit is preferably formed in a pattern so as to shield at least a part of light emitted from the light source.
  • FIGS. FIG. 4 is a schematic diagram illustrating a configuration example of a headlight unit
  • FIG. 5 is a schematic perspective view illustrating a configuration example of a light blocking unit of the headlight unit. As shown in FIG.
  • the headlight unit 10 includes a light source 12, a light shielding unit 14, and a lens 16, and the light source 12, the light shielding unit 14, and the lens 16 are arranged in this order.
  • the light shielding part 14 has a base 20 and a light shielding film 22 as shown in FIG.
  • the light-shielding film 22 has a pattern-shaped opening 23 for irradiating light emitted from the light source 12 in a specific shape.
  • the light distribution pattern emitted from the lens 16 is determined by the shape of the opening 23 of the light shielding film 22.
  • the lens 16 projects the light L from the light source 12 that has passed through the light shielding unit 14. If a specific light distribution pattern can be emitted from the light source 12, the lens 16 is not always necessary.
  • the lens 16 is appropriately determined according to the irradiation distance of the light L and the irradiation range.
  • the configuration of the base 20 is not particularly limited as long as the base 20 can hold the light-shielding film 22, but it is preferable that the base 20 is not deformed by heat of the light source 12, and is made of, for example, glass. You.
  • FIG. 5 shows an example of the light distribution pattern, but the present invention is not limited to this.
  • the number of the light sources 12 is not limited to one.
  • the light sources 12 may be arranged in a row or in a matrix.
  • a configuration in which one light shielding unit 14 is provided for one light source 12 may be employed. In this case, all the light shielding films 22 of the plurality of light shielding portions 14 may have the same pattern or different patterns.
  • FIG. 6 is a schematic diagram illustrating an example of a light distribution pattern by a headlight unit
  • FIG. 7 is a schematic diagram illustrating another example of a light distribution pattern by a headlight unit.
  • Each of the light distribution pattern 30 shown in FIG. 6 and the light distribution pattern 32 shown in FIG. 7 shows an area to be irradiated with light.
  • the region 31 shown in FIG. 6 and the region 31 shown in FIG. 7 indicate irradiation regions irradiated with the light source 12 (see FIG. 4) when the light shielding film 22 is not provided.
  • the light distribution pattern 30 shown in FIG. 6 is, for example, a pattern that does not illuminate oncoming vehicles when traveling on the left. Further, like the light distribution pattern 32 shown in FIG. 7, a part of the light distribution pattern 30 shown in FIG. 6 may be cut out. Also in this case, similarly to the light distribution pattern 30 shown in FIG. 6, the intensity of the light is sharply reduced at the edge 32a. For example, the pattern does not illuminate the oncoming vehicle when traveling on the left. Further, the intensity of the light is also sharply reduced in the notch 33. For this reason, in the area corresponding to the notch 33, for example, a mark indicating a state such as a curved road, an upward slope, a downward slope, or the like can be displayed. As a result, safety during night driving can be improved.
  • the light shielding unit 14 is not limited to being fixedly arranged between the light source 12 and the lens 16, and may be disposed between the light source 12 and the lens 16 by a driving mechanism (not shown) as necessary. , And a specific light distribution pattern can be obtained. Further, a shade member capable of blocking the light from the light source 12 may be configured by the light shielding unit 14. In this case, it is also possible to adopt a configuration in which a specific light distribution pattern is obtained by entering the light source 12 and the lens 16 as needed by a driving mechanism (not shown).
  • a coloring material composition containing the following black coloring material was prepared and used for preparing a light-shielding composition.
  • the obtained mixture was treated at a revolution speed of 1360 rpm and a revolution speed of 1047 rpm for 20 minutes using MAZERSTAR KK-400W manufactured by KURABO to obtain a uniform dispersion.
  • This dispersion was filled in a quartz container and heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Corporation). Thereafter, the atmosphere was replaced with nitrogen, and a nitriding reduction treatment was performed by flowing ammonia gas at the same temperature at 100 mL / min for 5 hours. After completion of the nitridation reduction treatment, the recovered powder was pulverized in a mortar to obtain a powdery titanium black (coloring material a-1) having a specific surface area of 73 m 2 / g.
  • the dispersion resin X-1 (5.5 parts by mass) having a structure represented by the following formula (X-1) was added to the coloring material a-1 (20 parts by mass) obtained above, Propylene glycol monomethyl ether acetate (hereinafter, referred to as “PGMEA”) was further added so that the concentration of the components became 35% by mass.
  • PGMEA Propylene glycol monomethyl ether acetate
  • the number given to each repeating unit means the molar ratio of each repeating unit.
  • the weight average molecular weight of the above-mentioned dispersed resin X-1 was 32,000.
  • the obtained dispersion was sufficiently stirred by a stirrer to perform premixing.
  • the obtained dispersion is subjected to a dispersion treatment using a dispersing machine NPM Pilot (trade name, manufactured by Shinmaru Enterprises Co., Ltd.) under the following conditions to obtain a color which is a dispersion containing the coloring material a-1.
  • a material composition A-1 was obtained.
  • Organic pigment containing a benzofuranone compound (trade name “Irgaphor Black S0100CF”, manufactured by BASF) (150 parts by mass), dispersing resin X-1 (75 parts by mass), Solsperse 20000 (pigment derivative, Lubri (Zol Co.) (25 parts by mass) and 3-methoxybutyl acetate (MBA) (750 parts by mass).
  • the dispersion resin X-1 is the same as that used for preparing the dispersion of the coloring material composition A-2.
  • the obtained mixture was stirred with a homomixer (manufactured by Primix) for 20 minutes to obtain a preliminary dispersion.
  • the obtained preliminary dispersion liquid was subjected to a dispersion treatment under the following dispersion conditions for 3 hours using an Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.) equipped with a centrifugal separator to obtain a dispersion composition. .
  • the beads and the dispersion were separated by a filter to obtain a colorant composition A-2 as a dispersion containing the colorant a-2.
  • the solid content concentration of the obtained dispersion was 25% by mass, and the ratio of the coloring material a-2 / the resin component (the total of the dispersion resin X-1 and the pigment derivative) was 60/40 (mass ratio).
  • Solsperse 20000 is a compound having an amine value of 29 mgKOH / g, no acid value, and having a tertiary amine as a pigment adsorbing group.
  • Coloring Material Composition A-3 ⁇ Preparation of Organic Pigment Dispersion (Coloring Material Composition A-3)> The above-described coloring material composition A- was used except that an organic pigment containing a perylene compound (trade name “PALIOGEN Black S0084”, manufactured by BASF) was used as the coloring material a-3 instead of the coloring material a-2. According to the production method 2, a coloring material composition A-3 which is a dispersion containing the coloring material a-3 was obtained.
  • an organic pigment containing a perylene compound trade name “PALIOGEN Black S0084”, manufactured by BASF
  • Carbon black was produced by the usual oil furnace method. However, as a raw material oil, ethylene bottom oil having a small Na content, a small Ca content, and a small S content was used, and combustion was performed using gas fuel. Further, pure water treated with an ion exchange resin was used as reaction stop water. Using a homomixer, the obtained carbon black (540 g) was stirred with pure water (14500 g) at 5,000 to 6,000 rpm for 30 minutes to obtain a slurry.
  • This slurry was transferred to a container equipped with a screw-type stirrer, and while mixing at about 1,000 rpm, toluene (600 g) in which epoxy resin “Epicoat 828” (manufactured by Japan Epoxy Resin) (60 g) was dissolved in the container. Was added in small portions. In about 15 minutes, all of the carbon black dispersed in the water migrated to the toluene side, and became particles having a particle size of about 1 mm. Next, after draining with a 60-mesh wire net, the separated granules are put into a vacuum drier and dried at 70 ° C.
  • the resin coating amount of the obtained resin-coated carbon black was 10% by mass based on the total amount of the carbon black and the resin.
  • the coloring material a-4 (20 parts by mass) obtained above, the dispersing resin X-1 (4.5 parts by mass), and Solsperse 12000 (manufactured by Nippon Lubrizol) (1 part by mass) were mixed to obtain a mixture.
  • PGMEA was added to the obtained mixture so that the solid content concentration became 35% by mass.
  • the dispersion resin X-1 is the same as that used in the preparation of the coloring material composition A-1.
  • the obtained dispersion was sufficiently stirred by a stirrer to perform premixing.
  • the obtained dispersion was subjected to a dispersion treatment using Ultra Apex Mill UAM015 manufactured by Kotobuki Industries Co., Ltd. under the following conditions to obtain a dispersion composition. After the dispersion was completed, the beads and the dispersion were separated by a filter to obtain a colorant composition A-4, which is a dispersion containing the colorant a-4.
  • the number given to each repeating unit means the molar ratio of each repeating unit.
  • the weight average molecular weight of the above-mentioned dispersed resin X-2 was 33,000.
  • alkali-soluble resin B-2 a resin having a structure represented by the following formula (B-2) was used.
  • a polymerization initiator C-1 a compound represented by the following formula (C-1) -Polymerization initiator C-2: IRGACURE OXE-02 (trade name, manufactured by BASF) -Polymerization initiator C-3: IRGACURE 369 (trade name, manufactured by BASF)
  • C-1 and C-2 are oxime ester-based polymerization initiators.
  • a polymerizable compound D-1 represented by the following formula (D-1) and a polymerizable compound D-2 represented by the following formula (D-2) were used for preparing a composition.
  • the value of the above “functionality” indicates the number of ethylenically unsaturated groups in one molecule of the polymerizable compound.
  • the surfactant represented by the following formula (S-1) was used for preparing a composition.
  • the weight average molecular weight of the surfactant represented by the formula (S-1) is 15,000.
  • Polymerization inhibitor As a polymerization inhibitor, p-methoxyphenol was used for preparing a light-shielding composition.
  • Example 1 ⁇ Preparation of light-shielding composition 1>
  • the light-shielding composition 1 of Example 1 was prepared by mixing the following components with a stirrer. -63 parts by mass of the coloring material composition A-1 prepared above ⁇ 3.5 parts by mass of alkali-soluble resin B-1 ⁇ 1.8 parts by mass of polymerization initiator C-1 -Polymerizable compound D-1 6.1 parts by mass ⁇ Surfactant 0.02 parts by mass ⁇ Polymerization inhibitor 0.003 parts by mass ⁇ Solvent 25.5 parts by mass
  • the light-shielding composition 1 obtained above was applied on a glass substrate by a spin coating method to form a coating film having a thickness of 1.7 ⁇ m.
  • the coated substrate was prebaked at 100 ° C. for 120 seconds.
  • a UX-1000SM-EH04 trade name, manufactured by Ushio Inc.
  • L / S line and space
  • a high-pressure mercury lamp lamp power 50 mW / cm.
  • exposure by the proximity method was performed on the substrate with the coating film.
  • a developing solution “CD-2060” (trade name, manufactured by Fuji Film Electronics Materials Co., Ltd.) was developed with a paddle using AD-1200 (manufactured by Mikasa Corporation) for 15 seconds.
  • AD-1200 manufactured by Mikasa Corporation
  • the substrate was washed with pure water for 30 seconds using a shower nozzle to remove uncured portions, thereby forming a black layer on the substrate.
  • ⁇ Formation of oxygen barrier layer E-1> A mixed gas of argon and oxygen (oxygen: 40% by volume) is introduced into a vacuum chamber of a sputtering apparatus (trade name “SRV-4300” manufactured by Shinko Seiki Co., Ltd.) and sputtering is performed using a silicon target. As a result, an oxygen barrier layer E-1 (thickness: 100 nm) made of silicon oxide (SiO 2 ) was formed on the surface of the black layer prepared above. Thus, the light-shielding film of Example 1 in which the black layer and the oxygen blocking layer E-1 were formed on the substrate in this order, was obtained.
  • Examples 2 to 6, 8, 9, 14 to 17 Except that the components used were changed or the addition amount of the coloring material composition A-1 was adjusted so that the composition of the light-shielding composition became the composition described in Tables 1 and 2, According to the method described in Example 1, the light-shielding compositions of each Example were prepared. Examples 2 to 6, 8 in which a black layer and an oxygen blocking layer are formed in this order on a substrate according to the method described in Example 1 except that each light-shielding composition obtained above is used. , 9 and 14 to 17 were produced, respectively.
  • Example 7 In the sputtering process, by introducing a mixed gas of argon and nitrogen (nitrogen: 50% by volume) into the vacuum chamber and performing sputtering, the surface of the black layer is blocked from oxygen made of silicon nitride (Si 3 N 4 ).
  • a black layer and an oxygen barrier layer E-2 are formed in this order on a substrate according to the method described in Example 1 except that a layer E-2 (thickness: 100 nm) is formed. 7 light-shielding films were produced.
  • Example 10 to 13 In the sputtering step, the procedure was performed except that the discharge power and the film formation time were adjusted, and the oxygen barrier layers E-3 to E-6 made of silicon oxide (SiO 2 ) having the thicknesses shown in Table 2 were formed. According to the method described in Example 1, the light-shielding films of Examples 10 to 13 each having a black layer and an oxygen blocking layer formed in this order on a substrate were produced.
  • Comparative Example 1 ⁇ Preparation of composition for forming oxygen barrier layer> The following components were mixed to prepare Comparative Composition 1.
  • -Polyvinyl alcohol (PVA): 32.2 parts by mass (trade name: PVA205, manufactured by Kuraray Co., Ltd., saponification degree 88%, polymerization degree 550)
  • PVA205 32.2 parts by mass
  • PVA205 32.2 parts by mass
  • PVP205 Polyvinyl pyrrolidone
  • Distilled water 524 parts by mass
  • Methanol 429 parts by mass
  • a black layer was formed on a substrate.
  • Composition 1 was applied to the surface of the produced black layer using a spin coater. The coating amount of the composition 1 was adjusted so that the thickness of the layer after drying was 1000 nm. Thereafter, the coating film of the resin composition 1 was dried at 100 ° C. for 120 seconds using a hot plate to form a comparative oxygen barrier layer CE-1 (thickness: 1000 nm).
  • the light-shielding film of Comparative Example 1 in which the black layer and the oxygen blocking layer CE-1 were formed on the substrate in this order was obtained.
  • Comparative Example 2 In the step of forming the oxygen blocking layer, a black layer and a black layer were formed on the substrate according to the method described in Comparative Example 1 except that the amount of the composition 1 was adjusted so that the thickness of the layer after drying was 500 nm. A light-shielding film of Comparative Example 2 in which the oxygen blocking layer CE-2 was formed in this order was produced.
  • Comparative Example 3 In the step of preparing the light-shielding composition, a black layer and an oxygen-blocking layer were formed on a substrate according to the method described in Comparative Example 1, except that the alkali-soluble resin B-2 was used instead of the alkali-soluble resin B-1. A light-shielding film of Comparative Example 3 in which CE-1 was formed in this order was produced.
  • composition for forming oxygen barrier layer A hydrolyzate of tetramethoxysilane (TMOS) and trifluoropropyltrimethoxysilane (TFPTMS) according to the method described in paragraphs 0032 to 0034 and 0042 (Example 1-1) of JP-A-2013-253145, and A silica sol in which beaded colloidal silica particles were dispersed was mixed to prepare Comparative Composition 2.
  • TMOS tetramethoxysilane
  • TFPTMS trifluoropropyltrimethoxysilane
  • Comparative Oxygen Blocking Layer CE-6 ⁇ Formation of Comparative Oxygen Blocking Layer CE-6>
  • the comparative composition 2 prepared above was used in place of the composition 1, and the comparative composition 2 was dried so that the thickness of the layer after drying was 190 nm.
  • a light-shielding film of Comparative Example 7 was formed by forming a black layer and an oxygen-blocking layer CE-6 on a substrate in this order according to the method described in Comparative Example 1 except that the amount of coating was adjusted.
  • the surface of the oxygen blocking layer CE-6 was polished to form a smooth surface, and then the formed smooth surface was analyzed with an electron beam microanalyzer (“JXA-8530F” (trade name) manufactured by JEOL Ltd.). And analyzed.
  • JXA-8530F electron beam microanalyzer
  • the thickness of the light-shielding film before and after the irradiation test was measured using a contact-type film thickness meter.
  • the rate of change in the thickness of the light-shielding film before and after the irradiation test was calculated using the following equation, and evaluated from the following viewpoints.
  • the “film thickness of the light-shielding film” means the sum of the thickness of the black layer and the thickness of the oxygen blocking layer, and does not include the thickness of the substrate.
  • Change rate of film thickness ((film thickness of light-shielding film before irradiation test ⁇ film thickness of light-shielding film after irradiation test) / (film thickness of light-shielding film before irradiation test) ⁇ 100)
  • D Change rate of film thickness is 10% or more
  • Change rate (%) of transmittance ((transmittance before irradiation test-transmittance after irradiation test) / transmittance before irradiation test x 100)
  • Change rate of reflectance (%) ((reflectance before irradiation test ⁇ reflectance after irradiation test) / reflectance before irradiation test ⁇ 100)
  • Both the rate of change of transmittance and the rate of change of reflectance are 2% or more.
  • the light-shielding film obtained above was placed in an oven and subjected to a heat resistance test at 150 ° C. for 500 hours.
  • the thickness of the light-shielding film before and after the heat test was measured using a contact-type film thickness meter.
  • the rate of change in the thickness of the light-shielding film before and after the heat resistance test was calculated using the following equation, and evaluated from the following viewpoints.
  • Rate of change of film thickness ((film thickness before heat resistance test ⁇ film thickness after heat resistance test) / (film thickness of light-shielding film before heat resistance test ⁇ substrate thickness) ⁇ 100)
  • Tables 1 to 3 show the compositions of the light-shielding compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 10, and the results of each test for the light-shielding films produced using those light-shielding compositions. Is shown.
  • the column of "colorant content” means the ratio (% by mass) of the content of the black colorant to the total solid content of each light-shielding composition.
  • the column of “Composition” of “Oxygen barrier layer” means that the oxygen barrier layer is a layer composed of the following materials.
  • the column of “thickness” of “oxygen blocking layer” means the thickness (nm) of each oxygen blocking layer measured using a contact type film thickness meter.
  • the column of “thickness of black layer / thickness of oxygen blocking layer” indicates the thickness of the black layer with respect to the thickness of the oxygen blocking layer measured using a contact-type film thickness meter. Means the ratio of
  • the content of the black coloring material is preferably 70% by mass or less, and more preferably 65% by mass or less, from the viewpoint that the moisture resistance of the light-shielding film is more excellent (comparison of Example 1, Examples 15 and 17). ). It was confirmed that the content of the black coloring material is preferably 30% by mass or more, and more preferably 50% by mass or more from the viewpoint that the heat resistance of the light-shielding film is more excellent (comparison of Example 1, Examples 14 and 16). ).
  • the black coloring material preferably contains a titanium oxynitride, a benzofuranone compound, or a perylene compound from the viewpoint that the moisture resistance of the light-shielding film is more excellent (Examples 1, 3, 4, and 5). Comparison). In addition, it was confirmed that the black coloring material preferably contains titanium oxynitride or carbon black from the viewpoint that the light resistance of the light-shielding film is more excellent (comparison of Examples 1, 3, 4 and 5). ).
  • the black color material containing vanadium nitride, niobium nitride or zirconium nitride is more suitable for black color containing titanium oxynitride because the light-shielding film is more excellent in moisture resistance and light resistance. It was confirmed that it was preferable as well as the material.
  • the dispersing resin preferably contains an ethylenically unsaturated group from the viewpoint of more excellent light resistance, heat resistance, and moisture resistance of the light-shielding film (comparison between Example 1 and Example 9).
  • the alkali-soluble resin is preferably a polyimide resin because the light resistance and the heat resistance of the light-shielding film are more excellent (comparison between Example 1 and Example 6).
  • a resin composed of a polybenzoxazole precursor was preferable, similarly to the polyimide resin, from the viewpoint that the light resistance and the moisture resistance of the light-shielding film were more excellent. .
  • the polymerization initiator it was confirmed that the polymerization initiator C-1 was preferable because the light resistance and the heat resistance of the light-shielding film were more excellent (comparison between Example 1 and Example 8).
  • the polymerizable compound it was confirmed that the polymerizable compound D-1 was preferable because the heat resistance and the moisture resistance of the light-shielding film were more excellent (comparison between Example 1 and Example 2).
  • the oxygen blocking layer preferably contains silicon oxide in terms of the light resistance and the moisture resistance of the light-shielding film being more excellent (comparison between Example 1 and Example 7). It was confirmed that the thickness of the oxygen blocking layer is preferably more than 50 nm and less than 250 nm from the viewpoint that the moisture resistance and the heat resistance of the light-shielding film are more excellent (comparison between Examples 1, 24 and 25 and Examples 10 and 11). ). It has been confirmed that the ratio of the thickness of the black layer to the thickness of the oxygen blocking layer is preferably 7 to 30 from the viewpoint that the light-shielding film has more excellent moisture resistance and heat resistance (Example 1 and Examples 10 and 11). And comparison).
  • Example 18 to 20 Except for using the following coloring materials a-5 to a-7 instead of titanium black (coloring material a-1), the coloring material composition A was prepared in accordance with the above-described method for preparing the coloring material composition A-1. -6 to A-8 were prepared respectively.
  • Coloring material a-5 Vanadium nitride (trade name “VN-O”, manufactured by Nippon Shinkin Co., Ltd.)
  • -Coloring material a-6 niobium nitride (trade name "NbN-O", manufactured by Nippon Shinmetal Co., Ltd.)
  • Coloring material a-7 zirconium nitride (prepared by the method of Example 1 in JP-A-2017-222559) Except that each of the coloring material compositions A-6 to A-8 prepared above was used in place of the coloring material composition A-1, the procedure was performed in accordance with the method for preparing the light-shielding composition 1 of Example 1. Light-shielding compositions of Examples 18 to 20 were respectively prepared.
  • a black layer and an oxygen blocking layer are formed in this order on a substrate according to the method described in Example 1, except that each of the obtained light-shielding compositions is used in place of the light-shielding composition 1.
  • the light-shielding films of Examples 18 to 20 were produced.
  • the evaluation results of the light-shielding films of Examples 18 to 20 were all the same as Example 1.
  • a coloring material composition was prepared according to the above-described method for preparing the coloring material composition A-1, except that the coloring material a-8 was used instead of titanium black (coloring material a-1). The same evaluation was performed.
  • Coloring material a-8 silica-coated zirconium nitride (Japanese Patent Laid-Open No.
  • Example 1 The evaluation results were the same as in Example 1.
  • a colorant composition was prepared according to the method for preparing the colorant composition A-1 described above, and the same evaluation as in Example 1 was performed.
  • the evaluation results were the same as in Example 1.
  • the evaluation results were the same as in Example 1.
  • Example 21 A light-shielding composition of Example 21 was prepared in accordance with the preparation method of light-shielding composition 1 of Example 1, except that alkali-soluble resin B-3 was used instead of alkali-soluble resin B-1. Except that the obtained light-shielding composition is used instead of light-shielding composition 1, a black layer and an oxygen-shielding layer are formed in this order on a substrate according to the method described in Example 1. A light-shielding film of Example 21 was produced. The evaluation results of the light-shielding film of Example 21 were all the same as those of Example 1.
  • Example 22 A light-shielding composition of Example 22 was prepared in accordance with the preparation method of light-shielding composition 1 of Example 1, except that polymerization initiator C-3 was used instead of polymerization initiator C-2. Except that the obtained light-shielding composition is used instead of light-shielding composition 1, a black layer and an oxygen-shielding layer are formed in this order on a substrate according to the method described in Example 1. A light-shielding film of Example 22 was produced. The evaluation result of the light-shielding film of Example 22 was the same as that of Example 8 except that the heat resistance was C.
  • Example 23 In the preparation of the light-shielding composition 1, a mixture of the polymerizable compound D-1 and the polymerizable compound D-2 having a mass ratio of 1: 1 was replaced with 6.1 parts by mass of the polymerizable compound D-1. Except for using 0.1 part by mass, the light-shielding composition of Example 23 was prepared according to the method of Example 1. Except that the obtained light-shielding composition is used instead of light-shielding composition 1, a black layer and an oxygen-shielding layer are formed in this order on a substrate according to the method described in Example 1. A light-shielding film of Example 23 was produced. The evaluation result of the light-shielding film of Example 23 was the same as that of Example 1 except that the moisture resistance was B.
  • Examples 24 and 25 Except that in the sputtering process, the discharge power and the film formation time were adjusted, and oxygen barrier layers E-7 and E-8 made of silicon oxide (SiO 2 ) having a thickness of 70 nm and 200 nm were formed, respectively. According to the method described in No. 1, the light-shielding films of Examples 24 and 25 each having a black layer and an oxygen blocking layer formed in this order on a substrate were produced. The evaluation results of the light-shielding films of Examples 24 and 25 were the same as those of Example 1.
  • Example 26 A light-shielding composition of Example 26 was prepared in accordance with the preparation method of light-shielding composition 1 of Example 1, except that the polymerization inhibitor was not used. Further, a light-shielding composition of Example 27 was prepared in accordance with the preparation method of light-shielding composition 1 of Example 1, except that no surfactant was used. According to the method described in Example 1, except that each obtained light-shielding composition is used in place of light-shielding composition 1, a black layer and an oxygen-shielding layer are formed in this order on a substrate. The light-shielding films of Examples 26 and 27 were produced, respectively. The evaluation results of the light-shielding films of Examples 26 and 27 were the same as those of Example 1.
  • Example 28 ⁇ Production of color filter with black matrix>
  • the light-shielding composition 1 of Example 1 was applied to a glass wafer by spin coating to form a composition layer.
  • the glass wafer was placed on a hot plate and prebaked at 120 ° C. for 2 minutes.
  • the composition layer was exposed at an exposure amount of 500 mJ / cm 2 through a photomask having a 0.1 mm Island pattern using an i-line stepper.
  • the exposed composition layer was paddle-developed with a 0.3% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds to obtain a cured film.
  • the obtained cured film was rinsed using a spin shower, and further washed with pure water to form a patterned black layer.
  • an oxygen barrier layer made of silicon oxide was formed on the surface of the black layer produced above in accordance with the method for forming the oxygen barrier layer E-1 of Example 1, whereby a black layer was formed on the glass wafer.
  • a light-shielding film (black matrix) in which an oxygen barrier layer was formed in this order.
  • Example 29 ⁇ Preparation of solid-state imaging device including light-shielding film> 1% by mass of an arylsulfonium salt derivative (trade name “SP-172” manufactured by ADEKA Corporation) was added to a curable composition for lenses (alicyclic epoxy resin (trade name “EHPE-3150” manufactured by Daicel Chemical Industries, Ltd.)). Composition) (2 mL) was applied on a 5 ⁇ 5 cm glass substrate (1 mm thick, manufactured by Schott, trade name “BK7”), and the coating was cured by heating at 200 ° C. for 1 minute. A lens film was formed from which the residue could be evaluated.
  • an arylsulfonium salt derivative trade name “SP-172” manufactured by ADEKA Corporation
  • the light-shielding composition 1 of Example 1 was applied on a glass wafer on which the lens film was formed to form a composition layer.
  • the glass wafer was placed on a hot plate and prebaked at 120 ° C. for 120 seconds.
  • the thickness of the composition layer after heating was 2.0 ⁇ m.
  • the composition layer was exposed using a high-pressure mercury lamp at an exposure amount of 500 mJ / cm 2 through a photomask having a hole pattern of 10 mm.
  • the exposed composition layer was paddle-developed with a 0.3% aqueous solution of tetramethylammonium hydroxide at a temperature of 23 ° C. for 60 seconds to obtain a cured film.
  • the obtained cured film was rinsed using a spin shower, and further washed with pure water to form a patterned black layer.
  • an oxygen barrier layer made of silicon oxide was formed on the surface of the black layer produced above in accordance with the method for forming the oxygen barrier layer E-1 of Example 1, whereby a black layer was formed on the glass wafer. And a light-shielding film in which an oxygen blocking layer was formed in this order.
  • a curable composition for lenses (alicyclic epoxy resin (manufactured by Daicel Chemical Industries, trade name “EHPE-3150”) and an arylsulfonium salt derivative (manufactured by ADEKA Co.) And a composition (trade name “SP-172”) added at 1% by mass) to form a curable resin layer.
  • a wafer-level lens having a plurality of wafer-level lenses is obtained by transferring the shape with a quartz mold having a lens shape, exposing it with a high-pressure mercury lamp at an exposure amount of 400 mJ / cm 2 , and curing the curable resin layer. An array was made.
  • Example 30 ⁇ Production of headlight unit with light-shielding film>
  • the light-shielding composition 1 of Example 1 obtained above was applied on a 10 cm square glass substrate by a spin coating method to form a composition layer.
  • the glass substrate was placed on a hot plate and prebaked at 120 ° C. for 2 minutes.
  • the obtained composition layer was exposed through a mask (exposure amount: 1000 mJ / cm 2 ) using an i-line stepper so that a cured film having a light distribution pattern shown in FIG. 6 was obtained.
  • development processing was performed using a developing device (Act-8 manufactured by Tokyo Electron).

Abstract

This light-shielding film comprises: a black layer containing a black coloring material; and an oxygen barrier layer formed on the black layer. The oxygen barrier layer is a single layer made from an inorganic material, and the thickness of the oxygen barrier layer is 10-500 nm. This method for manufacturing a light-shielding film comprises: a step in which a support is coated with a light-shielding composition containing a black coloring material, a resin, a polymerizable compound and a polymerization initiator, and the obtained coating film is cured to form a black layer; and a step in which an oxygen barrier layer is formed on the black layer.

Description

遮光膜、遮光膜の製造方法、光学素子、固体撮像素子、ヘッドライトユニットLight-shielding film, method of manufacturing light-shielding film, optical element, solid-state imaging device, headlight unit

　本発明は、遮光膜、遮光膜の製造方法、光学素子、固体撮像素子、及び、ヘッドライトユニットに関する。
The present invention relates to a light-shielding film, a method for manufacturing the light-shielding film, an optical element, a solid-state imaging device, and a headlight unit.

　液晶表示装置に用いられるカラーフィルタには、着色画素間の光を遮蔽し、コントラストを向上させる等の目的で、ブラックマトリクスと呼ばれる遮光膜が備えられている。

　また、現在、携帯電話及びＰＤＡ（Ｐｅｒｓｏｎａｌ　Ｄｉｇｉｔａｌ　Ａｓｓｉｓｔａｎｔ）等の電子機器の携帯端末には、小型で薄型な撮像ユニットが搭載されている。ＣＣＤ（Ｃｈａｒｇｅ　Ｃｏｕｐｌｅｄ　Ｄｅｖｉｃｅ）イメージセンサ及びＣＭＯＳ（Ｃｏｍｐｌｅｍｅｎｔａｒｙ　Ｍｅｔａｌ－Ｏｘｉｄｅ　Ｓｅｍｉｃｏｎｄｕｃｔｏｒ）イメージセンサ等の固体撮像素子には、ノイズ発生防止、及び、画質の向上等を目的として遮光膜が設けられている。
A color filter used in a liquid crystal display device is provided with a light-shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast.

Currently, portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with small and thin imaging units. A solid-state imaging device such as a charge coupled device (CCD) image sensor and a complementary metal-oxide semiconductor (CMOS) image sensor is provided with a light shielding film for the purpose of preventing noise generation and improving image quality.

　このようなカラーフィルタにおいて、遮光膜及び着色画素上に酸素遮断層を設ける技術が知られている。例えば特許文献１には、基板上に、ブラックマトリクスと、カラーフィルタ層と、ブラックマトリクスとカラーフィルタ層を覆い、少なくとも酸素遮断性化合物を含有する酸素遮断層と、カラーフィルタ層と酸素遮断層の間に染料と酸素遮断性化合物とを含有する混合層とを備える、カラーフィルタが開示されている。
In such a color filter, a technique of providing an oxygen blocking layer on a light shielding film and a colored pixel is known. For example, in Patent Document 1, a black matrix, a color filter layer, an oxygen blocking layer that covers the black matrix and the color filter layer and contains at least an oxygen blocking compound, and a color filter layer and an oxygen blocking layer There is disclosed a color filter including a mixed layer containing a dye and an oxygen-blocking compound therebetween.

特開２０１１－２４８１９７号公報JP 2011-248197 A

　本発明者らは、特許文献１に記載の酸素遮断層を備えるブラックマトリクスについて検討したところ、ブラックマトリクス（遮光膜）の耐光性及び耐湿性を、十分満足し得ない可能性があることを知見した。
The present inventors have examined the black matrix including the oxygen barrier layer described in Patent Document 1, and found that the black matrix (light-shielding film) may not be able to sufficiently satisfy the light resistance and the moisture resistance. did.

　そこで、本発明は、耐光性及び耐湿性に優れた遮光膜の提供を課題とする。また、本発明は、遮光膜の製造方法、光学素子、固体撮像素子及びヘッドライトユニットの提供も課題とする。
Therefore, an object of the present invention is to provide a light-shielding film having excellent light resistance and moisture resistance. Another object of the present invention is to provide a method for manufacturing a light-shielding film, an optical element, a solid-state imaging device, and a headlight unit.

　本発明者は、鋭意検討した結果、以下の構成により上記課題を解決できることを見出し、本発明を完成させた。
As a result of intensive studies, the present inventor has found that the following problems can be solved by the following configuration, and has completed the present invention.

　〔１〕

　黒色色材を含有する黒色層と、上記黒色層上に形成された酸素遮断層と、を備える遮光膜であって、上記酸素遮断層が、無機材料からなる単層であり、上記酸素遮断層の厚さが、１０～５００ｎｍである、遮光膜。

　〔２〕

　上記黒色色材が、チタン、バナジウム、ジルコニウム及びニオブからなる群より選択される少なくとも１種の金属の酸窒化物を含有する、〔１〕に記載の遮光膜。

　〔３〕

　上記黒色色材が、カーボンブラック、ベンゾフラノン化合物又はペリレン化合物を含有する、〔１〕に記載の遮光膜。

　〔４〕

　上記黒色色材の含有量が、上記黒色層の総質量に対して２０～８０質量％である、〔１〕～〔３〕のいずれかに記載の遮光膜。

　〔５〕

　上記酸素遮断層が、酸化ケイ素を含有する、〔１〕～〔４〕のいずれかに記載の遮光膜。

　〔６〕

　上記酸素遮断層の厚さに対する、上記黒色層の厚さの比率が、２～１００である、〔１〕～〔５〕のいずれかに記載の遮光膜。

　〔７〕

　上記酸素遮断層の酸素透過率が、１０ｍｌ／（ｍ２・ｄａｙ・ａｔｍ）以下である、〔１〕～〔６〕のいずれかに記載の遮光膜。

　〔８〕

　上記酸素遮断層が、実質的に粒子を含まない、〔１〕～〔７〕のいずれかに記載の遮光膜。

　〔９〕

　支持体上に、黒色色材、樹脂、重合性化合物、及び、重合開始剤を含有する遮光性組成物を塗布し、得られた塗膜を硬化して、黒色層を形成する工程と、上記黒色層上に、酸素遮断層を形成する工程と、を備える、遮光膜の製造方法であって、上記酸素遮断層が、無機材料からなる単層であり、上記酸素遮断層の厚さが、１０～５００ｎｍである、製造方法。

　〔１０〕

　上記酸素遮断層を形成する工程が、無機材料を蒸着する工程を含む、〔９〕に記載の遮光膜の製造方法。

　〔１１〕

　上記樹脂が、ポリイミド前駆体、ポリベンゾオキサゾール前駆体、及び、それらの共重合体からなる群より選択される少なくとも１種を含有するアルカリ可溶性樹脂を含有する、〔９〕又は〔１０〕に記載の遮光膜の製造方法。

　〔１２〕

　上記遮光性組成物が、少なくとも２種の重合性化合物を含有する、〔９〕～〔１１〕のいずれかに記載の遮光膜の製造方法。

　〔１３〕

　上記重合開始剤が、後述する式（Ｃ－１３）で表わされる化合物である、〔９〕～〔１２〕のいずれかに記載の遮光膜の製造方法。

　〔１４〕

　上記樹脂が、エチレン性不飽和基を有する樹脂を含有する、〔９〕～〔１３〕のいずれかに記載の遮光膜の製造方法。

　〔１５〕

　〔１〕～〔８〕のいずれかに記載の遮光膜を含有する光学素子。

　〔１６〕

　〔１〕～〔８〕のいずれかに記載の遮光膜を含有する固体撮像素子。

　〔１７〕

　車両用灯具のヘッドライトユニットであって、光源と、上記光源から出射された光の少なくとも一部を遮光する遮光部とを有し、上記遮光部が、〔１〕～〔８〕のいずれかに記載の遮光膜を含有する、ヘッドライトユニット。
[1]

A black layer containing a black color material, and a light shielding film including an oxygen barrier layer formed on the black layer, wherein the oxygen barrier layer is a single layer made of an inorganic material, and the oxygen barrier layer Having a thickness of 10 to 500 nm.

[2]

The light-shielding film according to [1], wherein the black color material contains at least one metal oxynitride selected from the group consisting of titanium, vanadium, zirconium, and niobium.

[3]

The light-shielding film according to [1], wherein the black color material contains carbon black, a benzofuranone compound or a perylene compound.

[4]

The light-shielding film according to any one of [1] to [3], wherein the content of the black colorant is 20 to 80% by mass based on the total mass of the black layer.

[5]

The light-shielding film according to any one of [1] to [4], wherein the oxygen barrier layer contains silicon oxide.

[6]

The light-shielding film according to any one of [1] to [5], wherein a ratio of a thickness of the black layer to a thickness of the oxygen barrier layer is 2 to 100.

[7]

The light-shielding film according to any one of [1] to [6], wherein the oxygen barrier layer has an oxygen permeability of 10 ml / (m 2 · day · atm) or less.

[8]

The light-shielding film according to any one of [1] to [7], wherein the oxygen-barrier layer contains substantially no particles.

[9]

On a support, a black colorant, a resin, a polymerizable compound, and a light-shielding composition containing a polymerization initiator is applied, and the obtained coating film is cured to form a black layer, and Forming a oxygen blocking layer on the black layer, comprising: a method for manufacturing a light-shielding film, wherein the oxygen blocking layer is a single layer made of an inorganic material, and the thickness of the oxygen blocking layer is: A manufacturing method, which is 10 to 500 nm.

[10]

The method for producing a light-shielding film according to [9], wherein the step of forming the oxygen barrier layer includes a step of depositing an inorganic material.

[11]

The resin according to [9] or [10], wherein the resin contains an alkali-soluble resin containing at least one selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a copolymer thereof. Method for manufacturing a light-shielding film.

[12]

The method for producing a light-shielding film according to any one of [9] to [11], wherein the light-shielding composition contains at least two kinds of polymerizable compounds.

[13]

The method for producing a light-shielding film according to any one of [9] to [12], wherein the polymerization initiator is a compound represented by the following formula (C-13).

[14]

The method for producing a light-shielding film according to any one of [9] to [13], wherein the resin contains a resin having an ethylenically unsaturated group.

[15]

An optical element containing the light-shielding film according to any one of [1] to [8].

[16]

A solid-state imaging device containing the light-shielding film according to any one of [1] to [8].

[17]

A headlight unit for a vehicular lamp, comprising: a light source; and a light shielding unit that shields at least a part of light emitted from the light source, wherein the light shielding unit is any one of [1] to [8]. A headlight unit comprising the light-shielding film according to item 1.

　本発明によれば、耐光性及び耐湿性に優れた遮光膜を提供できる。また、本発明は、遮光膜の製造方法、光学素子、固体撮像素子、及び、ヘッドライトユニットを提供できる。
According to the present invention, a light-shielding film having excellent light resistance and moisture resistance can be provided. Further, the present invention can provide a method for manufacturing a light-shielding film, an optical element, a solid-state imaging device, and a headlight unit.

固体撮像装置の構成例を示す概略断面図である。FIG. 3 is a schematic sectional view illustrating a configuration example of a solid-state imaging device. 図１で示す固体撮像装置が備える撮像部を拡大して示す概略断面図である。FIG. 2 is a schematic cross-sectional view showing, on an enlarged scale, an imaging unit provided in the solid-state imaging device shown in FIG. 1. 赤外線センサの構成例を示す概略断面図である。FIG. 3 is a schematic sectional view illustrating a configuration example of an infrared sensor. ヘッドライトユニットの構成例を示す模式図である。It is a schematic diagram which shows the example of a structure of a headlight unit. ヘッドライトユニットの遮光部の構成例を示す模式的斜視図である。FIG. 3 is a schematic perspective view illustrating a configuration example of a light shielding unit of the headlight unit. ヘッドライトユニットによる配光パターンの一例を示す模式図である。It is a schematic diagram which shows an example of the light distribution pattern by a headlight unit. ヘッドライトユニットによる配光パターンの他の例を示す模式図である。It is a schematic diagram which shows the other example of the light distribution pattern by a headlight unit.

　以下、本発明について詳細に説明する。

　以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされる場合があるが、本発明はそのような実施態様に制限されない。

　なお、本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含有する範囲を意味する。
Hereinafter, the present invention will be described in detail.

The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

In this specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.

　また、本明細書における基（原子団）の表記において、置換及び無置換を記していない表記は、置換基を含有しない基と共に置換基を含有する基をも包含する。例えば、「アルキル基」とは、置換基を含有しないアルキル基（無置換アルキル基）のみならず、置換基を含有するアルキル基（置換アルキル基）をも包含する。
Further, in the notation of a group (atomic group) in the present specification, the notation of not indicating substituted or unsubstituted includes a group having a substituent as well as a group having no substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

　また、本明細書中における「活性光線」又は「放射線」とは、例えば、遠紫外線、極紫外線（ＥＵＶ：Ｅｘｔｒｅｍｅ　ｕｌｔｒａｖｉｏｌｅｔ　ｌｉｔｈｏｇｒａｐｈｙ）、Ｘ線、及び、電子線等を意味する。また本明細書において光とは、活性光線及び放射線を意味する。本明細書中における「露光」とは、特に断らない限り、遠紫外線、Ｘ線、及びＥＵＶ光等による露光のみならず、電子線及びイオンビーム等の粒子線による描画も包含する。
In the present specification, “actinic rays” or “radiation” means, for example, far ultraviolet rays, extreme ultraviolet (EUV), X-rays, electron beams, and the like. Further, in this specification, light means actinic rays and radiation. Unless otherwise specified, the term “exposure” in this specification includes not only exposure with far ultraviolet rays, X-rays, EUV light, and the like, but also drawing with particle beams such as electron beams and ion beams.

　また、本明細書において、「（メタ）アクリレート」はアクリレート及びメタアクリレートを表す。本明細書において、「（メタ）アクリル」はアクリル及びメタアクリルを表す。本明細書において、「（メタ）アクリロイル」は、アクリロイル及びメタクリロイルを表す。本明細書において、「（メタ）アクリルアミド」は、アクリルアミド及びメタアクリルアミドを表す。本明細書中において、「単量体」と「モノマー」とは同義である。
In this specification, “(meth) acrylate” represents acrylate and methacrylate. In the present specification, “(meth) acryl” represents acryl and methacryl. In the present specification, “(meth) acryloyl” represents acryloyl and methacryloyl. In this specification, “(meth) acrylamide” represents acrylamide and methacrylamide. In this specification, “monomer” and “monomer” have the same meaning.

　本明細書において、「ｐｐｍ」は「ｐａｒｔｓ－ｐｅｒ－ｍｉｌｌｉｏｎ（１０－６）」を意味し、「ｐｐｂ」は「ｐａｒｔｓ－ｐｅｒ－ｂｉｌｌｉｏｎ（１０－９）」を意味し、「ｐｐｔ」は「ｐａｒｔｓ－ｐｅｒ－ｔｒｉｌｌｉｏｎ（１０－１２）」を意味する。
In the present specification, “ppm” means “parts-per-million (10 −6 )”, “ppb” means “parts-per-billion (10 −9 )”, and “ppt” is “ppt”. parts-per-trillion (10 -12 ) ".

　また、本明細書において重量平均分子量（Ｍｗ）は、ＧＰＣ（Ｇｅｌ　Ｐｅｒｍｅａｔｉｏｎ　Ｃｈｒｏｍａｔｏｇｒａｐｈｙ：ゲル浸透クロマトグラフィー）法によるポリスチレン換算値である。

　本明細書においてＧＰＣ法は、ＨＬＣ－８０２０ＧＰＣ（東ソー社製）を用い、カラムとしてＴＳＫｇｅｌ　ＳｕｐｅｒＨＺＭ－Ｈ、ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺ４０００、ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺ２０００（東ソー社製、４．６ｍｍＩＤ×１５ｃｍ）を、溶離液としてＴＨＦ（テトラヒドロフラン）を用いる方法に基づく。
In the present specification, the weight average molecular weight (Mw) is a value in terms of polystyrene measured by a GPC (Gel Permeation Chromatography) method.

In this specification, the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), and uses TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as a column and THF (tetrahydrofuran) as an eluent. ).

〔遮光膜〕

　本発明の遮光膜は、黒色色材を含有する黒色層と、黒色層上に設けられた酸素遮断層と、を備える。

　上記酸素遮断層は、無機材料からなる単層である。

　上記酸素遮断層の厚さは、１０～５００ｎｍである。
(Light shielding film)

The light-shielding film of the present invention includes a black layer containing a black coloring material, and an oxygen blocking layer provided on the black layer.

The oxygen barrier layer is a single layer made of an inorganic material.

The thickness of the oxygen barrier layer is 10 to 500 nm.

　また、本発明の遮光膜は、支持体上に、黒色色材、樹脂、重合性化合物、及び、重合開始剤を含有する遮光性組成物を塗布し、得られた塗布膜を硬化して、黒色層を形成する工程と、上記黒色層上に、酸素遮断層を形成する工程と、を備える製造方法により、製造できる。
Further, the light-shielding film of the present invention, on a support, a black colorant, a resin, a polymerizable compound, and a light-shielding composition containing a polymerization initiator is applied, and the obtained coating film is cured, It can be manufactured by a manufacturing method including a step of forming a black layer and a step of forming an oxygen barrier layer on the black layer.

［黒色層］

　本発明の遮光膜に含まれる黒色層は、黒色色材を含有する。

　黒色層は、その製造方法によって制限されないが、例えば、上記遮光性組成物を用いて形成された塗膜を硬化することにより得られる黒色層（パターン状の黒色層を含む）である。
[Black layer]

The black layer contained in the light-shielding film of the present invention contains a black color material.

The black layer is not limited by the manufacturing method, and is, for example, a black layer (including a patterned black layer) obtained by curing a coating film formed using the light-shielding composition.

〔遮光性組成物〕

　黒色層を形成するために用いられる遮光性組成物（以下、単に「組成物」とも記載する）について、説明する。遮光性組成物は、黒色色材、樹脂、重合性化合物、及び、重合開始剤を少なくとも含有する。
(Light-shielding composition)

The light-shielding composition used for forming the black layer (hereinafter, simply referred to as “composition”) will be described. The light-shielding composition contains at least a black coloring material, a resin, a polymerizable compound, and a polymerization initiator.

＜黒色色材＞

　遮光性組成物は黒色色材を含有する。

　黒色色材としては、黒色顔料及び黒色染料からなる群から選択される１種以上が挙げられる。

　黒色色材は１種単独で使用してもよく、２種以上を使用してもよい。
<Black color material>

The light-shielding composition contains a black coloring material.

As the black color material, at least one selected from the group consisting of black pigments and black dyes can be used.

One type of black color material may be used alone, or two or more types may be used.

　黒色層中における黒色色材の含有量は、特に制限されず、例えば黒色層の総質量に対して、２０～８０質量％であってよい。黒色色材の含有量は、遮光膜の耐熱性がより優れる点から、黒色層の総質量に対して、２０質量％超が好ましく、３０質量％以上がより好ましく、５０質量％以上が更に好ましい。また、黒色色材の含有量は、遮光膜の耐湿性がより優れる点から、黒色層の総質量に対して、８０質量％未満が好ましく、７０質量％以下がより好ましく、６５質量％以下が更に好ましい。
The content of the black color material in the black layer is not particularly limited, and may be, for example, 20 to 80% by mass based on the total mass of the black layer. The content of the black colorant is preferably more than 20% by mass, more preferably 30% by mass or more, even more preferably 50% by mass or more based on the total mass of the black layer, from the viewpoint that the heat resistance of the light-shielding film is more excellent. . In addition, the content of the black colorant is preferably less than 80% by mass, more preferably 70% by mass or less, and more preferably 65% by mass or less based on the total mass of the black layer, from the viewpoint that the moisture resistance of the light-shielding film is more excellent. More preferred.

　また、遮光性組成物中の黒色色材の含有量は、例えば遮光性組成物の全固形分に対して、２０～８０質量％であってよく、遮光膜の耐熱性がより優れる点から、遮光性組成物の全固形分に対して、２０質量％超が好ましく、３０質量％以上がより好ましく、５０質量％以上が更に好ましい。また、遮光性組成物中の黒色色材の含有量は、遮光膜の耐湿性がより優れる点から、遮光性組成物の全固形分に対して、８０質量％未満が好ましく、７０質量％以下がより好ましく、６５質量％以下が更に好ましい。

　なお、本明細書において、組成物の「全固形分」とは、硬化等により層又は膜を形成する成分を意味し、組成物が溶剤（有機溶剤、水等）を含有する場合、溶剤を除いたすべての成分を意味する。また、膜を形成する成分であれば、液体状の成分も固形分とみなす。

　即ち、遮光性組成物の全固形分に対する黒色色材の含有量を調整することにより、黒色層中の黒色色材の含有量を所望の値に調整できる。
Further, the content of the black colorant in the light-shielding composition may be, for example, 20 to 80% by mass based on the total solid content of the light-shielding composition, and from the viewpoint that the heat resistance of the light-shielding film is more excellent, It is preferably more than 20% by mass, more preferably 30% by mass or more, even more preferably 50% by mass or more based on the total solid content of the light-shielding composition. Further, the content of the black colorant in the light-shielding composition is preferably less than 80% by mass, and more preferably 70% by mass or less based on the total solid content of the light-shielding composition, from the viewpoint that the moisture resistance of the light-shielding film is more excellent. Is more preferable, and 65% by mass or less is further preferable.

In the present specification, the “total solid content” of the composition means a component that forms a layer or a film by curing or the like, and when the composition contains a solvent (organic solvent, water, or the like), the solvent is used. Means all components except. Liquid components are also considered as solids as long as they form a film.

That is, by adjusting the content of the black coloring material with respect to the total solid content of the light-shielding composition, the content of the black coloring material in the black layer can be adjusted to a desired value.

　また、単独では黒色色材として使用できない着色剤を複数組み合わせ、全体として黒色になるように調整して黒色色材としてもよい。

　例えば、単独では黒色以外の色を有する顔料を複数組み合わせて黒色顔料として使用してもよい。同様に、単独では黒色以外の色を有する染料を複数組み合わせて黒色染料として使用してもよく、単独では黒色以外の色を有する顔料と単独では黒色以外の色を有する染料とを組み合わせて黒色染料として使用してもよい。
Alternatively, a plurality of colorants that cannot be used alone as a black color material may be combined and adjusted so as to be black as a whole to be used as a black color material.

For example, a single pigment may be used as a black pigment by combining a plurality of pigments having colors other than black. Similarly, a black dye may be used alone as a black dye by combining a plurality of dyes having colors other than black, and a pigment having a color other than black alone and a dye having a color other than black alone may be used. You may use as.

　本明細書において、黒色色材とは、波長４００～７００ｎｍの全ての範囲にわたって吸収がある色材を意味する。

　より具体的には、例えば、以下に説明する評価基準Ｚに適合する黒色色材が好ましい。

　まず、色材と、透明な樹脂マトリックス（アクリル樹脂等）と、溶剤とを含有し、全固形分に対する色材の含有量が６０質量％である組成物を調製する。得られた組成物を、ガラス基板上に、乾燥後の塗膜の膜厚が１μｍになるように塗布し、塗膜を形成する。乾燥後の塗膜の遮光性を、分光光度計（日立株式会社製ＵＶ－３６００等）を用いて評価する。乾燥後の塗膜の波長４００～７００ｎｍにおける透過率の最大値が１０％未満であれば、上記色材は評価基準Ｚに適合する黒色色材であると判断できる。
In this specification, a black colorant means a colorant that absorbs over the entire wavelength range of 400 to 700 nm.

More specifically, for example, a black color material that meets the evaluation criteria Z described below is preferable.

First, a composition containing a coloring material, a transparent resin matrix (such as an acrylic resin), and a solvent, and having a coloring material content of 60% by mass based on the total solid content is prepared. The obtained composition is applied on a glass substrate so that the thickness of the coating film after drying becomes 1 μm to form a coating film. The light-shielding properties of the dried coating film are evaluated using a spectrophotometer (UV-3600 manufactured by Hitachi, Ltd.). If the maximum value of the transmittance of the coating film after drying at a wavelength of 400 to 700 nm is less than 10%, it can be determined that the coloring material is a black coloring material that meets the evaluation criterion Z.

（黒色顔料）

　黒色顔料としては、各種公知の黒色顔料を使用できる。黒色顔料は、無機顔料であっても有機顔料であってもよい。

　黒色色材は、黒色層の耐光性がより優れる点から、黒色顔料が好ましい。
(Black pigment)

Various known black pigments can be used as the black pigment. The black pigment may be an inorganic pigment or an organic pigment.

As the black coloring material, a black pigment is preferable because the light resistance of the black layer is more excellent.

　黒色顔料としては、単独で黒色を発現する顔料が好ましく、単独で黒色を発現し、かつ、赤外線を吸収する顔料がより好ましい。

　ここで、赤外線を吸収する黒色顔料は、例えば、赤外領域（好ましくは、波長６５０～１３００ｎｍ）の波長領域に吸収を有する。波長６７５～９００ｎｍの波長領域に極大吸収波長を有する黒色顔料も好ましい。
As the black pigment, a pigment that independently expresses black is preferable, and a pigment that independently expresses black and absorbs infrared light is more preferable.

Here, the black pigment that absorbs infrared rays has, for example, absorption in a wavelength region of an infrared region (preferably, a wavelength of 650 to 1300 nm). A black pigment having a maximum absorption wavelength in a wavelength range of 675 to 900 nm is also preferable.

　黒色顔料の粒径は、特に制限されないが、ハンドリング性と組成物の経時安定性（黒色顔料が沈降しない）とのバランスがより優れる点から、５～１００ｎｍが好ましく、５～５０ｎｍがより好ましく、５～３０ｎｍが更に好ましい。
The particle size of the black pigment is not particularly limited, but is preferably 5 to 100 nm, more preferably 5 to 50 nm, since the balance between the handleability and the stability over time of the composition (the black pigment does not settle out) is more excellent. 5 to 30 nm is more preferred.

　なお、本明細書において「粒径」とは、以下の方法により測定した粒子の平均一次粒子径を意味する。平均一次粒子径は、透過型電子顕微鏡（Ｔｒａｎｓｍｉｓｓｉｏｎ　Ｅｌｅｃｔｒｏｎ　Ｍｉｃｒｏｓｃｏｐｅ、ＴＥＭ）を用いて測定できる。透過型電子顕微鏡としては、例えば、日立ハイテクノロジーズ社製の透過型顕微鏡ＨＴ７７００を使用できる。

　透過型電子顕微鏡を用いて得た粒子像の最大長（Ｄｍａｘ：粒子画像の輪郭上の２点における最大長さ）、及び最大長垂直長（ＤＶ－ｍａｘ：最大長に平行な２本の直線で画像を挟んだ時、２直線間を垂直に結ぶ最短の長さ）を測長し、その相乗平均値（Ｄｍａｘ×ＤＶ－ｍａｘ）１／２を粒子径とした。この方法で１００個の粒子の粒子径を測定し、その算術平均値を粒子の平均一次粒子径とした。
In addition, in this specification, "particle diameter" means the average primary particle diameter of the particle measured by the following method. The average primary particle diameter can be measured using a transmission electron microscope (TEM). As the transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.

The maximum length of a particle image obtained using a transmission electron microscope (Dmax: the maximum length at two points on the contour of the particle image), and the maximum vertical length (DV-max: two straight lines parallel to the maximum length) When the image was sandwiched, the shortest length connecting the two straight lines vertically was measured, and the geometric mean value (Dmax × DV-max) 1/2 was defined as the particle diameter. The particle diameter of 100 particles was measured by this method, and the arithmetic average value was defined as the average primary particle diameter of the particles.

・無機顔料

　無機顔料としては、遮光性を有し、無機化合物を含有する粒子であれば、特に制限されず、公知の無機顔料が使用できる。

　黒色層の低反射性及び遮光性がより優れる点から、黒色色材としては、無機顔料が好ましい。
・ Inorganic pigment

The inorganic pigment is not particularly limited as long as it has a light-shielding property and is a particle containing an inorganic compound, and a known inorganic pigment can be used.

As the black color material, an inorganic pigment is preferable because the black layer has more excellent low reflectivity and light blocking properties.

　無機顔料としては、チタン（Ｔｉ）及びジルコニウム（Ｚｒ）等の第４族の金属元素、バナジウム（Ｖ）及びニオブ（Ｎｂ）等の第５族の金属元素、コバルト（Ｃｏ）、クロム（Ｃｒ）、銅（Ｃｕ）、マンガン（Ｍｎ）、ルテニウム（Ｒｕ）、鉄（Ｆｅ）、ニッケル（Ｎｉ）、錫（Ｓｎ）、並びに、銀（Ａｇ）からなる群より選ばれた１種又は２種以上の金属元素を含有する、金属酸化物、金属窒化物、及び金属酸窒化物等が挙げられる。

　上記の金属酸化物、金属窒化物、及び金属酸窒化物としては、更に他の原子が混在した粒子を使用してもよい。例えば、更に周期表１３～１７族元素から選択される原子（好ましくは酸素原子、及び／又は、硫黄原子）を含有する金属窒化物含有粒子が、使用できる。
Examples of inorganic pigments include Group 4 metal elements such as titanium (Ti) and zirconium (Zr), Group 5 metal elements such as vanadium (V) and niobium (Nb), cobalt (Co), and chromium (Cr). , Copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and one or more selected from the group consisting of silver (Ag) Metal oxides, metal nitrides, metal oxynitrides, and the like containing the above metal element.

As the metal oxide, metal nitride, and metal oxynitride, particles in which other atoms are mixed may be used. For example, metal nitride-containing particles further containing an atom (preferably an oxygen atom and / or a sulfur atom) selected from the elements of Groups 13 to 17 of the periodic table can be used.

　上記の金属窒化物、金属酸化物又は金属酸窒化物の製造方法としては、所望とする物性を有する黒色顔料が得られるものであれば、特に制限されず、気相反応法等の公知の製造方法を使用できる。気相反応法としては、電気炉法、及び、熱プラズマ法等が挙げられるが、不純物の混入が少なく、粒径が揃いやすく、また、生産性が高い点で、熱プラズマ法が好ましい。

　上記の金属窒化物、金属酸化物又は金属酸窒化物には、表面修飾処理が施されていてもよい。例えば、シリコーン基とアルキル基とを併せ持つ表面処理剤で表面修飾処理が施されていてもよい。そのような無機粒子としては、「ＫＴＰ－０９」シリーズ（信越化学工業社製）等が挙げられる。
The method for producing the above-described metal nitride, metal oxide or metal oxynitride is not particularly limited as long as a black pigment having desired physical properties can be obtained. You can use any method. Examples of the gas phase reaction method include an electric furnace method and a thermal plasma method, and a thermal plasma method is preferable in that impurities are less mixed, particle diameters are easily formed, and productivity is high.

The above-mentioned metal nitride, metal oxide or metal oxynitride may be subjected to a surface modification treatment. For example, the surface modification treatment may be performed with a surface treatment agent having both a silicone group and an alkyl group. Examples of such inorganic particles include the “KTP-09” series (manufactured by Shin-Etsu Chemical Co., Ltd.).

　中でも、黒色層を形成する際のアンダーカットの発生を抑制できる点から、チタン、バナジウム、ジルコニウム及びニオブからなる群より選択される少なくとも１種の金属の窒化物又は酸窒化物は、より好ましい。また、黒色色材は、遮光膜の耐光性及び耐湿性がより優れる点から、チタン、バナジウム、ジルコニウム及びニオブからなる群より選択される少なくとも１種の金属の酸窒化物を含有することが更に好ましく、チタン酸窒化物（チタンブラック）を含有することが特に好ましい。
Above all, a nitride or oxynitride of at least one metal selected from the group consisting of titanium, vanadium, zirconium and niobium is more preferable, since generation of an undercut when forming a black layer can be suppressed. In addition, the black color material further contains at least one metal oxynitride selected from the group consisting of titanium, vanadium, zirconium and niobium, in that the light resistance and the moisture resistance of the light-shielding film are more excellent. It is particularly preferable to contain a titanium oxynitride (titanium black).

　チタンブラックは、チタン酸窒化物を含有する黒色粒子である。チタンブラックは、分散性向上、凝集性抑制などの目的で必要に応じ、表面を修飾することが可能である。チタンブラックは、酸化ケイ素、酸化チタン、酸化ゲルマニウム、酸化アルミニウム、酸化マグネシウム、又は、酸化ジルコニウムで被覆することが可能であり、また、特開２００７－３０２８３６号公報に表されるような撥水性物質での処理も可能である。
Titanium black is black particles containing titanium oxynitride. The surface of titanium black can be modified as needed for the purpose of improving dispersibility, suppressing cohesion, and the like. Titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and a water-repellent substance as disclosed in JP-A-2007-302636. Processing is also possible.

　チタンブラックの製造方法としては、二酸化チタンと金属チタンの混合体を還元雰囲気で加熱し還元する方法（特開昭４９－５４３２号公報）、四塩化チタンの高温加水分解で得られた超微細二酸化チタンを水素を含有する還元雰囲気中で還元する方法（特開昭５７－２０５３２２号公報）、二酸化チタン又は水酸化チタンをアンモニア存在下で高温還元する方法（特開昭６０－６５０６９号公報、特開昭６１－２０１６１０号公報）、及び、二酸化チタン又は水酸化チタンにバナジウム化合物を付着させ、アンモニア存在下で高温還元する方法（特開昭６１－２０１６１０号公報）などがあるが、これらに制限されるものではない。
As a method for producing titanium black, a method in which a mixture of titanium dioxide and metallic titanium is reduced by heating in a reducing atmosphere (Japanese Patent Application Laid-Open No. 49-5432), an ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a hydrogen-containing reducing atmosphere (Japanese Patent Application Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia (Japanese Patent Application Laid-Open No. 60-65069), Japanese Patent Application Laid-Open No. 61-201610) and a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at a high temperature in the presence of ammonia (Japanese Patent Application Laid-Open No. 61-201610). It is not something to be done.

　チタンブラックの粒径は、特に制限されないが、１０～４５ｎｍが好ましく、１２～２０ｎｍがより好ましい。チタンブラックの比表面積は、特に制限されないが、撥水化剤で表面処理した後の撥水性が所定の性能となるために、ＢＥＴ（Ｂｒｕｎａｕｅｒ，Ｅｍｍｅｔｔ，Ｔｅｌｌｅｒ）法にて測定した値が５～１５０ｍ２／ｇであることが好ましく、２０～１００ｍ２／ｇであることがより好ましい。
The particle size of titanium black is not particularly limited, but is preferably from 10 to 45 nm, more preferably from 12 to 20 nm. The specific surface area of titanium black is not particularly limited, but the value measured by the BET (Brunauer, Emmett, Teller) method is 5 to 5 because the water repellency after surface treatment with a water repellent has a predetermined performance. It is preferably 150 m 2 / g, more preferably 20 to 100 m 2 / g.

　チタンブラックの市販品の例としては、チタンブラック１０Ｓ、１２Ｓ、１３Ｒ、１３Ｍ、１３Ｍ－Ｃ、１３Ｒ、１３Ｒ－Ｎ、１３Ｍ－Ｔ（商品名、三菱マテリアル株式会社製）、ティラック（Ｔｉｌａｃｋ）Ｄ（商品名、赤穂化成株式会社製）、ＭＴ－１５０Ａ（商品名、テイカ株式会社製）等が挙げられる。
Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name, manufactured by Mitsubishi Materials Corporation), Tilac D (Trade name, manufactured by Ako Kasei Co., Ltd.) and MT-150A (trade name, manufactured by Teika Co., Ltd.).

　遮光性組成物は、チタンブラックを、チタンブラック及びＳｉ原子を含有する被分散体として含有することも好ましい。この形態において、チタンブラックは、組成物中において被分散体として含有される。被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）が質量換算で０．０５～０．５であることが好ましく、０．０７～０．４であることがより好ましい。ここで、上記被分散体は、チタンブラックが一次粒子の状態であるもの、凝集体（二次粒子）の状態であるものの双方を包含する。

　また、被分散体のＳｉ／Ｔｉが小さすぎると、被分散体を使用した塗膜を光リソグラフィー等によりパターニングした際に、除去部に残渣が残りやすくなり、被分散体のＳｉ／Ｔｉは大きすぎると遮光能が低下する傾向となる。
The light-shielding composition also preferably contains titanium black as a dispersion containing titanium black and Si atoms. In this embodiment, titanium black is contained in the composition as a dispersion. The content ratio of Si atoms to Ti atoms (Si / Ti) in the dispersion is preferably 0.05 to 0.5 in terms of mass, more preferably 0.07 to 0.4. Here, the above-mentioned dispersion target includes both those in which titanium black is in the state of primary particles and those in the form of aggregates (secondary particles).

Further, if the Si / Ti of the dispersion is too small, a residue tends to remain in the removed portion when the coating film using the dispersion is patterned by photolithography or the like, and the Si / Ti of the dispersion is large. If too much, the light-shielding ability tends to decrease.

　被分散体のＳｉ／Ｔｉを変更する（例えば０．０５以上とする）ためには、以下のような手段を用いることができる。先ず、酸化チタン粒子と酸化ケイ素粒子とを分散機を用いて分散することにより分散物を得て、この混合物を高温（例えば、８５０～１０００℃）にて還元処理することにより、チタンブラック粒子を主成分とし、ＳｉとＴｉとを含有する被分散体を得ることができる。Ｓｉ／Ｔｉが調整されたチタンブラックは、例えば、特開２００８－２６６０４５公報の段落番号公報の段落０００５及び００１６～００２１に記載の方法により作製できる。

　なお、被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）は、例えば、ＷＯ２０１１/０４９０９０号公報の段落００５４～００５６に記載の方法（２－１）又は方法（２－３）を用いて測定できる。
In order to change the Si / Ti of the object to be dispersed (for example, 0.05 or more), the following means can be used. First, a dispersion is obtained by dispersing titanium oxide particles and silicon oxide particles using a dispersing machine, and the mixture is subjected to a reduction treatment at a high temperature (for example, 850 to 1000 ° C.), whereby titanium black particles are reduced. A dispersed object containing Si and Ti as a main component can be obtained. Titanium black with adjusted Si / Ti can be produced, for example, by the method described in paragraphs 0005 and 0016 to 0021 of paragraph number publication of JP-A-2008-266045.

The content ratio of Si atoms to Ti atoms (Si / Ti) in the dispersion is determined, for example, by the method (2-1) or the method (2-3) described in paragraphs 0054 to 0056 of WO2011 / 049090. ) Can be measured.

　チタンブラック及びＳｉ原子を含有する被分散体において、チタンブラックは、上記したものを使用できる。また、この被分散体においては、チタンブラックと共に、分散性、着色性等を調整する目的で、Ｃｕ、Ｆｅ、Ｍｎ、Ｖ及びＮｉ等から選択される複数の金属の複合酸化物、酸化コバルト、酸化鉄、カーボンブラック、並びに、アニリンブラック等からなる黒色顔料を、１種又は２種以上を組み合わせて、被分散体として併用してもよい。この場合、全被分散体中の５０質量％以上をチタンブラックからなる被分散体が占めることが好ましい。

　遮光性組成物は、窒化ジルコニウム、または、酸窒化ジルコニウムを含有することも好ましい。窒化ジルコニウム、または、酸窒化ジルコニウムは、無機化合物で被覆されていることが好ましい。窒化ジルコニウム、または、酸窒化ジルコニウムの表面を無機化合物で被覆することにより、顔料（遮光顔料）の遮光性を損なうことなく、遮光顔料の光触媒活性を抑制し、遮光性組成物の劣化を防止し易くなる。無機化合物の好ましい具体例は、二酸化チタン、ジルコニア、シリカ、アルミナ等があるが、シリカ、アルミナが挙げられる。チタンブラックと窒化ジルコニウム、チタンブラックと酸窒化ジルコニウム、チタンブラックとシリカ被覆窒化ジルコニウム、チタンブラックとアルミナ被覆窒化ジルコニウムの組み合わせで、併用することも好ましい。
In the dispersion containing titanium black and Si atoms, the above-mentioned titanium black can be used. In addition, in the object to be dispersed, a composite oxide of a plurality of metals selected from Cu, Fe, Mn, V, Ni, etc., together with titanium black, for the purpose of adjusting dispersibility, coloring property, etc., cobalt oxide, A black pigment composed of iron oxide, carbon black, aniline black, or the like may be used alone or in combination of two or more as a dispersion. In this case, it is preferable that 50% by mass or more of the entirety of the dispersion is occupied by the dispersion composed of titanium black.

The light-shielding composition also preferably contains zirconium nitride or zirconium oxynitride. Zirconium nitride or zirconium oxynitride is preferably coated with an inorganic compound. By coating the surface of zirconium nitride or zirconium oxynitride with an inorganic compound, the photocatalytic activity of the light-shielding pigment is suppressed without deteriorating the light-shielding properties of the pigment (light-shielding pigment), and the deterioration of the light-shielding composition is prevented. It will be easier. Preferred specific examples of the inorganic compound include titanium dioxide, zirconia, silica, and alumina, and examples thereof include silica and alumina. It is also preferable to use a combination of titanium black and zirconium nitride, titanium black and zirconium oxynitride, titanium black and zirconium nitride coated with silica, and titanium black and zirconium nitride coated with alumina.

　無機顔料としては、カーボンブラックも挙げられる。

　黒色色材は、遮光性の耐光性が優れ、特に耐光試験後の光学特性の変動抑制がより優れる点から、カーボンブラックを含有することが好ましい。
Examples of the inorganic pigment include carbon black.

The black coloring material preferably contains carbon black from the viewpoint of excellent light-shielding light resistance and more excellent suppression of fluctuations in optical characteristics after a light resistance test.

　カーボンブラックとしては、例えば、ファーネスブラック、チャンネルブラック、サーマルブラック、アセチレンブラック及びランプブラックが挙げられる。

　カーボンブラックとしては、オイルファーネス法等の公知の方法で製造されたカーボンブラックを使用してもよく、市販品を使用してもよい。カーボンブラックの市販品の具体例としては、Ｃ．Ｉ．ピグメントブラック１等の有機顔料、及び、Ｃ．Ｉ．ピグメントブラック７等の無機顔料が挙げられる。
Examples of the carbon black include furnace black, channel black, thermal black, acetylene black, and lamp black.

As the carbon black, a carbon black produced by a known method such as an oil furnace method may be used, or a commercially available product may be used. Specific examples of commercially available carbon black include C.I. I. An organic pigment such as CI Pigment Black 1; I. Pigment Black 7 and the like.

　カーボンブラックとしては、表面処理がされたカーボンブラックが好ましい。表面処理により、カーボンブラックの粒子表面状態を改質でき、組成物中での分散安定性を向上させることができる。表面処理としては、樹脂による被覆処理、酸性基を導入する表面処理、及び、シランカップリング剤による表面処理が挙げられる。
As the carbon black, surface-treated carbon black is preferable. By the surface treatment, the particle surface state of the carbon black can be modified, and the dispersion stability in the composition can be improved. Examples of the surface treatment include a coating treatment with a resin, a surface treatment for introducing an acidic group, and a surface treatment with a silane coupling agent.

　カーボンブラックとしては、樹脂による被覆処理がされたカーボンブラックが好ましい。カーボンブラックの粒子表面を絶縁性の樹脂で被覆することにより、黒色層の遮光性及び絶縁性を向上させることができる。また、リーク電流の低減などにより、画像表示装置の信頼性などを向上させることができる。このため、黒色層を絶縁性が要求される用途に用いる場合などに好適である。

　被覆樹脂としては、エポキシ樹脂、ポリアミド、ポリアミドイミド、ノボラック樹脂、フェノール樹脂、ウレア樹脂、メラミン樹脂、ポリウレタン、ジアリルフタレート樹脂、アルキルベンゼン樹脂、ポリスチレン、ポリカーボネート、ポリブチレンテレフタレート及び変性ポリフェニレンオキサイドが挙げられる。

　被覆樹脂の含有量は、黒色層の遮光性及び絶縁性がより優れる点から、カーボンブラック及び被覆樹脂の合計に対して、０．１～４０質量％が好ましく、０．５～３０質量％がより好ましい。
As the carbon black, carbon black coated with a resin is preferable. By coating the surface of the carbon black particles with an insulating resin, the light-shielding properties and insulating properties of the black layer can be improved. In addition, reliability of the image display device can be improved by reducing a leak current or the like. For this reason, it is suitable when the black layer is used for applications requiring insulation.

Examples of the coating resin include epoxy resin, polyamide, polyamideimide, novolak resin, phenol resin, urea resin, melamine resin, polyurethane, diallyl phthalate resin, alkylbenzene resin, polystyrene, polycarbonate, polybutylene terephthalate, and modified polyphenylene oxide.

The content of the coating resin is preferably from 0.1 to 40% by mass, more preferably from 0.5 to 30% by mass, based on the total of the carbon black and the coating resin, from the viewpoint that the black layer has more excellent light-shielding properties and insulating properties. More preferred.

・有機顔料

　有機顔料としては、遮光性を有し、有機化合物を含有する粒子であれば、特に制限されず、公知の有機顔料が使用できる。

　有機顔料の具体例としては、例えば、ベンゾフラノン化合物、アゾメチン化合物、ペリレン化合物、及び、アゾ系化合物が挙げられる。

　黒色色材は、遮光膜の耐湿性がより優れる点から、ベンゾフラノン化合物又はペリレン化合物を含有することが好ましい。
・ Organic pigment

The organic pigment is not particularly limited as long as it has a light-shielding property and contains an organic compound, and a known organic pigment can be used.

Specific examples of the organic pigment include a benzofuranone compound, an azomethine compound, a perylene compound, and an azo compound.

The black coloring material preferably contains a benzofuranone compound or a perylene compound from the viewpoint that the moisture resistance of the light-shielding film is more excellent.

（ベンゾフラノン化合物）

　ベンゾフラノン化合物は、分子内にベンゾフラン－２（３Ｈ）－オン構造又はベンゾフラン－３（２Ｈ）－オン構造を有する、可視光線の波長の光を吸収することで黒色に着色する化合物である。
(Benzofuranone compound)

The benzofuranone compound is a compound having a benzofuran-2 (3H) -one structure or a benzofuran-3 (2H) -one structure in a molecule and which is colored black by absorbing light having a visible light wavelength.

　ベンゾフラノン化合物としては、特表２０１０－５３４７２６号公報、特表２０１２－５１５２３３号公報、及び、特表２０１２－５１５２３４号公報に記載された化合物が挙げられる。

　また、ベンゾフラノン化合物としては、一般式（６３）～（６８）のいずれかで表される化合物が好ましい。
Examples of the benzofuranone compound include compounds described in JP-T-2010-534726, JP-T-2012-515233, and JP-T-2012-515234.

Further, as the benzofuranone compound, a compound represented by any of the general formulas (63) to (68) is preferable.

Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002

　一般式（６３）～（６５）において、Ｒ２０６、Ｒ２０７、Ｒ２１２、Ｒ２１３、Ｒ２１８及びＲ２１９は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～１０のアルキル基又はフッ素原子を１～２０個有する炭素数１～１０のアルキル基を表す。Ｒ２０８、Ｒ２０９、Ｒ２１４、Ｒ２１５、Ｒ２２０及びＲ２２１は、それぞれ独立して、水素原子、ハロゲン原子、Ｒ２５１、ＣＯＯＨ、ＣＯＯＲ２５１、ＣＯＯ－、ＣＯＮＨ２、ＣＯＮＨＲ２５１、ＣＯＮＲ２５１Ｒ２５２、ＣＮ、ＯＨ、ＯＲ２５１、ＯＣＯＲ２５１、ＯＣＯＮＨ２、ＯＣＯＮＨＲ２５１、ＯＣＯＮＲ２５１Ｒ２５２、ＮＯ２、ＮＨ２、ＮＨＲ２５１、ＮＲ２５１Ｒ２５２、ＮＨＣＯＲ２５１、ＮＲ２５１ＣＯＲ２５２、Ｎ＝ＣＨ２、Ｎ＝ＣＨＲ２５１、Ｎ＝ＣＲ２５１Ｒ２５２、ＳＨ、ＳＲ２５１、ＳＯＲ２５１、ＳＯ２Ｒ２５１、ＳＯ３Ｒ２５１、ＳＯ３Ｈ、ＳＯ３ －、ＳＯ２ＮＨ２、ＳＯ２ＮＨＲ２５１又はＳＯ２ＮＲ２５１Ｒ２５２を表し、Ｒ２５１及びＲ２５２は、それぞれ独立して、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数２～１０のアルケニル基、炭素数４～１０のシクロアルケニル基又は炭素数２～１０のアルキニル基を表す。複数のＲ２０８、Ｒ２０９、Ｒ２１４、Ｒ２１５、Ｒ２２０又はＲ２２１は、直接結合、又は、酸素原子ブリッジ、硫黄原子ブリッジ、ＮＨブリッジもしくはＮＲ２５１ブリッジで環を形成してもよい。Ｒ２１０、Ｒ２１１、Ｒ２１６、Ｒ２１７、Ｒ２２２及びＲ２２３は、それぞれ独立して、水素原子、炭素数１～１０のアルキル基又は炭素数６～１５のアリール基を表す。ａ、ｂ、ｃ、ｄ、ｅ及びｆは、それぞれ独立して、０～４の整数を表す。一般式（６３）～（６５）において、Ｒ２０６、Ｒ２０７、Ｒ２１２、Ｒ２１３、Ｒ２１８及びＲ２１９は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～６のアルキル基又はフッ素原子を１～１２個有する炭素数１～６のアルキル基が好ましい。また、Ｒ２５１及びＲ２５２は、それぞれ独立して、炭素数１～６のアルキル基、炭素数４～７のシクロアルキル基、炭素数２～６のアルケニル基、炭素数４～７のシクロアルケニル基又は炭素数２～６のアルキニル基が好ましい。また、Ｒ２１０、Ｒ２１１、Ｒ２１６、Ｒ２１７、Ｒ２２２及びＲ２２３は、それぞれ独立して、水素原子、炭素数１～６のアルキル基又は炭素数６～１０のアリール基が好ましい。上記のアルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アルキニル基及びアリール基は、ヘテロ原子を有してもよく、無置換体又は置換体のいずれであってもよい。
In the general formulas (63) to (65), R 206 , R 207 , R 212 , R 213 , R 218 and R 219 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or Represents an alkyl group having 1 to 20 carbon atoms and having 1 to 20 fluorine atoms. R 208 , R 209 , R 214 , R 215 , R 220 and R 221 each independently represent a hydrogen atom, a halogen atom, R 251 , COOH, COOR 251 , COO − , CONH 2 , CONHR 251 , CONR 251 R 252, CN, OH, OR 251 , OCOR 251, OCONH 2, OCONHR 251, OCONR 251 R 252, NO 2, NH 2, NHR 251, NR 251 R 252, NHCOR 251, NR 251 COR 252, N = CH 2, N = CHR 251 , N = CR 251 R 252 , SH, SR 251 , SOR 251 , SO 2 R 251 , SO 3 R 251 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR 251 or SO 2 represents NR 251 R 252, R 51 and R 252, which may be the independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkenyl group or C 4 to 10 carbon atoms Represents an alkynyl group of Formulas 2 to 10. A plurality of R 208 , R 209 , R 214 , R 215 , R 220 or R 221 may form a ring by a direct bond or an oxygen atom bridge, a sulfur atom bridge, an NH bridge or an NR 251 bridge. R 210 , R 211 , R 216 , R 217 , R 222 and R 223 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms. a, b, c, d, e and f each independently represent an integer of 0 to 4. In the general formulas (63) to (65), R 206 , R 207 , R 212 , R 213 , R 218 and R 219 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or An alkyl group having 1 to 6 carbon atoms and having 1 to 12 fluorine atoms is preferable. R 251 and R 252 each independently represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a cycloalkenyl having 4 to 7 carbon atoms. A group or an alkynyl group having 2 to 6 carbon atoms is preferred. Further, R 210 , R 211 , R 216 , R 217 , R 222 and R 223 are each independently preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. The above-mentioned alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group and aryl group may have a hetero atom, and may be unsubstituted or substituted.

Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003

　一般式（６６）～（６８）において、Ｒ２５３、Ｒ２５４、Ｒ２５９、Ｒ２６０、Ｒ２６５及びＲ２６６は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～１０のアルキル基又はフッ素原子を１～２０個有する炭素数１～１０のアルキル基を表す。Ｒ２５５、Ｒ２５６、Ｒ２６１、Ｒ２６２、Ｒ２６７及びＲ２６８は、それぞれ独立して、水素原子、ハロゲン原子、Ｒ２７１、ＣＯＯＨ、ＣＯＯＲ２７１、ＣＯＯ－、ＣＯＮＨ２、ＣＯＮＨＲ２７１、ＣＯＮＲ２７１Ｒ２７２、ＣＮ、ＯＨ、ＯＲ２７１、ＯＣＯＲ２７１、ＯＣＯＮＨ２、ＯＣＯＮＨＲ２７１、ＯＣＯＮＲ２７１Ｒ２７２、ＮＯ２、ＮＨ２、ＮＨＲ２７１、ＮＲ２７１Ｒ２７２、ＮＨＣＯＲ２７１、ＮＲ２７１ＣＯＲ２７２、Ｎ＝ＣＨ２、Ｎ＝ＣＨＲ２７１、Ｎ＝ＣＲ２７１Ｒ２７２、ＳＨ、ＳＲ２７１、ＳＯＲ２７１、ＳＯ２Ｒ２７１、ＳＯ３Ｒ２７１、ＳＯ３Ｈ、ＳＯ３ －、ＳＯ２ＮＨ２、ＳＯ２ＮＨＲ２７１又はＳＯ２ＮＲ２７１Ｒ２７２を表し、Ｒ２７１及びＲ２７２は、それぞれ独立して、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数２～１０のアルケニル基、炭素数４～１０のシクロアルケニル基又は炭素数２～１０のアルキニル基を表す。複数のＲ２５５、Ｒ２５６、Ｒ２６１、Ｒ２６２、Ｒ２６７又はＲ２６８は、直接結合、又は、酸素原子ブリッジ、硫黄原子ブリッジ、ＮＨブリッジもしくはＮＲ２７１ブリッジで環を形成してもよい。Ｒ２５７、Ｒ２５８、Ｒ２６３、Ｒ２６４、Ｒ２６９及びＲ２７０は、それぞれ独立して、水素原子、炭素数１～１０のアルキル基又は炭素数６～１５のアリール基を表す。ａ、ｂ、ｃ、ｄ、ｅ及びｆは、それぞれ独立して、０～４の整数を表す。一般式（６６）～（６８）において、Ｒ２５３、Ｒ２５４、Ｒ２５９、Ｒ２６０、Ｒ２６５及びＲ２６６は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～６のアルキル基又はフッ素原子を１～１２個有する炭素数１～６のアルキル基が好ましい。また、Ｒ２７１及びＲ２７２は、それぞれ独立して、炭素数１～６のアルキル基、炭素数４～７のシクロアルキル基、炭素数２～６のアルケニル基、炭素数４～７のシクロアルケニル基又は炭素数２～６のアルキニル基が好ましい。また、Ｒ２５７、Ｒ２５８、Ｒ２６３、Ｒ２６４、Ｒ２６９及びＲ２７０は、それぞれ独立して、水素原子、炭素数１～６のアルキル基又は炭素数６～１０のアリール基が好ましい。上記のアルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アルキニル基及びアリール基は、ヘテロ原子を有してもよく、無置換体又は置換体のいずれであってもよい。
In the general formulas (66) to (68), R 253 , R 254 , R 259 , R 260 , R 265 and R 266 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or Represents an alkyl group having 1 to 20 carbon atoms and having 1 to 20 fluorine atoms. R 255 , R 256 , R 261 , R 262 , R 267 and R 268 each independently represent a hydrogen atom, a halogen atom, R 271 , COOH, COOR 271 , COO − , CONH 2 , CONHR 271 , CONR 271 R 272, CN, OH, OR 271 , OCOR 271, OCONH 2, OCONHR 271, OCONR 271 R 272, NO 2, NH 2, NHR 271, NR 271 R 272, NHCOR 271, NR 271 COR 272, N = CH 2, N = CHR 271 , N = CR 271 R 272 , SH, SR 271 , SOR 271 , SO 2 R 271 , SO 3 R 271 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR 271 or SO 2 It represents the NR 271 R 272, R 71 and R 272 are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkenyl group or C 4 to 10 carbon atoms Represents an alkynyl group of Formulas 2 to 10. A plurality of R 255 , R 256 , R 261 , R 262 , R 267 or R 268 may form a direct bond or a ring with an oxygen atom bridge, a sulfur atom bridge, an NH bridge or an NR 271 bridge. R 257 , R 258 , R 263 , R 264 , R 269 and R 270 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms. a, b, c, d, e and f each independently represent an integer of 0 to 4. In the general formulas (66) to (68), R 253 , R 254 , R 259 , R 260 , R 265 and R 266 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or An alkyl group having 1 to 6 carbon atoms and having 1 to 12 fluorine atoms is preferable. R 271 and R 272 each independently represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a cycloalkenyl having 4 to 7 carbon atoms. A group or an alkynyl group having 2 to 6 carbon atoms is preferred. Further, R 257 , R 258 , R 263 , R 264 , R 269 and R 270 are each independently preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. The above-mentioned alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group and aryl group may have a hetero atom, and may be unsubstituted or substituted.

　ベンゾフラノン化合物は、例えば、Ｉｒｇａｐｈｏｒ　Ｂｌａｃｋ　Ｓ０１００ＣＦ（商品名、ＢＡＳＦ社製）として入手可能である。
The benzofuranone compound is available, for example, as Irgaphor Black S0100CF (trade name, manufactured by BASF).

（ペリレン化合物）

　ペリレン化合物は、分子内にペリレン構造を有する、可視光線の波長の光を吸収することで黒色に着色する化合物である。
(Perylene compound)

A perylene compound is a compound that has a perylene structure in the molecule and is colored black by absorbing light having a wavelength of visible light.

　ペリレン化合物としては、特開昭６２－１７５３号公報、及び、特公昭６３－２６７８４号公報に記載された化合物が挙げられる。

　また、ペリレン化合物としては、一般式（６９）～（７１）のいずれかで表されるペリレン化合物が好ましい。
Examples of the perylene compound include compounds described in JP-A-62-1753 and JP-B-63-26784.

Further, as the perylene compound, a perylene compound represented by any of the general formulas (69) to (71) is preferable.

Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004

　一般式（６９）～（７１）において、Ｘ９２、Ｘ９３、Ｘ９４及びＸ９５は、それぞれ独立して、炭素数１～１０のアルキレン基を表す。Ｒ２２４及びＲ２２５は、それぞれ独立して、水素、ヒドロキシ基、炭素数１～６のアルコキシ基又は炭素数２～６のアシル基を表す。Ｒ２７３及びＲ２７４は、それぞれ独立して、水素原子又は炭素数１～１０のアルキル基を表す。ａ及びｂは、それぞれ独立して、０～５の整数を表す。一般式（６９）～（７１）において、Ｘ９２、Ｘ９３、Ｘ９４及びＸ９５は、それぞれ独立して、炭素数１～６のアルキレン基が好ましい。また、Ｒ２２４及びＲ２２５は、それぞれ独立して、水素原子、ヒドロキシ基、炭素数１～４のアルコキシ基又は炭素数２～４のアシル基が好ましい。Ｒ２７３及びＲ２７４は、それぞれ独立して、水素又は炭素数１～６のアルキル基が好ましい。上記のアルキレン基、アルコキシ基、アシル基及びアルキル基は、ヘテロ原子を有してもよく、無置換体又は置換体のいずれであってもよい。
In the general formulas (69) to (71), X 92 , X 93 , X 94 and X 95 each independently represent an alkylene group having 1 to 10 carbon atoms. R 224 and R 225 each independently represent hydrogen, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms. R 273 and R 274 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. a and b each independently represent an integer of 0 to 5. In the general formulas (69) to (71), X 92 , X 93 , X 94 and X 95 are each independently preferably an alkylene group having 1 to 6 carbon atoms. R 224 and R 225 are each independently preferably a hydrogen atom, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, or an acyl group having 2 to 4 carbon atoms. Each of R 273 and R 274 is preferably independently hydrogen or an alkyl group having 1 to 6 carbon atoms. The above-mentioned alkylene group, alkoxy group, acyl group and alkyl group may have a hetero atom and may be either unsubstituted or substituted.

　ペリレン化合物は、例えば、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　２１、３０、３１、３２、３３及び３４、並びに、Ｐａｌｉｏｇｅｎ　Ｂｌａｃｋ　Ｓ００８４、同Ｋ００８４、同Ｌ００８６、同Ｋ００８６、同ＥＨ０７８８及び同ＦＫ４２８１（以上商品名、いずれもＢＡＳＦ社製）として入手可能である。
Perylene compounds are described, for example, in C.I. I. Pigment Black 21, 30, 31, 32, 33, and 34, and Paliogen Black S0084, K0084, L0086, K0086, EH0788, and FK4281 (all of which are brand names, all manufactured by BASF). .

（黒色染料）

　黒色染料としては、単独で黒色を発現する染料が使用でき、例えば、ピラゾールアゾ化合物、ピロメテン化合物、アニリノアゾ化合物、トリフェニルメタン化合物、アントラキノン化合物、ベンジリデン化合物、オキソノール化合物、ピラゾロトリアゾールアゾ化合物、ピリドンアゾ化合物、シアニン化合物、フェノチアジン化合物、及び、ピロロピラゾールアゾメチン化合物等を使用できる。

　また、黒色染料としては、特開昭６４－９０４０３号公報、特開昭６４－９１１０２号公報、特開平１－９４３０１号公報、特開平６－１１６１４号公報、特登２５９２２０７号公報、米国特許４８０８５０１号明細書、米国特許５６６７９２０号明細書、米国特許５０５９５０号明細書、特開平５－３３３２０７号公報、特開平６－３５１８３号公報、特開平６－５１１１５号公報、及び、特開平６－１９４８２８号公報等に記載の化合物を参照でき、これらの内容は本明細書に組み込まれる。
(Black dye)

As the black dye, a dye that expresses black alone can be used, for example, a pyrazole azo compound, a pyrromethene compound, an anilino azo compound, a triphenylmethane compound, an anthraquinone compound, a benzylidene compound, an oxonol compound, a pyrazolotriazole azo compound, and a pyridone azo compound. , A cyanine compound, a phenothiazine compound, a pyrrolopyrazole azomethine compound, and the like.

Examples of black dyes include JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-T-2592207, and US Pat. No. 4,808,501. Specification, US Pat. No. 5,679,920, US Pat. No. 505,950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, and JP-A-6-194828. Reference can be made to compounds described in gazettes and the like, the contents of which are incorporated herein.

　これらの黒色染料の具体例としては、ソルベントブラック２７～４７のカラーインデックス（Ｃ．Ｉ．）で規定される染料が挙げられ、ソルベントブラック２７、２９又は３４のＣ．Ｉ．で規定される染料が好ましい。

　また、これらの黒色染料の市販品としては、スピロン　Ｂｌａｃｋ　ＭＨ、Ｂｌａｃｋ　ＢＨ（以上、保土谷化学工業株式会社製）、ＶＡＬＩＦＡＳＴ　Ｂｌａｃｋ　３８０４、３８１０、３８２０、３８３０（以上、オリエント化学工業株式会社製）、Ｓａｖｉｎｙｌ　Ｂｌａｃｋ　ＲＬＳＮ（以上、クラリアント社製）、ＫＡＹＡＳＥＴ　Ｂｌａｃｋ　Ｋ－Ｒ、Ｋ－ＢＬ（以上、日本化薬株式会社製）等の染料が挙げられる。
Specific examples of these black dyes include dyes defined by the color index (CI) of Solvent Black 27 to 47, and C.I. of Solvent Black 27, 29 or 34. I. Are preferred.

Also, commercially available products of these black dyes include Spiron Black MH, Black BH (all manufactured by Hodogaya Chemical Industry Co., Ltd.), VALIFAST Black 3804, 3810, 3820, 3830 (all manufactured by Orient Chemical Industry Co., Ltd.), Dyes such as Savinyl Black RLSN (all manufactured by Clariant), KAYASET Black KR and K-BL (all manufactured by Nippon Kayaku Co., Ltd.).

　また、黒色染料としては色素多量体を用いてもよい。色素多量体としては、特開２０１１－２１３９２５号公報、及び、特開２０１３－０４１０９７号公報に記載されている化合物が挙げられる。また、分子内に重合性を有する重合性染料を用いてもよく、市販品としては、例えば、和光純薬工業社製ＲＤＷシリーズが挙げられる。

　更に、上述の通り、単独では黒色以外の色を有する染料を複数組み合わせて黒色染料として使用してもよい。このような着色染料としては、例えば、Ｒ（レッド）、Ｇ（グリーン）、及び、Ｂ（ブルー）等の有彩色系の染料（有彩色染料）の他、特開２０１４－４２３７５の段落００２７～０２００に記載の染料も使用できる。
Further, a dye multimer may be used as the black dye. Examples of the dye multimer include compounds described in JP-A-2011-213925 and JP-A-2013-041097. Further, a polymerizable dye having polymerizability in the molecule may be used, and examples of commercially available products include RDW series manufactured by Wako Pure Chemical Industries.

Further, as described above, a single dye having a color other than black may be used alone as a black dye. Examples of such coloring dyes include chromatic dyes (chromatic dyes) such as R (red), G (green), and B (blue), as well as paragraphs 0027 to 264 of JP-A-2014-42375. No. 0200 can also be used.

　黒色色材は、黒色層を形成する際のアンダーカットの発生を抑制できる点から、チタン、バナジウム、ジルコニウム及びニオブからなる群より選択される少なくとも１種の金属の窒化物又は酸窒化物を含有することがより好ましく、遮光膜の耐光性及び耐湿性がより優れる点から、チタン、バナジウム、ジルコニウム及びニオブからなる群より選択される少なくとも１種の金属の酸窒化物を含有することが更に好ましく、チタン酸窒化物（チタンブラック）を含有することが特に好ましい。

　また、黒色色材は、カーボンブラック、ベンゾフラノン化合物又はペリレン化合物を含有することも好ましい。
The black coloring material contains a nitride or oxynitride of at least one metal selected from the group consisting of titanium, vanadium, zirconium and niobium from the viewpoint of suppressing the occurrence of undercut when forming the black layer. More preferably, from the viewpoint that the light resistance and moisture resistance of the light-shielding film are more excellent, it is further preferable that the light-shielding film contains at least one metal oxynitride selected from the group consisting of titanium, vanadium, zirconium and niobium. It is particularly preferable to contain titanium oxynitride (titanium black).

Further, the black coloring material preferably contains carbon black, a benzofuranone compound or a perylene compound.

（着色剤）

　遮光性組成物は、黒色色材以外の着色剤を含有してもよい。黒色色材と、１種以上の着色剤との両方を使用して、黒色層（遮光膜）の遮光特性を調整できる。また、例えば、黒色層を光減衰膜として使用する場合に、広い波長成分を含有する光に対して、各波長を均等に減衰しやすい。

　着色剤としては、上述した黒色色材以外の顔料及び染料が挙げられる。

　組成物が着色剤を含有する場合、黒色色材と着色剤との合計含有量は、組成物の固形分の全質量に対して、１０～９０質量％が好ましく、３０～７０質量％がより好ましく、４０～６０質量％が更に好ましい。

　なお、遮光性組成物から形成される黒色層を、光減衰膜として使用する場合、黒色色材と着色剤との合計含有量は、上記好適範囲より少ないことも好ましい。

　また、黒色色材の含有量に対する、着色剤の含有量との質量比（着色剤の含有量／黒色色材の含有量）は、０．１～９．０が好ましい。
(Colorant)

The light-shielding composition may contain a coloring agent other than the black coloring material. The light-shielding characteristics of the black layer (light-shielding film) can be adjusted by using both the black colorant and one or more colorants. Further, for example, when a black layer is used as a light attenuating film, it is easy to uniformly attenuate each wavelength with respect to light containing a wide wavelength component.

Examples of the coloring agent include pigments and dyes other than the above-described black coloring material.

When the composition contains a colorant, the total content of the black colorant and the colorant is preferably from 10 to 90% by mass, more preferably from 30 to 70% by mass, based on the total mass of the solid content of the composition. Preferably, it is 40 to 60% by mass.

When a black layer formed from the light-shielding composition is used as a light attenuating film, the total content of the black coloring material and the coloring agent is preferably smaller than the above preferred range.

Further, the mass ratio of the content of the coloring agent to the content of the black coloring material (the content of the coloring agent / the content of the black coloring material) is preferably 0.1 to 9.0.

（赤外線吸収剤）

　組成物は、更に、赤外線吸収剤を含有してもよい。

　赤外線吸収剤は、赤外領域（好ましくは、波長６５０～１３００ｎｍ）の波長領域に吸収を有する化合物を意味する。赤外線吸収剤としては、波長６７５～９００ｎｍの波長領域に極大吸収波長を有する化合物が好ましい。

　このような分光特性を有する着色剤としては、例えば、ピロロピロール化合物、銅化合物、シアニン化合物、フタロシアニン化合物、イミニウム化合物、チオール錯体系化合物、遷移金属酸化物系化合物、スクアリリウム化合物、ナフタロシアニン化合物、クアテリレン化合物、ジチオール金属錯体系化合物、及び、クロコニウム化合物等が挙げられる。

　フタロシアニン化合物、ナフタロシアニン化合物、イミニウム化合物、シアニン化合物、スクアリリウム化合物、及び、クロコニウム化合物は、特開２０１０－１１１７５０号公報の段落００１０～００８１に開示の化合物を使用してもよく、この内容は本明細書に組み込まれる。シアニン化合物は、例えば、「機能性色素、大河原信／松岡賢／北尾悌次郎／平嶋恒亮・著、講談社サイエンティフィック」を参酌でき、この内容は本願明細書に組み込まれる。
(Infrared absorber)

The composition may further contain an infrared absorber.

The infrared absorbing agent means a compound having absorption in a wavelength region of an infrared region (preferably, a wavelength of 650 to 1300 nm). As the infrared absorber, a compound having a maximum absorption wavelength in a wavelength range of 675 to 900 nm is preferable.

Examples of colorants having such spectral characteristics include, for example, pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterylene Compounds, dithiol metal complex-based compounds, croconium compounds, and the like.

As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP-A-2010-11110 may be used. Will be incorporated into the book. The cyanine compound can be referred to, for example, “Functional Dye, Shin Ogawara / Sen Matsuoka / Teijiro Kitao / Tsunaki Hirashima, Kodansha Scientific”, the contents of which are incorporated herein.

　上記分光特性を有する着色剤として、特開平０７－１６４７２９号公報の段落０００４～００１６に開示の化合物及び／又は特開２００２－１４６２５４号公報の段落００２７～００６２に開示の化合物、特開２０１１－１６４５８３号公報の段落００３４～００６７に開示のＣｕ及び／又はＰを含有する酸化物の結晶子からなり数平均凝集粒子径が５～２００ｎｍである近赤外線吸収粒子を使用することもできる。
Examples of the colorant having the above-mentioned spectral characteristics include compounds disclosed in paragraphs 0004 to 0016 of JP-A-07-164729 and / or compounds disclosed in paragraphs 0027 to 0062 of JP-A-2002-146254. Near-infrared absorbing particles comprising a crystallite of an oxide containing Cu and / or P disclosed in Paragraphs 0034 to 0067 of JP-A No. 003-0067 and having a number average agglomerated particle size of 5 to 200 nm can also be used.

　波長６７５～９００ｎｍの波長領域に極大吸収波長を有する化合物としては、シアニン化合物、ピロロピロール化合物、スクアリリウム化合物、フタロシアニン化合物、及び、ナフタロシアニン化合物からなる群から選択される少なくとも１種が好ましい。

　また、赤外線吸収剤は、２５℃の水に１質量％以上溶解する化合物が好ましく、２５℃の水に１０質量％以上溶解する化合物がより好ましい。このような化合物を用いることで、耐溶剤性が良化する。

　ピロロピロール化合物は、特開２０１０－２２２５５７号公報の段落００４９～００６２を参酌でき、この内容は本明細書に組み込まれる。シアニン化合物及びスクアリリウム化合物は、国際公開２０１４／０８８０６３号公報の段落００２２～００６３、国際公開２０１４／０３０６２８号公報の段落００５３～０１１８、特開２０１４－５９５５０号公報の段落００２８～００７４、国際公開２０１２／１６９４４７号公報の段落００１３～００９１、特開２０１５－１７６０４６号公報の段落００１９～００３３、特開２０１４－６３１４４号公報の段落００５３～００９９、特開２０１４－５２４３１号公報の段落００８５～０１５０、特開２０１４－４４３０１号公報の段落００７６～０１２４、特開２０１２－８５３２号公報の段落００４５～００７８、特開２０１５－１７２１０２号公報の段落００２７～００６７、特開２０１５－１７２００４号公報の段落００２９～００６７、特開２０１５－４０８９５号公報の段落００２９～００８５、特開２０１４－１２６６４２号公報の段落００２２～００３６、特開２０１４－１４８５６７号公報の段落００１１～００１７、特開２０１５－１５７８９３号公報の段落００１０～００２５、特開２０１４－０９５００７号公報の段落００１３～００２６、特開２０１４－８０４８７号公報の段落００１３～００４７、及び、特開２０１３－２２７４０３号公報の段落０００７～００２８等を参酌でき、この内容は本明細書に組み込まれる。
As the compound having a maximum absorption wavelength in a wavelength range of 675 to 900 nm, at least one selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound is preferable.

Further, the infrared absorbent is preferably a compound that dissolves in water at 25 ° C in an amount of 1% by mass or more, and more preferably a compound that dissolves in water at 25 ° C in an amount of 10% by mass or more. By using such a compound, the solvent resistance is improved.

For the pyrrolopyrrole compound, paragraphs 0049 to 0062 of JP-A-2010-222557 can be referred to, and the contents thereof are incorporated herein. The cyanine compound and the squarylium compound are described in paragraphs 0022 to 0063 of WO 2014/088063, paragraphs 0053 to 0118 of WO 2014/030628, paragraphs 0028 to 0074 of JP-A-2014-59550, and WO 2012/2012. Paragraphs 0013 to 0091 of JP-A-169947, paragraphs 0019 to 0033 of JP-A-2015-176046, paragraphs 0053 to 0099 of JP-A-2014-63144, paragraphs 0085 to 0150 of JP-A-2014-52431, Paragraphs 0076 to 0124 of JP-A-2014-44301, paragraphs 0045 to 0078 of JP-A-2012-8532, paragraphs 0027 to 0067 of JP-A-2015-172102, and paragraph 002 of JP-A-2015-172004. To 0067, paragraphs 0029 to 0085 of JP-A-2015-40895, paragraphs 0022 to 0036 of JP-A-2014-126642, paragraphs 0011 to 0017 of JP-A-2014-148567, and JP-A-2015-157893. Paragraphs 0010 to 0025, paragraphs 0013 to 0026 of JP-A-2014-095007, paragraphs 0013 to 0047 of JP-A-2014-80487, and paragraphs 0007 to 0028 of JP-A-2013-227403 can be referred to. This content is incorporated herein.

＜樹脂＞

　遮光性組成物は樹脂を含有する。樹脂としては例えば、分散樹脂及びアルカリ可溶性樹脂等が挙げられる。

　組成物中における樹脂の含有量としては特に制限されないが、組成物の全固形分に対して、３～６０質量％が好ましく、１０～４０質量％がより好ましく、１５～３５質量％が更に好ましい。樹脂は、１種を単独で用いても、２種以上を併用してもよい。例えば、樹脂として後述の分散樹脂と後述のアルカリ可溶性樹脂とを併用してもよい。２種以上の樹脂を併用する場合には、合計含有量が上記範囲内であることが好ましい。

　なお、樹脂とは、組成物中に溶解している成分であって、分子量が２０００超である成分を意味する。樹脂の分子量が多分散である場合、樹脂の重量平均分子量が２０００超である。
<Resin>

The light-shielding composition contains a resin. Examples of the resin include a dispersion resin and an alkali-soluble resin.

The content of the resin in the composition is not particularly limited, but is preferably 3 to 60% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 35% by mass based on the total solid content of the composition. . One type of resin may be used alone, or two or more types may be used in combination. For example, a dispersion resin described below and an alkali-soluble resin described later may be used in combination as the resin. When two or more resins are used in combination, the total content is preferably within the above range.

The resin is a component dissolved in the composition and means a component having a molecular weight of more than 2000. When the molecular weight of the resin is polydisperse, the weight average molecular weight of the resin is more than 2,000.

（分散樹脂）

　遮光性組成物は、分散樹脂を含有することが好ましい。なお、本明細書において、分散樹脂とは、後述するアルカリ可溶性樹脂とは異なる化合物を意味する。

　組成物中における分散樹脂の含有量としては特に制限されないが、組成物の全固形分に対して２～４０質量％が好ましく、５～３０質量％がより好ましく、１０～２０質量％が更に好ましい。

　分散樹脂は、１種を単独で用いても、２種以上を併用してもよい。２種以上の分散樹脂を併用する場合には、合計含有量が上記範囲内であることが好ましい。

　また、組成物における、黒色色材の含有量に対する、分散樹脂（好ましくはグラフト型高分子）の含有量の質量比（分散樹脂の含有量／黒色色材の含有量）は、０．０５～１．００が好ましく、０．０５～０．３５がより好ましく、０．２０～０．３５が更に好ましい。
(Dispersed resin)

The light-shielding composition preferably contains a dispersion resin. In addition, in this specification, a dispersion resin means a compound different from an alkali-soluble resin described below.

The content of the dispersing resin in the composition is not particularly limited, but is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 20% by mass based on the total solid content of the composition. .

As the dispersion resin, one type may be used alone, or two or more types may be used in combination. When two or more dispersing resins are used in combination, the total content is preferably within the above range.

In the composition, the mass ratio of the content of the dispersing resin (preferably the graft polymer) to the content of the black coloring material (content of the dispersing resin / content of the black coloring material) is from 0.05 to 0.05. 1.00 is preferred, 0.05 to 0.35 is more preferred, and 0.20 to 0.35 is even more preferred.

　分散樹脂としては、例えば、公知の分散剤を適宜選択して使用できる。中でも、高分子化合物が好ましい。

　分散樹脂としては、高分子分散剤（例えば、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ（メタ）アクリレート、（メタ）アクリル系共重合体、ナフタレンスルホン酸ホルマリン縮合物）、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンアルキルアミン、及び、顔料誘導体等を挙げられる。

　高分子化合物は、その構造から更に直鎖状高分子、末端変性型高分子、グラフト型高分子、及び、ブロック型高分子に分類できる。
As the dispersing resin, for example, a known dispersing agent can be appropriately selected and used. Among them, a polymer compound is preferable.

Examples of the dispersing resin include polymer dispersants (eg, polyamidoamine and its salts, polycarboxylic acids and its salts, high-molecular unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic-based resins). Copolymer, naphthalenesulfonic acid formalin condensate), polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, and pigment derivatives.

The polymer compound can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer based on its structure.

・高分子化合物

　高分子化合物は、黒色顔料及び所望により併用するその他の顔料（以下黒色顔料及びその他の顔料を総称して、単に「顔料」とも記載する）等の被分散体の表面に吸着し、被分散体の再凝集を防止するように作用する。そのため、顔料表面へのアンカー部位を含有する、末端変性型高分子、グラフト型（高分子鎖を含有する）高分子、又は、ブロック型高分子が好ましい。
・ Polymer compound

The high molecular compound is adsorbed on the surface of a dispersion target such as a black pigment and other pigments used in combination as required (hereinafter, the black pigment and the other pigments are collectively referred to simply as “pigment”) and the like, Acts to prevent re-aggregation of Therefore, a terminal-modified polymer, a graft-type (containing a polymer chain) polymer, or a block-type polymer containing an anchor site to the pigment surface is preferable.

　上記高分子化合物は硬化性基を有してもよい。

　硬化性基としては、例えば、エチレン性不飽和結合を含有する基（以下、「エチレン性不飽和基」とも記載する）（例えば、（メタ）アクリロイル基、ビニル基、及び、スチリル基等）、及び、環状エーテル基（例えば、エポキシ基、オキセタニル基等）等が挙げられるが、これらに制限されない。

　中でも、ラジカル反応で重合制御が可能な点で、硬化性基としては、エチレン性不飽和基が好ましく、（メタ）アクリロイル基がより好ましい。
The polymer compound may have a curable group.

Examples of the curable group include a group containing an ethylenically unsaturated bond (hereinafter, also referred to as an “ethylenically unsaturated group”) (eg, a (meth) acryloyl group, a vinyl group, and a styryl group), And a cyclic ether group (for example, an epoxy group, an oxetanyl group, and the like) and the like, but are not limited thereto.

Among them, the ethylenically unsaturated group is preferable as the curable group, and a (meth) acryloyl group is more preferable, since polymerization can be controlled by a radical reaction.

　遮光性組成物は、遮光膜の耐光性、耐湿性及び耐熱性がより優れる点から、硬化性基（より好ましくはエチレン性不飽和基）を有する分散樹脂を含有することが好ましい。

　硬化性基を含有する分散樹脂としては、例えば、硬化性基（より好ましくは（メタ）アクリロイル基等のエチレン性不飽和基）を有する構造単位を有する高分子化合物が挙げられる。なお、本明細書において、「構造単位」とは「繰り返し単位」と同義である。

　例えば、下記のグラフト鎖を含有する構造単位のグラフト鎖の末端に硬化性基が導入されていてもよい。より具体的には、高分子化合物を構成する構造単位のうち、（メタ）アクリル酸に由来する単位及び／又は他の付加重合性ビニルモノマーに由来する単位の１種以上の、一部又は全部に、硬化性基（好ましくは（メタ）アクリロイル基等のエチレン性不飽和基）が導入されていてもよい。

　高分子化合物において、硬化性基を有する構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、２～９０質量％が好ましく、５～３０質量％がより好ましい。
The light-shielding composition preferably contains a dispersion resin having a curable group (more preferably, an ethylenically unsaturated group) from the viewpoint that the light-shielding film has more excellent light resistance, moisture resistance, and heat resistance.

Examples of the dispersion resin containing a curable group include a polymer compound having a structural unit having a curable group (more preferably, an ethylenically unsaturated group such as a (meth) acryloyl group). In this specification, “structural unit” is synonymous with “repeating unit”.

For example, a curable group may be introduced at a terminal of a graft chain of a structural unit containing the following graft chain. More specifically, among the structural units constituting the polymer compound, part or all of one or more of units derived from (meth) acrylic acid and / or units derived from other addition-polymerizable vinyl monomers A curable group (preferably, an ethylenically unsaturated group such as a (meth) acryloyl group) may be introduced.

In the polymer compound, the content of the structural unit having a curable group is preferably from 2 to 90% by mass, more preferably from 5 to 30% by mass, based on the total mass of the polymer compound in terms of mass.

　硬化性基を含有する樹脂は、ポリエステル構造、及び、ポリエーテル構造からなる群から選択される少なくとも１種を含有することが好ましい。この場合、主鎖にポリエステル構造、及び／又は、ポリエーテル構造を含有していてもよいし、後述するように、上記樹脂がグラフト鎖を含有する構造単位を含有する場合には、上記高分子鎖がポリエステル構造、及び／又は、ポリエーテル構造を含有していてもよい。

　上記樹脂としては、上記高分子鎖がポリエステル構造を含有することがより好ましい。
The resin containing a curable group preferably contains at least one selected from the group consisting of a polyester structure and a polyether structure. In this case, the main chain may contain a polyester structure and / or a polyether structure. As described later, when the resin contains a structural unit containing a graft chain, the polymer may be used. The chains may have a polyester structure and / or a polyether structure.

As the resin, it is more preferable that the polymer chain has a polyester structure.

　高分子化合物は、グラフト鎖を含有する構造単位を含有することが好ましい。なお、本明細書において、「構造単位」とは「繰り返し単位」と同義である。

　このようなグラフト鎖を含有する構造単位を含有する高分子化合物は、グラフト鎖によって溶剤との親和性を有するために、顔料等の分散性、及び、経時後の分散安定性（経時安定性）に優れる。また、グラフト鎖の存在により、グラフト鎖を含有する構造単位を含有する高分子化合物は重合性化合物又はその他の併用可能な樹脂等との親和性を有する。

結果として、アルカリ現像で残渣を生じにくくなる。

　グラフト鎖が長くなると立体反発効果が高くなり顔料等の分散性は向上する。一方、グラフト鎖が長すぎると顔料等への吸着力が低下して、顔料等の分散性は低下する傾向となる。このため、グラフト鎖は、水素原子を除いた原子数が４０～１００００であることが好ましく、水素原子を除いた原子数が５０～２０００であることがより好ましく、水素原子を除いた原子数が６０～５００であることが更に好ましい。

　ここで、グラフト鎖とは、共重合体の主鎖の根元（主鎖から枝分かれしている基において主鎖に結合する原子）から、主鎖から枝分かれしている基の末端までを示す。
The polymer compound preferably contains a structural unit containing a graft chain. In this specification, “structural unit” is synonymous with “repeating unit”.

Since the polymer compound containing a structural unit containing such a graft chain has an affinity for a solvent due to the graft chain, the dispersibility of a pigment or the like and the dispersion stability after aging (stability with time) Excellent. In addition, due to the presence of the graft chain, the polymer compound containing the structural unit containing the graft chain has an affinity for a polymerizable compound or another resin that can be used in combination.

As a result, residues are less likely to be generated in alkali development.

As the graft chain becomes longer, the steric repulsion effect increases and the dispersibility of pigments and the like improves. On the other hand, if the graft chain is too long, the adsorptive power to the pigment or the like decreases, and the dispersibility of the pigment or the like tends to decrease. Therefore, the number of atoms in the graft chain excluding hydrogen atoms is preferably from 40 to 10,000, more preferably from 50 to 2000 except for hydrogen atoms, and the number of atoms excluding hydrogen atoms is more preferably 50 to 2000. More preferably, it is 60 to 500.

Here, the term “graft chain” refers to the range from the base of the main chain of the copolymer (the atom bonded to the main chain in the group branched from the main chain) to the terminal of the group branched from the main chain.

　グラフト鎖は、ポリマー構造を含有することが好ましく、このようなポリマー構造としては、例えば、ポリ（メタ）アクリレート構造（例えば、ポリ（メタ）アクリル構造）、ポリエステル構造、ポリウレタン構造、ポリウレア構造、ポリアミド構造、及び、ポリエーテル構造等を挙げられる。

　グラフト鎖と溶剤との相互作用性を向上させ、それにより顔料等の分散性を高めるために、グラフト鎖は、ポリエステル構造、ポリエーテル構造、及び、ポリ（メタ）アクリレート構造からなる群から選ばれた少なくとも１種を含有するグラフト鎖であることが好ましく、ポリエステル構造及びポリエーテル構造の少なくともいずれかを含有するグラフト鎖であることがより好ましい。
The graft chain preferably contains a polymer structure. Examples of such a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acryl structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide. And a polyether structure.

The graft chain is selected from the group consisting of a polyester structure, a polyether structure, and a poly (meth) acrylate structure in order to improve the interaction between the graft chain and the solvent and thereby enhance the dispersibility of the pigment or the like. Further, it is preferable that the graft chain contains at least one kind, and it is more preferable that the graft chain contains at least one of a polyester structure and a polyether structure.

　このようなグラフト鎖を含有するマクロモノマー（ポリマー構造を有し、共重合体の主鎖に結合してグラフト鎖を構成するモノマー）としては、特に制限されないが、エチレン性不飽和基を含有するマクロモノマーを好適に使用できる。

　また、上記高分子化合物は、遮光膜の耐光性、耐湿性及び耐熱性がより優れる点から、硬化性基を含有することが好ましく、（メタ）アクリロイル基等のエチレン性不飽和基を含有することがより好ましい。
The macromonomer containing such a graft chain (a monomer having a polymer structure and binding to the main chain of the copolymer to form a graft chain) is not particularly limited, but contains an ethylenically unsaturated group. Macromonomers can be suitably used.

In addition, the polymer compound preferably contains a curable group, and contains an ethylenically unsaturated group such as a (meth) acryloyl group, from the viewpoint of more excellent light resistance, moisture resistance, and heat resistance of the light-shielding film. Is more preferable.

　高分子化合物が含有するグラフト鎖を含有する構造単位に対応し、高分子化合物の合成に好適に用いられる市販のマクロモノマーとしては、ＡＡ－６、ＡＡ－１０、ＡＢ－６、ＡＳ－６、ＡＮ－６、ＡＷ－６、ＡＡ－７１４、ＡＹ－７０７、ＡＹ－７１４、ＡＫ－５、ＡＫ－３０、及び、ＡＫ－３２（いずれも商品名、東亞合成社製）、並びに、ブレンマーＰＰ－１００、ブレンマーＰＰ－５００、ブレンマーＰＰ－８００、ブレンマーＰＰ－１０００、ブレンマー５５－ＰＥＴ－８００、ブレンマーＰＭＥ－４０００、ブレンマーＰＳＥ－４００、ブレンマーＰＳＥ－１３００、及び、ブレンマー４３ＰＡＰＥ－６００Ｂ（いずれも商品名、日油社製）が用いられる。この中でも、ＡＡ－６、ＡＡ－１０、ＡＢ－６、ＡＳ－６、ＡＮ－６、又は、ブレンマーＰＭＥ－４０００が好ましい。
Commercially available macromonomers corresponding to the structural unit containing the graft chain contained in the polymer compound and preferably used for the synthesis of the polymer compound include AA-6, AA-10, AB-6, AS-6, AN-6, AW-6, AA-714, AY-707, AY-714, AK-5, AK-30, and AK-32 (all trade names, manufactured by Toagosei Co., Ltd.), and Blemmer PP- 100, Blemmer PP-500, Blemmer PP-800, Blemmer PP-1000, Blemmer 55-PET-800, Blemmer PME-4000, Blemmer PSE-400, Blemmer PSE-1300, and Blemmer 43PAPE-600B (all trade names) , Manufactured by NOF CORPORATION). Among them, AA-6, AA-10, AB-6, AS-6, AN-6 or Blemmer PME-4000 are preferred.

　上記分散樹脂は、ポリアクリル酸メチル、ポリメタクリル酸メチル、及び、環状又は鎖状のポリエステルからなる群より選択される少なくとも１種の構造を含有することが好ましく、ポリアクリル酸メチル、ポリメタクリル酸メチル、及び、鎖状のポリエステルからなる群より選択される少なくとも１種の構造を含有することがより好ましく、ポリアクリル酸メチル構造、ポリメタクリル酸メチル構造、ポリカプロラクトン構造、及び、ポリバレロラクトン構造からなる群より選択される少なくとも１種の構造を含有することが更に好ましい。分散樹脂は、一の樹脂中に上記構造を単独で含有してもよいし、一の樹脂中にこれらの構造を複数含有してもよい。

　ここで、ポリカプロラクトン構造とは、ε－カプロラクトンを開環した構造を繰り返し単位として含有する構造をいう。ポリバレロラクトン構造とは、δ－バレロラクトンを開環した構造を繰り返し単位として含有する構造をいう。

　ポリカプロラクトン構造を含有する分散樹脂の具体例としては、下記式（１）及び下記式（２）におけるｊ及びｋが５である樹脂が挙げられる。また、ポリバレロラクトン構造を含有する分散樹脂の具体例としては、下記式（１）及び下記式（２）におけるｊ及びｋが４である樹脂が挙げられる。

　ポリアクリル酸メチル構造を含有する分散樹脂の具体例としては、下記式（４）におけるＸ５が水素原子であり、Ｒ４がメチル基である樹脂が挙げられる。また、ポリメタクリル酸メチル構造を含有する分散樹脂の具体例としては、下記式（４）におけるＸ５がメチル基であり、Ｒ４がメチル基である樹脂が挙げられる。
The dispersion resin preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and a cyclic or linear polyester, and includes polymethyl acrylate and polymethacrylic acid. Methyl and more preferably contain at least one structure selected from the group consisting of linear polyesters, polymethyl acrylate structure, polymethyl methacrylate structure, polycaprolactone structure, and polyvalerolactone structure More preferably, it contains at least one structure selected from the group consisting of The dispersed resin may contain the above structure alone in one resin, or may contain a plurality of these structures in one resin.

Here, the polycaprolactone structure refers to a structure containing a ring-opened structure of ε-caprolactone as a repeating unit. The polyvalerolactone structure refers to a structure containing a ring-opened structure of δ-valerolactone as a repeating unit.

Specific examples of the dispersed resin having a polycaprolactone structure include resins in which j and k in the following formulas (1) and (2) are 5: Further, specific examples of the dispersion resin having a polyvalerolactone structure include resins in which j and k in the following formulas (1) and (2) are 4.

Specific examples of the dispersed resin having a polymethyl acrylate structure include a resin in which X 5 in the following formula (4) is a hydrogen atom and R 4 is a methyl group. Further, specific examples of the dispersion resin having a polymethyl methacrylate structure include a resin in which X 5 in the following formula (4) is a methyl group, and R 4 is a methyl group.

・グラフト鎖を含有する構造単位

　高分子化合物は、グラフト鎖を含有する構造単位として、下記式（１）～式（４）のいずれかで表される構造単位を含有することが好ましく、下記式（１Ａ）、下記式（２Ａ）、下記式（３Ａ）、下記式（３Ｂ）、及び、下記（４）のいずれかで表される構造単位を含有することがより好ましい。
.Structural units containing graft chains

The polymer compound preferably contains a structural unit represented by any one of the following formulas (1) to (4) as a structural unit containing a graft chain, and includes the following formulas (1A) and (2A) ), The following formula (3A), the following formula (3B), and more preferably a structural unit represented by any of the following (4).

Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005

　式（１）～（４）において、Ｗ１、Ｗ２、Ｗ３、及び、Ｗ４は、それぞれ独立に、酸素原子又はＮＨを表す。Ｗ１、Ｗ２、Ｗ３、及び、Ｗ４は酸素原子であることが好ましい。

　式（１）～（４）において、Ｘ１、Ｘ２、Ｘ３、Ｘ４、及び、Ｘ５は、それぞれ独立に、水素原子又は１価の有機基を表す。Ｘ１、Ｘ２、Ｘ３、Ｘ４、及び、Ｘ５は、合成上の制約の点からは、それぞれ独立に、水素原子又は炭素数（炭素原子数）１～１２のアルキル基が好ましく、それぞれ独立に、水素原子又はメチル基がより好ましく、メチル基が更に好ましい。
In the formulas (1) to (4), W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH. W 1 , W 2 , W 3 and W 4 are preferably oxygen atoms.

In the formulas (1) to (4), X 1 , X 2 , X 3 , X 4 and X 5 each independently represent a hydrogen atom or a monovalent organic group. X 1 , X 2 , X 3 , X 4 and X 5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (number of carbon atoms) from the viewpoint of synthesis restrictions. Independently, a hydrogen atom or a methyl group is more preferred, and a methyl group is even more preferred.

　式（１）～（４）において、Ｙ１、Ｙ２、Ｙ３、及び、Ｙ４は、それぞれ独立に、２価の連結基を表し、連結基は特に構造上制約されない。Ｙ１、Ｙ２、Ｙ３、及び、Ｙ４で表される２価の連結基として、具体的には、下記の（Ｙ－１）～（Ｙ－２１）の連結基等が挙げられる。下記に示した構造において、Ａ及びＢはそれぞれ、式（１）～（４）における左末端基、右末端基との結合部位を意味する。下記に示した構造のうち、合成の簡便性から、（Ｙ－２）又は（Ｙ－１３）がより好ましい。
In Formulas (1) to (4), Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure. Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following linking groups (Y-1) to (Y-21). In the structures shown below, A and B mean the binding sites to the left terminal group and right terminal group in formulas (1) to (4), respectively. Among the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of convenience of synthesis.

Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006

　式（１）～（４）において、Ｚ１、Ｚ２、Ｚ３、及び、Ｚ４は、それぞれ独立に１価の有機基を表す。有機基の構造は、特に制限されないが、具体的には、アルキル基、水酸基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオエーテル基、アリールチオエーテル基、ヘテロアリールチオエーテル基、及び、アミノ基等が挙げられる。これらの中でも、Ｚ１、Ｚ２、Ｚ３、及び、Ｚ４で表される有機基としては、特に分散性向上の点から、立体反発効果を含有する基が好ましく、それぞれ独立に炭素数５～２４のアルキル基又はアルコキシ基がより好ましく、その中でも、特にそれぞれ独立に炭素数５～２４の分岐アルキル基、炭素数５～２４の環状アルキル基、又は、炭素数５～２４のアルコキシ基が更に好ましい。なお、アルコキシ基中に含まれるアルキル基は、直鎖状、分岐鎖状、及び、環状のいずれでもよい。
In Formulas (1) to (4), Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a monovalent organic group. Although the structure of the organic group is not particularly limited, specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group And the like. Among these, as the organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 , a group having a steric repulsion effect is particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 carbon atoms. An alkyl group or an alkoxy group having up to 24 carbon atoms is more preferable, and among them, a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable. More preferred. The alkyl group contained in the alkoxy group may be linear, branched, or cyclic.

　式（１）～（４）において、ｎ、ｍ、ｐ、及び、ｑは、それぞれ独立に、１～５００の整数である。

　また、式（１）及び（２）において、ｊ及びｋは、それぞれ独立に、２～８の整数を表す。式（１）及び（２）におけるｊ及びｋは、組成物の経時安定性及び現像性の点から、４～６の整数が好ましく、５がより好ましい。

　また、式（１）及び（２）において、ｎ、及び、ｍは、１０以上の整数が好ましく、２０以上の整数がより好ましい。また、分散樹脂が、ポリカプロラクトン構造、及び、ポリバレロラクトン構造を含有する場合、ポリカプロラクトン構造の繰り返し数と、ポリバレロラクトンの繰返し数の和としては、１０以上の整数が好ましく、２０以上の整数がより好ましい。
In the formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500.

In the formulas (1) and (2), j and k each independently represent an integer of 2 to 8. In the formulas (1) and (2), j and k are preferably integers of 4 to 6, and more preferably 5 from the viewpoint of the stability over time and the developability of the composition.

In the formulas (1) and (2), n and m are preferably integers of 10 or more, and more preferably integers of 20 or more. Further, when the dispersion resin has a polycaprolactone structure and a polyvalerolactone structure, the number of repetitions of the polycaprolactone structure and the sum of the number of repetitions of the polyvalerolactone are preferably integers of 10 or more, and 20 or more. Integers are more preferred.

　式（３）中、Ｒ３は分岐鎖状又は直鎖状のアルキレン基を表し、炭素数１～１０のアルキレン基が好ましく、炭素数２又は３のアルキレン基がより好ましい。ｐが２～５００のとき、複数存在するＲ３は互いに同じであっても異なっていてもよい。

　式（４）中、Ｒ４は水素原子又は１価の有機基を表し、この１価の有機基の構造は特に制限されない。Ｒ４としては、水素原子、アルキル基、アリール基、又は、ヘテロアリール基が好ましく、水素原子又はアルキル基がより好ましい。Ｒ４がアルキル基である場合、アルキル基としては、炭素数１～２０の直鎖状アルキル基、炭素数３～２０の分岐鎖状アルキル基、又は、炭素数５～２０の環状アルキル基が好ましく、炭素数１～２０の直鎖状アルキル基がより好ましく、炭素数１～６の直鎖状アルキル基が更に好ましい。式（４）において、ｑが２～５００のとき、グラフト共重合体中に複数存在するＸ５及びＲ４は互いに同じであっても異なっていてもよい。
In the formula (3), R 3 represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different.

In the formula (4), R 4 represents a hydrogen atom or a monovalent organic group, and the structure of the monovalent organic group is not particularly limited. As R 4 , a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group is preferable, and a hydrogen atom or an alkyl group is more preferable. When R 4 is an alkyl group, examples of the alkyl group include a linear alkyl group having 1 to 20 carbon atoms, a branched chain alkyl group having 3 to 20 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms. Preferably, a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is further preferable. In the formula (4), when q is 2 to 500, a plurality of X 5 and R 4 present in the graft copolymer may be the same or different.

　また、高分子化合物は、２種以上の構造が異なる、グラフト鎖を含有する構造単位を含有できる。即ち、高分子化合物の分子中に、互いに構造の異なる式（１）～（４）で示される構造単位を含んでいてもよく、また、式（１）～（４）においてｎ、ｍ、ｐ、及び、ｑがそれぞれ２以上の整数を表す場合、式（１）及び（２）においては、側鎖中にｊ及びｋが互いに異なる構造を含んでいてもよく、式（３）及び（４）においては、分子内に複数存在するＲ３、Ｒ４、及び、Ｘ５は互いに同じであっても異なっていてもよい。
Further, the polymer compound may contain a graft chain-containing structural unit having two or more different structures. That is, in the molecule of the polymer compound, structural units represented by formulas (1) to (4) having different structures may be included, and in the formulas (1) to (4), n, m, p , And q each represent an integer of 2 or more, in formulas (1) and (2), j and k may include different structures in the side chain, and formulas (3) and (4) )), A plurality of R 3 , R 4 and X 5 present in the molecule may be the same or different.

　式（１）で表される構造単位としては、組成物の経時安定性及び現像性の点から、下記式（１Ａ）で表される構造単位であることがより好ましい。

　また、式（２）で表される構造単位としては、組成物の経時安定性及び現像性の点から、下記式（２Ａ）で表される構造単位であることがより好ましい。
The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of stability over time and developability of the composition.

In addition, the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of stability over time and developability of the composition.

Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007

　式（１Ａ）中、Ｘ１、Ｙ１、Ｚ１、及び、ｎは、式（１）におけるＸ１、Ｙ１、Ｚ１、及び、ｎと同義であり、好ましい範囲も同様である。式（２Ａ）中、Ｘ２、Ｙ２、Ｚ２、及び、ｍは、式（２）におけるＸ２、Ｙ２、Ｚ２、及び、ｍと同義であり、好ましい範囲も同様である。
Wherein (1A), X 1, Y 1, Z 1 and, n is, X 1, Y 1, Z 1 in Formula (1), and has the same meaning as n, preferred ranges are also the same. Wherein (2A), X 2, Y 2, Z 2 and, m is, X 2, Y 2, Z 2 in Formula (2), and has the same meaning as m, the preferred range is also the same.

　また、式（３）で表される構造単位としては、組成物の経時安定性及び現像性の点から、下記式（３Ａ）又は式（３Ｂ）で表される構造単位であることがより好ましい。
In addition, the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or (3B) from the viewpoint of stability over time and developability of the composition. .

Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008

　式（３Ａ）又は（３Ｂ）中、Ｘ３、Ｙ３、Ｚ３、及び、ｐは、式（３）におけるＸ３、Ｙ３、Ｚ３、及び、ｐと同義であり、好ましい範囲も同様である。
Wherein (3A) or (3B), X 3, Y 3, Z 3 and, p is, X 3, Y 3, Z 3 in Formula (3), and has the same meaning as p, preferred ranges are also the same It is.

　高分子化合物は、グラフト鎖を含有する構造単位として、式（１Ａ）で表される構造単位を含有することがより好ましい。
More preferably, the polymer compound contains a structural unit represented by the formula (1A) as a structural unit containing a graft chain.

　高分子化合物において、グラフト鎖を含有する構造単位（例えば、上記式（１）～（４）で表される構造単位）の含有量は、質量換算で、高分子化合物の総質量に対して、２～９０質量％が好ましく、５～３０質量％がより好ましい。グラフト鎖を含有する構造単位がこの範囲内で含まれると、顔料の分散性が高く、黒色層を形成する際の現像性が良好である。
In the polymer compound, the content of the structural unit containing the graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is calculated in terms of mass with respect to the total mass of the polymer compound. It is preferably from 2 to 90% by mass, more preferably from 5 to 30% by mass. When the structural unit containing a graft chain is contained within this range, the dispersibility of the pigment is high and the developability when forming a black layer is good.

・疎水性構造単位

　また、高分子化合物は、グラフト鎖を含有する構造単位とは異なる（すなわち、グラフト鎖を含有する構造単位には相当しない）疎水性構造単位を含有することが好ましい。ただし、本明細書において、疎水性構造単位は、酸基（例えば、カルボン酸基、スルホン酸基、リン酸基、フェノール性水酸基等）を有さない構造単位である。
・ Hydrophobic structural unit

Further, the polymer compound preferably contains a hydrophobic structural unit different from the structural unit containing the graft chain (that is, does not correspond to the structural unit containing the graft chain). However, in the present specification, the hydrophobic structural unit is a structural unit having no acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, and the like).

　疎水性構造単位は、ＣｌｏｇＰ値が１．２以上の化合物（モノマー）に由来する（対応する）構造単位であることが好ましく、ＣｌｏｇＰ値が１．２～８の化合物に由来する構造単位であることがより好ましい。これにより、本発明の効果をより確実に発現できる。
The hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, and is a structural unit derived from a compound having a ClogP value of 1.2 to 8. Is more preferable. Thereby, the effect of the present invention can be more reliably achieved.

　ＣｌｏｇＰ値は、Ｄａｙｌｉｇｈｔ　Ｃｈｅｍｉｃａｌ　Ｉｎｆｏｒｍａｔｉｏｎ　Ｓｙｓｔｅｍ，　Ｉｎｃ．から入手できるプログラム「ＣＬＯＧＰ」で計算された値である。このプログラムは、Ｈａｎｓｃｈ，　Ｌｅｏのフラグメントアプローチ（下記文献参照）により算出される「計算ｌｏｇＰ」の値を提供する。フラグメントアプローチは化合物の化学構造に基づいており、化学構造を部分構造（フラグメント）に分割し、そのフラグメントに対して割り当てられたｌｏｇＰ寄与分を合計して化合物のｌｏｇＰ値を推算している。その詳細は以下の文献に記載されている。本明細書では、プログラムＣＬＯＧＰ　ｖ４．８２により計算したＣｌｏｇＰ値を用いる。

　Ａ．　Ｊ．　Ｌｅｏ，　Ｃｏｍｐｒｅｈｅｎｓｉｖｅ　Ｍｅｄｉｃｉｎａｌ　Ｃｈｅｍｉｓｔｒｙ，　Ｖｏｌ．４，　Ｃ．　Ｈａｎｓｃｈ，　Ｐ．　Ｇ．　Ｓａｍｍｎｅｎｓ，　Ｊ．　Ｂ．　Ｔａｙｌｏｒ　ａｎｄ　Ｃ．　Ａ．　Ｒａｍｓｄｅｎ，　Ｅｄｓ．，　ｐ．２９５，　Ｐｅｒｇａｍｏｎ　Ｐｒｅｓｓ，　１９９０　Ｃ．　Ｈａｎｓｃｈ　＆　Ａ．　Ｊ．　Ｌｅｏ．　ＳＵｂｓｔｉｔｕｅｎｔ　Ｃｏｎｓｔａｎｔｓ　Ｆｏｒ　Ｃｏｒｒｅｌａｔｉｏｎ　Ａｎａｌｙｓｉｓ　ｉｎ　Ｃｈｅｍｉｓｔｒｙ　ａｎｄ　Ｂｉｏｌｏｇｙ．　Ｊｏｈｎ　Ｗｉｌｅｙ　＆　Ｓｏｎｓ．　Ａ．Ｊ．　Ｌｅｏ．　Ｃａｌｃｕｌａｔｉｎｇ　ｌｏｇＰｏｃｔ　ｆｒｏｍ　ｓｔｒｕｃｔｕｒｅ．　Ｃｈｅｍ．　Ｒｅｖ．，　９３，　１２８１－１３０６，　１９９３．
ClogP values are measured using Daylight Chemical Information System, Inc. This is a value calculated by the program “CLOGP” available from. This program provides the value of "calculated log P" calculated by the Hansch, Leo fragment approach (see literature below). The fragment approach is based on the chemical structure of a compound, dividing the chemical structure into substructures (fragments) and summing the logP contributions assigned to the fragments to estimate the logP value of the compound. The details are described in the following documents. In this specification, a ClogP value calculated by the program CLOGP v4.82 is used.

A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P .; G. FIG. Sammmens, J .; B. Taylor and C.I. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. Leo. Substitute Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. Leo. Calculating logPect from structure. Chem. Rev .. , 93, 1281-1306, 1993.

　ｌｏｇＰは、分配係数Ｐ（Ｐａｒｔｉｔｉｏｎ　Ｃｏｅｆｆｉｃｉｅｎｔ）の常用対数を意味し、ある有機化合物が油（一般的には１－オクタノール）と水の２相系の平衡でどのように分配されるかを定量的な数値として表す物性値であり、以下の式で示される。

　　ｌｏｇＰ＝ｌｏｇ（Ｃｏｉｌ／Ｃｗａｔｅｒ）

　式中、Ｃｏｉｌは油相中の化合物のモル濃度を、Ｃｗａｔｅｒは水相中の化合物のモル濃度を表す。

　ｌｏｇＰの値が０をはさんでプラスに大きくなると油溶性が増し、マイナスで絶対値が大きくなると水溶性が増し、有機化合物の水溶性と負の相関があり、有機化合物の親疎水性を見積るパラメータとして広く利用されている。
logP means a common logarithm of a partition coefficient P (Partition Coefficient), and quantitatively describes how an organic compound is distributed in an equilibrium of a two-phase system of an oil (generally, 1-octanol) and water. It is a physical property value expressed as a simple numerical value, and is represented by the following equation.

logP = log (Coil / Cwater)

In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase.

When the value of logP is increased to a positive value across 0, the oil solubility increases, and when the absolute value is increased to a negative value, the water solubility increases. There is a negative correlation with the water solubility of the organic compound. Widely used as.

　高分子化合物は、疎水性構造単位として、下記式（ｉ）～（ｉｉｉ）で表される単量体に由来の構造単位から選択された１種以上の構造単位を含有することが好ましい。
The polymer compound preferably contains, as a hydrophobic structural unit, at least one structural unit selected from structural units derived from monomers represented by the following formulas (i) to (iii).

Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009

　上記式（ｉ）～（ｉｉｉ）中、Ｒ１、Ｒ２、及び、Ｒ３は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素原子、塩素原子、及び、臭素原子等）、又は、炭素数が１～６のアルキル基（例えば、メチル基、エチル基、及び、プロピル基等）を表す。

　Ｒ１、Ｒ２、及び、Ｒ３は、水素原子又は炭素数が１～３のアルキル基であることが好ましく、水素原子又はメチル基であることがより好ましい。Ｒ２及びＲ３は、水素原子であることが更に好ましい。

　Ｘは、酸素原子（－Ｏ－）又はイミノ基（－ＮＨ－）を表し、酸素原子が好ましい。
In the above formulas (i) to (iii), R 1 , R 2 and R 3 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or Represents an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, and a propyl group).

R 1 , R 2 , and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R 2 and R 3 are more preferably a hydrogen atom.

X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.

　Ｌは、単結合又は２価の連結基である。２価の連結基としては、２価の脂肪族基（例えば、アルキレン基、置換アルキレン基、アルケニレン基、置換アルケニレン基、アルキニレン基、置換アルキニレン基）、２価の芳香族基（例えば、アリーレン基、置換アリーレン基）、２価の複素環基、酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、イミノ基（－ＮＨ－）、置換イミノ基（－ＮＲ３１－、ここでＲ３１は脂肪族基、芳香族基又は複素環基）、カルボニル基（－ＣＯ－）、及び、これらの組合せ等が挙げられる。
L is a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (eg, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group) and a divalent aromatic group (eg, an arylene group) , Substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 Represents an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), and a combination thereof.

　２価の脂肪族基は、環状構造又は分岐構造を有していてもよい。脂肪族基の炭素数は、１～２０が好ましく、１～１５がより好ましく、１～１０が更に好ましい。脂肪族基は不飽和脂肪族基であっても飽和脂肪族基であってもよいが、飽和脂肪族基が好ましい。また、脂肪族基は、置換基を有していてもよい。置換基の例は、ハロゲン原子、芳香族基、及び、複素環基等が挙げられる。
The divalent aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group.

　２価の芳香族基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。また、芳香族基は置換基を有していてもよい。置換基の例は、ハロゲン原子、脂肪族基、芳香族基、及び、複素環基等が挙げられる。
The carbon number of the divalent aromatic group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10. Further, the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.

　２価の複素環基は、複素環として５員環又は６員環を含有することが好ましい。複素環に他の複素環、脂肪族環、又は、芳香族環が縮合していてもよい。また、複素環基は置換基を有していてもよい。置換基の例としては、ハロゲン原子、水酸基、オキソ基（＝Ｏ）、チオキソ基（＝Ｓ）、イミノ基（＝ＮＨ）、置換イミノ基（＝Ｎ－Ｒ３２、ここでＲ３２は脂肪族基、芳香族基、又は、複素環基）、脂肪族基、芳香族基、及び、複素環基が挙げられる。
The divalent heterocyclic group preferably contains a 5- or 6-membered ring as a heterocyclic ring. Another heterocycle, aliphatic ring, or aromatic ring may be condensed to the heterocycle. Further, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (＝ O), a thioxo group (＝ S), an imino group (＝ NH), a substituted imino group (＝ NR 32 , where R 32 is an aliphatic group). Group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.

　Ｌは、単結合、アルキレン基又はオキシアルキレン構造を含有する２価の連結基が好ましい。オキシアルキレン構造は、オキシエチレン構造又はオキシプロピレン構造がより好ましい。また、Ｌは、オキシアルキレン構造を２以上繰り返して含有するポリオキシアルキレン構造を含んでいてもよい。ポリオキシアルキレン構造としては、ポリオキシエチレン構造又はポリオキシプロピレン構造が好ましい。ポリオキシエチレン構造は、－（ＯＣＨ２ＣＨ２）ｎ－で表され、ｎは、２以上の整数が好ましく、２～１０の整数がより好ましい。
L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may include a polyoxyalkylene structure containing two or more oxyalkylene structures. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by-(OCH 2 CH 2 ) n-, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

　Ｚとしては、脂肪族基（例えば、アルキル基、置換アルキル基、不飽和アルキル基、置換不飽和アルキル基、）、芳香族基（例えば、アリール基、置換アリール基、アリーレン基、置換アリーレン基）、複素環基、及び、これらの組み合わせが挙げられる。これらの基には、酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、イミノ基（－ＮＨ－）、置換イミノ基（－ＮＲ３１－、ここでＲ３１は脂肪族基、芳香族基又は複素環基）、又は、カルボニル基（－ＣＯ－）が含まれていてもよい。
Z represents an aliphatic group (eg, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (eg, an aryl group, a substituted aryl group, an arylene group, a substituted arylene group) , A heterocyclic group, and a combination thereof. These groups include an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR 31 —, where R 31 is an aliphatic group or an aromatic group. Group or heterocyclic group) or a carbonyl group (—CO—).

　脂肪族基は、環状構造又は分岐構造を有していてもよい。脂肪族基の炭素数は、１～２０が好ましく、１～１５がより好ましく、１～１０が更に好ましい。脂肪族基には、更に環集合炭化水素基、架橋環式炭化水素基が含まれ、環集合炭化水素基の例としては、ビシクロヘキシル基、パーヒドロナフタレニル基、ビフェニル基、及び、４－シクロヘキシルフェニル基等が含まれる。架橋環式炭化水素環として、例えば、ピナン、ボルナン、ノルピナン、ノルボルナン、ビシクロオクタン環（ビシクロ［２．２．２］オクタン環、及び、ビシクロ［３．２．１］オクタン環等）等の２環式炭化水素環、ホモブレダン、アダマンタン、トリシクロ［５．２．１．０２，６］デカン、及び、トリシクロ［４．３．１．１２，５］ウンデカン環等の３環式炭化水素環、並びに、テトラシクロ［４．４．０．１２，５．１７，１０］ドデカン、及び、パーヒドロ－１，４－メタノ－５，８－メタノナフタレン環等の４環式炭化水素環等が挙げられる。また、架橋環式炭化水素環には、縮合環式炭化水素環、例えば、パーヒドロナフタレン（デカリン）、パーヒドロアントラセン、パーヒドロフェナントレン、パーヒドロアセナフテン、パーヒドロフルオレン、パーヒドロインデン、及び、パーヒドロフェナレン環等の５～８員シクロアルカン環が複数個縮合した縮合環も含まれる。

　脂肪族基は不飽和脂肪族基よりも飽和脂肪族基の方が好ましい。また、脂肪族基は、置換基を有していてもよい。置換基の例は、ハロゲン原子、芳香族基及び複素環基が挙げられる。ただし、脂肪族基は、置換基として酸基を有さない。
The aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10. The aliphatic group further includes a ring-assembled hydrocarbon group and a cross-linked cyclic hydrocarbon group. Examples of the ring-assembled hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -A cyclohexylphenyl group and the like. Examples of the bridged cyclic hydrocarbon ring include, for example, pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring and the like) and the like. Tricyclic hydrocarbon rings such as a cyclic hydrocarbon ring, homobredan, adamantane, tricyclo [5.2.1.0 2,6 ] decane, and tricyclo [4.3.1.1 2,5 ] undecane ring , And tetracyclo [4.4.0.1 2,5 . [ 7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. Further, the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring, for example, perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings such as a perhydrophenalene ring is also included.

As the aliphatic group, a saturated aliphatic group is more preferable than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.

　芳香族基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。また、芳香族基は置換基を有していてもよい。置換基の例は、ハロゲン原子、脂肪族基、芳香族基及び複素環基が挙げられる。ただし、芳香族基は、置換基として酸基を有さない。
The number of carbon atoms in the aromatic group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10. Further, the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.

　複素環基は、複素環として５員環又は６員環を含有することが好ましい。複素環に他の複素環、脂肪族環又は芳香族環が縮合していてもよい。また、複素環基は置換基を有していてもよい。置換基の例としては、ハロゲン原子、水酸基、オキソ基（＝Ｏ）、チオキソ基（＝Ｓ）、イミノ基（＝ＮＨ）、置換イミノ基（＝Ｎ－Ｒ３２、ここでＲ３２は脂肪族基、芳香族基又は複素環基）、脂肪族基、芳香族基、及び、複素環基が挙げられる。ただし、複素環基は、置換基として酸基を有さない。
The heterocyclic group preferably contains a 5- or 6-membered ring as a heterocyclic ring. Another heterocycle, aliphatic ring or aromatic ring may be fused to the heterocycle. Further, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (＝ O), a thioxo group (＝ S), an imino group (＝ NH), a substituted imino group (＝ NR 32 , where R 32 is an aliphatic group). Group, aromatic group or heterocyclic group), aliphatic group, aromatic group, and heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.

　上記式（ｉｉｉ）中、Ｒ４、Ｒ５、及びＲ６は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素原子、塩素原子、及び、臭素原子等）、炭素数が１～６のアルキル基（例えば、メチル基、エチル基、及び、プロピル基等）、Ｚ、又は、Ｌ－Ｚを表す。ここでＬ及びＺは、上記における基と同義である。Ｒ４、Ｒ５、及び、Ｒ６としては、水素原子、又は、炭素数が１～３のアルキル基が好ましく、水素原子がより好ましい。
In the above formula (iii), R 4 , R 5 , and R 6 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), and a C 1-6 carbon atom. Represents an alkyl group (eg, a methyl group, an ethyl group, and a propyl group), Z, or LZ. Here, L and Z have the same meaning as the above groups. As R 4 , R 5 and R 6 , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

　上記式（ｉ）で表される単量体として、Ｒ１、Ｒ２、及び、Ｒ３が水素原子、又は、メチル基であって、Ｌが単結合又はアルキレン基もしくはオキシアルキレン構造を含有する２価の連結基であって、Ｘが酸素原子又はイミノ基であって、Ｚが脂肪族基、複素環基、又は、芳香族基である化合物が好ましい。

　また、上記式（ｉｉ）で表される単量体として、Ｒ１が水素原子又はメチル基であって、Ｌがアルキレン基であって、Ｚが脂肪族基、複素環基、又は、芳香族基である化合物が好ましい。また、上記式（ｉｉｉ）で表される単量体として、Ｒ４、Ｒ５、及び、Ｒ６が水素原子又はメチル基であって、Ｚが脂肪族基、複素環基、又は、芳香族基である化合物が好ましい。
As the monomer represented by the above formula (i), R 1 , R 2 , and R 3 are a hydrogen atom or a methyl group, and L contains a single bond or an alkylene group or an oxyalkylene structure. Compounds that are divalent linking groups, wherein X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group are preferred.

Further, as the monomer represented by the above formula (ii), R 1 is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Compounds that are groups are preferred. Further, as the monomer represented by the above formula (iii), R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Compounds that are groups are preferred.

　式（ｉ）～（ｉｉｉ）で表される代表的な化合物の例としては、アクリル酸エステル類、メタクリル酸エステル類、及び、スチレン類等から選ばれるラジカル重合性化合物が挙げられる。

　なお、式（ｉ）～（ｉｉｉ）で表される代表的な化合物の例としては、特開２０１３－２４９４１７号公報の段落００８９～００９３に記載の化合物を参照でき、これらの内容は本明細書に組み込まれる。
Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylates, methacrylates, styrenes, and the like.

As examples of typical compounds represented by formulas (i) to (iii), compounds described in paragraphs 0089 to 0093 of JP-A-2013-249417 can be referred to, and the contents thereof are described in the present specification. Incorporated in

　高分子化合物において、疎水性構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、１０～９０質量％が好ましく、２０～８０質量％がより好ましい。含有量が上記範囲において十分なパターン形成が得られる。
In the polymer compound, the content of the hydrophobic structural unit in terms of mass is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, based on the total mass of the polymer compound. When the content is in the above range, a sufficient pattern formation can be obtained.

・顔料等と相互作用を形成しうる官能基

　高分子化合物は、顔料等（例えば、黒色顔料）と相互作用を形成しうる官能基を導入できる。ここで、高分子化合物は、顔料等と相互作用を形成しうる官能基を含有する構造単位を更に含有することが好ましい。

　この顔料等と相互作用を形成しうる官能基としては、例えば、酸基、塩基性基、配位性基、及び、反応性を有する官能基等が挙げられる。

　高分子化合物が、酸基、塩基性基、配位性基、又は、反応性を有する官能基を含有する場合、それぞれ、酸基を含有する構造単位、塩基性基を含有する構造単位、配位性基を含有する構造単位、又は、反応性を有する構造単位を含有することが好ましい。

　特に、高分子化合物が、更に、酸基として、カルボン酸基等のアルカリ可溶性基を含有すれば、高分子化合物に、アルカリ現像によるパターン形成のための現像性を付与できる。

　すなわち、高分子化合物にアルカリ可溶性基を導入すれば、上記組成物は、顔料等の分散に寄与する分散樹脂としての高分子化合物がアルカリ可溶性を含有することになる。このような高分子化合物を含有する組成物は、露光して形成される黒色層の遮光性に優れ、かつ、未露光部のアルカリ現像性が向上される。

　また、高分子化合物が酸基を含有する構造単位を含有すれば、高分子化合物が溶剤となじみやすくなり、塗布性も向上する傾向となる。

　これは、酸基を含有する構造単位における酸基が顔料等と相互作用しやすく、高分子化合物が顔料等を安定的に分散すると共に、顔料等を分散する高分子化合物の粘度が低くなっており、高分子化合物自体も安定的に分散されやすいためであると推測される。
.Functional groups capable of forming interactions with pigments, etc.

The polymer compound can introduce a functional group capable of forming an interaction with a pigment or the like (for example, a black pigment). Here, the polymer compound preferably further contains a structural unit having a functional group capable of forming an interaction with a pigment or the like.

Examples of the functional group capable of forming an interaction with the pigment or the like include an acid group, a basic group, a coordinating group, and a reactive functional group.

When the polymer compound contains an acid group, a basic group, a coordinating group, or a reactive functional group, the structural unit containing an acid group, the structural unit containing a basic group, It is preferable to contain a structural unit containing a coordinating group or a reactive structural unit.

In particular, if the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, developability for pattern formation by alkali development can be imparted to the polymer compound.

That is, if an alkali-soluble group is introduced into the polymer compound, the above-mentioned composition contains a polymer compound as a dispersing resin that contributes to dispersion of pigments and the like, which is alkali-soluble. The composition containing such a polymer compound is excellent in the light-shielding property of a black layer formed by exposure, and the alkali developability of an unexposed portion is improved.

Further, when the polymer compound contains a structural unit containing an acid group, the polymer compound is easily compatible with a solvent, and the coating property tends to be improved.

This is because the acid group in the structural unit containing an acid group easily interacts with the pigment and the like, and the polymer compound stably disperses the pigment and the like, and the viscosity of the polymer compound that disperses the pigment and the like becomes low. This is presumed to be because the polymer compound itself is easily dispersed stably.

　ただし、酸基としてのアルカリ可溶性基を含有する構造単位は、上記のグラフト鎖を含有する構造単位と同一の構造単位であっても、異なる構造単位であってもよいが、酸基としてのアルカリ可溶性基を含有する構造単位は、上記の疎水性構造単位とは異なる構造単位である（すなわち、上記の疎水性構造単位には相当しない）。
However, the structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the above-described structural unit containing a graft chain, or may be a different structural unit. The structural unit containing a soluble group is a structural unit different from the above-mentioned hydrophobic structural unit (that is, does not correspond to the above-mentioned hydrophobic structural unit).

　顔料等と相互作用を形成しうる官能基である酸基としては、例えば、カルボン酸基、スルホン酸基、リン酸基、及び、フェノール性水酸基等があり、カルボン酸基、スルホン酸基、及び、リン酸基のうち少なくとも１種が好ましく、カルボン酸基がより好ましい。カルボン酸基は、顔料等への吸着力が良好で、かつ、分散性が高い。

　すなわち、高分子化合物は、カルボン酸基、スルホン酸基、及び、リン酸基のうち少なくとも１種を含有する構造単位を更に含有することが好ましい。
Examples of the acid group, which is a functional group capable of forming an interaction with a pigment, include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. And at least one phosphoric acid group is preferable, and a carboxylic acid group is more preferable. Carboxylic acid groups have good adsorptivity to pigments and the like and have high dispersibility.

That is, the polymer compound preferably further contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

　高分子化合物は、酸基を含有する構造単位を１種又は２種以上有してもよい。

　高分子化合物は、酸基を含有する構造単位を含有してもしなくてもよいが、含有する場合、酸基を含有する構造単位の含有量は、高分子化合物の総質量に対して、５～８０質量％が好ましく、アルカリ現像による画像強度のダメージ抑制という点から、１０～６０質量％がより好ましい。
The polymer compound may have one or more structural units containing an acid group.

The polymer compound may or may not contain a structural unit containing an acid group, but if it does, the content of the structural unit containing an acid group is 5% based on the total mass of the polymer compound. The amount is preferably from 80 to 80% by mass, and more preferably from 10 to 60% by mass, from the viewpoint of suppressing damage to image strength due to alkali development.

　顔料等と相互作用を形成しうる官能基である塩基性基としては、例えば、第１級アミノ基、第２級アミノ基、第３級アミノ基、Ｎ原子を含有するヘテロ環、及び、アミド基等があり、好ましい塩基性基は、顔料等への吸着力が良好で、かつ、分散性が高い点で、第３級アミノ基である。高分子化合物は、これらの塩基性基を１種又は２種以上、含有できる。

　高分子化合物は、塩基性基を含有する構造単位を含有してもしなくてもよいが、含有する場合、塩基性基を含有する構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、０．０１～５０質量％が好ましく、現像性阻害抑制という点から、０．０１～３０質量％がより好ましい。
Examples of the basic group which is a functional group capable of forming an interaction with a pigment or the like include a primary amino group, a secondary amino group, a tertiary amino group, a hetero ring containing an N atom, and an amide. Preferred basic groups are tertiary amino groups because they have good adsorptivity to pigments and the like and have high dispersibility. The polymer compound can contain one or more of these basic groups.

The polymer compound may or may not contain a structural unit containing a basic group, but when it is contained, the content of the structural unit containing a basic group is calculated based on the total amount of the polymer compound in terms of mass. The amount is preferably 0.01 to 50% by mass, and more preferably 0.01 to 30% by mass, from the viewpoint of suppressing the inhibition of developing property.

　顔料等と相互作用を形成しうる官能基である配位性基、及び反応性を有する官能基としては、例えば、アセチルアセトキシ基、トリアルコキシシリル基、イソシアネート基、酸無水物、及び、酸塩化物等が挙げられる。好ましい官能基は、顔料等への吸着力が良好で、顔料等の分散性が高い点で、アセチルアセトキシ基である。高分子化合物は、これらの基を１種又は２種以上有してもよい。

　高分子化合物は、配位性基を含有する構造単位、又は、反応性を有する官能基を含有する構造単位を含有してもしなくてもよいが、含有する場合、これらの構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、１０～８０質量％が好ましく、現像性阻害抑制という点から、２０～６０質量％がより好ましい。
Examples of the coordinating group, which is a functional group capable of forming an interaction with a pigment, and the reactive functional group include, for example, acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, and acid chloride Objects and the like. A preferred functional group is an acetylacetoxy group in that it has good adsorptivity to pigments and the like and high dispersibility of the pigments and the like. The polymer compound may have one or more of these groups.

The polymer compound may or may not contain a structural unit containing a coordinating group, or a structural unit containing a reactive functional group, but if it contains, the content of these structural units Is preferably from 10 to 80% by mass, and more preferably from 20 to 60% by mass, in terms of suppression of development property inhibition, based on the total mass of the polymer compound.

　上記高分子化合物が、グラフト鎖以外に、顔料等と相互作用を形成しうる官能基を含有する場合、上記の各種の顔料等と相互作用を形成しうる官能基を含有していればよく、これらの官能基がどのように導入されているかは特に制限されないが、高分子化合物は、下記式（ｉｖ）～（ｖｉ）で表される単量体に由来の構造単位から選択された１種以上の構造単位を含有することが好ましい。
When the polymer compound, other than the graft chain, contains a functional group capable of forming an interaction with a pigment or the like, it is sufficient that the polymer compound contains a functional group capable of forming an interaction with the various pigments described above, The manner in which these functional groups are introduced is not particularly limited, and the polymer compound may be one selected from structural units derived from monomers represented by the following formulas (iv) to (vi). It is preferable to contain the above structural units.

Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010

　式（ｉｖ）～（ｖｉ）中、Ｒ１１、Ｒ１２、及びＲ１３は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素原子、塩素原子、及び、臭素原子等）、又は炭素数が１～６のアルキル基（例えば、メチル基、エチル基、プロピル基等）を表す。

　式（ｉｖ）～（ｖｉ）中、Ｒ１１、Ｒ１２、及びＲ１３としては、水素原子、又は炭素数が１～３のアルキル基が好ましく、水素原子又はメチル基がより好ましい。一般式（ｉｖ）中、Ｒ１２及びＲ１３としては、水素原子が更に好ましい。
In the formulas (iv) to (vi), R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or the like) or a carbon atom. Represents an alkyl group of 1 to 6 (eg, a methyl group, an ethyl group, a propyl group, etc.).

In Formulas (iv) to (vi), R 11 , R 12 , and R 13 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. In the general formula (iv), R 12 and R 13 are more preferably hydrogen atoms.

　式（ｉｖ）中のＸ１は、酸素原子（－Ｏ－）又はイミノ基（－ＮＨ－）を表し、酸素原子が好ましい。

　また、式（ｖ）中のＹは、メチン基又は窒素原子を表す。
X 1 in the formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.

Y in the formula (v) represents a methine group or a nitrogen atom.

　また、式（ｉｖ）～（ｖ）中のＬ１は、単結合又は２価の連結基を表す。２価の連結基の定義は、上述した式（ｉ）中のＬで表される２価の連結基の定義と同じである。
L 1 in the formulas (iv) to (v) represents a single bond or a divalent linking group. The definition of the divalent linking group is the same as the definition of the divalent linking group represented by L in the formula (i).

　Ｌ１は、単結合、アルキレン基又はオキシアルキレン構造を含有する２価の連結基が好ましい。オキシアルキレン構造は、オキシエチレン構造又はオキシプロピレン構造がより好ましい。また、Ｌ１は、オキシアルキレン構造を２以上繰り返して含有するポリオキシアルキレン構造を含んでいてもよい。ポリオキシアルキレン構造としては、ポリオキシエチレン構造又はポリオキシプロピレン構造が好ましい。ポリオキシエチレン構造は、－（ＯＣＨ２ＣＨ２）ｎ－で表され、ｎは、２以上の整数が好ましく、２～１０の整数がより好ましい。
L 1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L 1 may include a polyoxyalkylene structure containing two or more oxyalkylene structures. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by-(OCH 2 CH 2 ) n-, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

　式（ｉｖ）～（ｖｉ）中、Ｚ１は、グラフト鎖以外に顔料等と相互作用を形成しうる官能基を表し、カルボン酸基、又は、第３級アミノ基が好ましく、カルボン酸基がより好ましい。
In the formulas (iv) to (vi), Z 1 represents a functional group capable of forming an interaction with a pigment or the like other than the graft chain, and is preferably a carboxylic acid group or a tertiary amino group, and is preferably a carboxylic acid group. More preferred.

　式（ｖｉ）中、Ｒ１４、Ｒ１５、及びＲ１６は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素原子、塩素原子、及び、臭素原子等）、炭素数が１～６のアルキル基（例えば、メチル基、エチル基、及び、プロピル基等）、－Ｚ１、又はＬ１－Ｚ１を表す。ここでＬ１及びＺ１は、上記におけるＬ１及びＺ１と同義であり、好ましい例も同様である。Ｒ１４、Ｒ１５、及び、Ｒ１６としては、水素原子、又は炭素数が１～３のアルキル基が好ましく、水素原子がより好ましい。
In the formula (vi), R 14 , R 15 , and R 16 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms. group (e.g., methyl group, ethyl group, and propyl group), - Z 1, or an L 1 -Z 1. Here, L 1 and Z 1 have the same meanings as L 1 and Z 1 described above, and preferred examples are also the same. As R 14 , R 15 , and R 16 , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

　式（ｉｖ）で表される単量体として、Ｒ１１、Ｒ１２、及びＲ１３がそれぞれ独立に水素原子又はメチル基であって、Ｌ１がアルキレン基又はオキシアルキレン構造を含有する２価の連結基であって、Ｘ１が酸素原子又はイミノ基であって、Ｚ１がカルボン酸基である化合物が好ましい。

　また、式（ｖ）で表される単量体として、Ｒ１１が水素原子又はメチル基であって、Ｌ１がアルキレン基であって、Ｚ１がカルボン酸基であって、Ｙがメチン基である化合物が好ましい。

　更に、式（ｖｉ）で表される単量体として、Ｒ１４、Ｒ１５、及びＲ１６がそれぞれ独立に水素原子又はメチル基であって、Ｌ１が単結合又はアルキレン基であって、Ｚ１がカルボン酸基である化合物が好ましい。
As the monomer represented by the formula (iv), R 11 , R 12 , and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is a divalent group containing an alkylene group or an oxyalkylene structure. Preferred are compounds in which X 1 is an oxygen atom or an imino group and Z 1 is a carboxylic acid group.

Further, as the monomer represented by the formula (v), R 11 is a hydrogen atom or a methyl group, L 1 is an alkylene group, Z 1 is a carboxylic acid group, and Y is a methine group. Are preferred.

Further, as the monomer represented by the formula (vi), R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group, L 1 is a single bond or an alkylene group, and Z Compounds in which 1 is a carboxylic acid group are preferred.

　以下に、式（ｉｖ）～（ｖｉ）で表される単量体（化合物）の代表的な例を示す。

　単量体の例としては、メタクリル酸、クロトン酸、イソクロトン酸、分子内に付加重合性二重結合及び水酸基を含有する化合物（例えば、メタクリル酸２－ヒドロキシエチル）とコハク酸無水物との反応物、分子内に付加重合性二重結合及び水酸基を含有する化合物とフタル酸無水物との反応物、分子内に付加重合性二重結合及び水酸基を含有する化合物とテトラヒドロキシフタル酸無水物との反応物、分子内に付加重合性二重結合及び水酸基を含有する化合物と無水トリメリット酸との反応物、分子内に付加重合性二重結合及び水酸基を含有する化合物とピロメリット酸無水物との反応物、アクリル酸、アクリル酸ダイマー、アクリル酸オリゴマー、マレイン酸、イタコン酸、フマル酸、４－ビニル安息香酸、ビニルフェノール、及び、４－ヒドロキシフェニルメタクリルアミド等が挙げられる。
Hereinafter, typical examples of the monomers (compounds) represented by the formulas (iv) to (vi) are shown.

Examples of the monomer include methacrylic acid, crotonic acid, isocrotonic acid, a reaction of a compound containing an addition-polymerizable double bond and a hydroxyl group in a molecule (eg, 2-hydroxyethyl methacrylate) with succinic anhydride. Product, a reaction product of a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride, a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride Reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in a molecule with trimellitic anhydride, a compound containing an addition polymerizable double bond and a hydroxyl group in a molecule and pyromellitic anhydride With acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4 Hydroxyphenyl methacrylamide.

　顔料等と相互作用を形成しうる官能基を含有する構造単位の含有量は、顔料等との相互作用、経時安定性、及び現像液への浸透性の点から、質量換算で、高分子化合物の総質量に対して、０．０５～９０質量％が好ましく、１．０～８０質量％がより好ましく、１０～７０質量％が更に好ましい。
The content of the structural unit containing a functional group capable of forming an interaction with a pigment or the like is, in terms of the interaction with the pigment or the like, the stability over time, and the permeability into a developer, the amount of the polymer compound in terms of mass. Is preferably from 0.05 to 90% by mass, more preferably from 1.0 to 80% by mass, and still more preferably from 10 to 70% by mass, based on the total mass.

・その他の構造単位

　更に、高分子化合物は、画像強度等の諸性能を向上する目的で、本発明の効果を損なわない限りにおいて、グラフト鎖を含有する構造単位、疎水性構造単位、及び、顔料等と相互作用を形成しうる官能基を含有する構造単位とは異なる、種々の機能を有する他の構造単位（例えば、後述する溶剤との親和性を有する官能基等を含有する構造単位）を更に有していてもよい。

　このような、他の構造単位としては、例えば、アクリロニトリル類、及び、メタクリロニトリル類等から選ばれるラジカル重合性化合物に由来の構造単位が挙げられる。

　高分子化合物は、これらの他の構造単位を１種又は２種以上使用でき、その含有量は、質量換算で、高分子化合物の総質量に対して、０～８０質量％が好ましく、１０～６０質量％がより好ましい。含有量が上記範囲において、十分なパターン形成性が維持される。
.Other structural units

Furthermore, the polymer compound interacts with a graft chain-containing structural unit, a hydrophobic structural unit, and a pigment, for the purpose of improving various performances such as image strength, as long as the effects of the present invention are not impaired. It further has another structural unit having various functions different from the structural unit containing a functional group that can be formed (for example, a structural unit containing a functional group having an affinity for a solvent described below). Is also good.

Such other structural units include, for example, structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.

The polymer compound may use one or more of these other structural units, and its content is preferably from 0 to 80% by mass, and preferably from 10 to 80% by mass, based on the total mass of the polymer compound. 60 mass% is more preferable. When the content is in the above range, sufficient pattern formability is maintained.

・高分子化合物の物性

　高分子化合物の酸価は、０～２５０ｍｇＫＯＨ／ｇが好ましく、１０～２００ｍｇＫＯＨ／ｇがより好ましく、３０～１８０ｍｇＫＯＨ／ｇが更に好ましく、７０～１２０ｍｇＫＯＨ／ｇの範囲が特に好ましい。

　高分子化合物の酸価が１６０ｍｇＫＯＨ／ｇ以下であれば、黒色層を形成する際の現像時におけるパターン剥離がより効果的に抑えられる。また、高分子化合物の酸価が１０ｍｇＫＯＨ／ｇ以上であればアルカリ現像性がより良好となる。また、高分子化合物の酸価が２０ｍｇＫＯＨ／ｇ以上であれば、顔料等の沈降をより抑制でき、粗大粒子数をより少なくでき、組成物の経時安定性をより向上できる。
・ Physical properties of polymer compounds

The acid value of the polymer compound is preferably from 0 to 250 mgKOH / g, more preferably from 10 to 200 mgKOH / g, still more preferably from 30 to 180 mgKOH / g, particularly preferably from 70 to 120 mgKOH / g.

When the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development in forming a black layer can be more effectively suppressed. Further, when the acid value of the polymer compound is 10 mgKOH / g or more, the alkali developability becomes better. Further, when the acid value of the polymer compound is 20 mgKOH / g or more, sedimentation of pigments and the like can be further suppressed, the number of coarse particles can be reduced, and the stability over time of the composition can be further improved.

　本明細書において酸価は、例えば、化合物中における酸基の平均含有量から算出できる。また、樹脂の構成成分である酸基を含有する構造単位の含有量を変化させれば所望の酸価を有する樹脂を得られる。
In the present specification, the acid value can be calculated, for example, from the average content of acid groups in the compound. In addition, a resin having a desired acid value can be obtained by changing the content of the structural unit containing an acid group, which is a constituent component of the resin.

　高分子化合物の重量平均分子量は、４，０００～３００，０００が好ましく、５，０００～２００，０００がより好ましく、６，０００～１００，０００が更に好ましく、１０，０００～５０，０００が特に好ましい。

　高分子化合物は、公知の方法に基づいて合成できる。
The weight average molecular weight of the polymer compound is preferably from 4,000 to 300,000, more preferably from 5,000 to 200,000, still more preferably from 6,000 to 100,000, particularly preferably from 10,000 to 50,000. preferable.

The polymer compound can be synthesized based on a known method.

　高分子化合物の具体例としては、楠本化成社製「ＤＡ－７３０１」、ＢＹＫＣｈｅｍｉｅ社製「Ｄｉｓｐｅｒｂｙｋ－１０１（ポリアミドアミン燐酸塩）、１０７（カルボン酸エステル）、１１０（酸基を含有する共重合体）、１１１（リン酸系分散剤）、１３０（ポリアミド）、１６１、１６２、１６３、１６４、１６５、１６６、１７０、１９０（高分子共重合体）」、「ＢＹＫ－Ｐ１０４、Ｐ１０５（高分子量不飽和ポリカルボン酸）」、ＥＦＫＡ社製「ＥＦＫＡ４０４７、４０５０～４０１０～４１６５（ポリウレタン系）、ＥＦＫＡ４３３０～４３４０（ブロック共重合体）、４４００～４４０２（変性ポリアクリレート）、５０１０（ポリエステルアミド）、５７６５（高分子量ポリカルボン酸塩）、６２２０（脂肪酸ポリエステル）、６７４５（フタロシアニン誘導体）、６７５０（アゾ顔料誘導体）」、味の素ファインテクノ社製「アジスパーＰＢ８２１、ＰＢ８２２、ＰＢ８８０、ＰＢ８８１」、共栄社化学社製「フローレンＴＧ－７１０（ウレタンオリゴマー）」、「ポリフローＮｏ．５０Ｅ、Ｎｏ．３００（アクリル系共重合体）」、楠本化成社製「ディスパロンＫＳ－８６０、８７３ＳＮ、８７４、＃２１５０（脂肪族多価カルボン酸）、＃７００４（ポリエーテルエステル）、ＤＡ－７０３－５０、ＤＡ－７０５、ＤＡ－７２５」、花王社製「デモールＲＮ、Ｎ（ナフタレンスルホン酸ホルマリン重縮合物）、ＭＳ、Ｃ、ＳＮ－Ｂ（芳香族スルホン酸ホルマリン重縮合物）」、「ホモゲノールＬ－１８（高分子ポリカルボン酸）」、「エマルゲン９２０、９３０、９３５、９８５（ポリオキシエチレンノニルフェニルエーテル）」、「アセタミン８６（ステアリルアミンアセテート）」、日本ルーブリゾール製「ソルスパース５０００（フタロシアニン誘導体）、２２０００（アゾ顔料誘導体）、１３２４０（ポリエステルアミン）、３０００、１２０００、１７０００、２００００、２７０００（末端部に機能部を含有する高分子）、２４０００、２８０００、３２０００、３８５００（グラフト共重合体）」、日光ケミカルズ社製「ニッコールＴ１０６（ポリオキシエチレンソルビタンモノオレアート）、ＭＹＳ－ＩＥＸ（ポリオキシエチレンモノステアレート）」、川研ファインケミカル製　ヒノアクトＴ－８０００Ｅ等、信越化学工業製、オルガノシロキサンポリマーＫＰ－３４１、裕商製「Ｗ００１：カチオン系界面活性剤」、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル等のノニオン系界面活性剤、「Ｗ００４、Ｗ００５、Ｗ０１７」等のアニオン系界面活性剤、森下産業製「ＥＦＫＡ－４６、ＥＦＫＡ－４７、ＥＦＫＡ－４７ＥＡ、ＥＦＫＡポリマー１００、ＥＦＫＡポリマー４００、ＥＦＫＡポリマー４０１、ＥＦＫＡポリマー４５０」、サンノプコ製「ディスパースエイド６、ディスパースエイド８、ディスパースエイド１５、ディスパースエイド９１００」等の高分子分散剤、ＡＤＥＫＡ製「アデカプルロニックＬ３１、Ｆ３８、Ｌ４２、Ｌ４４、Ｌ６１、Ｌ６４、Ｆ６８、Ｌ７２、Ｐ９５、Ｆ７７、Ｐ８４、Ｆ８７、Ｐ９４、Ｌ１０１、Ｐ１０３、Ｆ１０８、Ｌ１２１、Ｐ－１２３」、及び、三洋化成製「イオネット（商品名）Ｓ－２０」等が挙げられる。また、アクリベースＦＦＳ－６７５２、及び、アクリベースＦＦＳ－１８７も使用できる。
Specific examples of the polymer compound include “DA-7301” manufactured by Kusumoto Kasei, “Disperbyk-101 (polyamideamine phosphate)” manufactured by BYK Chemie, 107 (carboxylate), and 110 (copolymer containing an acid group). ), 111 (phosphoric acid-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer) "," BYK-P104, P105 (high molecular weight non- EFKA 4047, 4050-4010-4165 (polyurethane), EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (polyester amide) High molecular weight polycarboxylate), 6220 (fatty acid polyester) ), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”,“ Ajispar PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fine-Techno,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical,“ Polyflow ” No. 50E, No. 300 (acrylic copolymer) ", manufactured by Kusumoto Kasei Co., Ltd." Dispalon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA " -703-50, DA-705, DA-725 ", Kao Corporation" Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) " , “Homogenol L-18 (high-molecular polycarboxylic acid)”, “Emulgen 920” 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," acetamine 86 (stearylamine acetate) ", Nippon Lubrizol" solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, 20,000, 27000 (polymer having a functional part at the terminal), 24000, 28000, 32000, 38500 (graft copolymer) ", Nikkor T106 (polyoxyethylene sorbitan mono) manufactured by Nikko Chemicals Co., Ltd. Oleate), MYS-IEX (polyoxyethylene monostearate) ", Hinoact T-8000E, manufactured by Kawaken Fine Chemical, Shin-Etsu Chemical Co., Ltd., organosiloxane polymer KP-341, Yu "W001: cationic surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol dilaurate Nonionic surfactants such as stearates and sorbitan fatty acid esters; anionic surfactants such as "W004, W005, W017";"EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA" manufactured by Morishita Sangyo Polymer 400, EFKA polymer 401, EFKA polymer 450 ", Sannopco's" Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid " Polymer dispersants such as "Persadeid 9100" and ADEKA "ADEKAPLLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 "and" Ionet (trade name) S-20 "manufactured by Sanyo Chemical Industries, and the like. Also, Acrybase FFS-6752 and Acrybase FFS-187 can be used.

　また、酸基及び塩基性基を含有する両性樹脂を使用することも好ましい。両性樹脂は、酸価が５ｍｇＫＯＨ／ｇ以上で、かつ、アミン価が５ｍｇＫＯＨ／ｇ以上である樹脂が好ましい。

　両性樹脂の市販品としては、例えば、ビックケミー社製のＤＩＳＰＥＲＢＹＫ－１３０、ＤＩＳＰＥＲＢＹＫ－１４０、ＤＩＳＰＥＲＢＹＫ－１４２、ＤＩＳＰＥＲＢＹＫ－１４５、ＤＩＳＰＥＲＢＹＫ－１８０、ＤＩＳＰＥＲＢＹＫ－１８７、ＤＩＳＰＥＲＢＹＫ－１９１、ＤＩＳＰＥＲＢＹＫ－２００１、ＤＩＳＰＥＲＢＹＫ－２０１０、ＤＩＳＰＥＲＢＹＫ－２０１２、ＤＩＳＰＥＲＢＹＫ－２０２５、ＢＹＫ－９０７６、味の素ファインテクノ社製のアジスパーＰＢ８２１、アジスパーＰＢ８２２、及び、アジスパーＰＢ８８１等が挙げられる。

　これらの高分子化合物は、１種を単独で用いても、２種以上を併用してもよい。
It is also preferable to use an amphoteric resin containing an acid group and a basic group. The amphoteric resin is preferably a resin having an acid value of 5 mgKOH / g or more and an amine value of 5 mgKOH / g or more.

Commercially available amphoteric resins include, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, and DISPERBY manufactured by BYK Chemie. DISPERBYK-2012, DISPERBYK-2025, BYK-9076, Ajispar PB821, Azispar PB822 and Azispar PB881 manufactured by Ajinomoto Fine-Techno.

One of these polymer compounds may be used alone, or two or more thereof may be used in combination.

　なお、高分子化合物の具体例の例としては、特開２０１３－２４９４１７号公報の段落０１２７～０１２９に記載の高分子化合物を参照でき、これらの内容は本明細書に組み込まれる。
As specific examples of the polymer compound, reference can be made to the polymer compounds described in paragraphs 0127 to 0129 of JP-A-2013-249417, the contents of which are incorporated herein.

　また、分散樹脂としては、上記の高分子化合物以外に、特開２０１０－１０６２６８号公報の段落００３７～０１１５（対応するＵＳ２０１１／０１２４８２４の段落００７５～０１３３欄）のグラフト共重合体が使用でき、これらの内容は援用でき、本明細書に組み込まれる。

　また、上記以外にも、特開２０１１－１５３２８３号公報の段落００２８～００８４（対応するＵＳ２０１１／０２７９７５９の段落００７５～０１３３欄）の酸性基が連結基を介して結合してなる側鎖構造を含有する構成成分を含有する高分子化合物が使用でき、これらの内容は援用でき、本明細書に組み込まれる。
Further, as the dispersing resin, besides the above-mentioned polymer compounds, graft copolymers described in paragraphs 0037 to 0115 of JP-A-2010-106268 (corresponding to columns 0075 to 0133 of US2011 / 0124824) can be used. Is incorporated herein by reference.

Further, in addition to the above, it contains a side chain structure in which an acidic group described in paragraphs 0028 to 0084 of JP-A-2011-153283 (corresponding to columns 2011 to 0133 of US2011 / 0279759) is bonded via a linking group. High molecular compounds containing the following constituents can be used, the contents of which are incorporated herein by reference.

　また、分散樹脂としては、特開２０１６－１０９７６３号公報の段落００３３～００４９に記載された樹脂も使用でき、この内容は本明細書に組み込まれる。
Further, as the dispersing resin, resins described in paragraphs 0033 to 0049 of JP-A-2016-109763 can also be used, and the contents thereof are incorporated herein.

（アルカリ可溶性樹脂）

　組成物は、アルカリ可溶性樹脂を含有することが好ましい。本明細書において、アルカリ可溶性樹脂とは、アルカリ可溶性を促進する基（アルカリ可溶性基。例えばカルボン酸基等の酸基）を含有する樹脂を意味し、既に説明した分散樹脂とは異なる樹脂を意味する。

　組成物中におけるアルカリ可溶性樹脂の含有量としては特に制限されないが、組成物の全固形分に対して、１～３０質量％が好ましく、２～２０質量％がより好ましく、５～１５質量％が更に好ましい。

　アルカリ可溶性樹脂は１種を単独で用いても、２種以上を併用してもよい。２種以上のアルカリ可溶性樹脂を併用する場合には、合計含有量が上記範囲内であることが好ましい。
(Alkali-soluble resin)

The composition preferably contains an alkali-soluble resin. In the present specification, the alkali-soluble resin means a resin containing a group that promotes alkali solubility (an alkali-soluble group, for example, an acid group such as a carboxylic acid group), and a resin different from the dispersion resin described above. I do.

The content of the alkali-soluble resin in the composition is not particularly limited, but is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and more preferably 5 to 15% by mass based on the total solid content of the composition. More preferred.

One alkali-soluble resin may be used alone, or two or more alkali-soluble resins may be used in combination. When two or more alkali-soluble resins are used in combination, the total content is preferably within the above range.

　アルカリ可溶性樹脂としては、分子中に少なくとも１個のアルカリ可溶性基を含有する樹脂が挙げられ、例えば、ポリヒドロキシスチレン樹脂、ポリシロキサン樹脂、（メタ）アクリル樹脂、（メタ）アクリルアミド樹脂、（メタ）アクリル／（メタ）アクリルアミド共重合樹脂、エポキシ系樹脂、及び、ポリイミド樹脂等が挙げられる。
Examples of the alkali-soluble resin include resins containing at least one alkali-soluble group in a molecule, such as polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide resin, and (meth) acrylic resin. An acryl / (meth) acrylamide copolymer resin, an epoxy resin, a polyimide resin, and the like can be given.

　アルカリ可溶性樹脂の具体例としては、不飽和カルボン酸とエチレン性不飽和化合物の共重合樹脂が挙げられる。

　不飽和カルボン酸としては特に制限されないが、（メタ）アクリル酸、クロトン酸、及び、ビニル酢酸等のモノカルボン酸類；イタコン酸、マレイン酸、及び、フマル酸等のジカルボン酸、又は、その酸無水物；並びに、フタル酸モノ（２－（メタ）アクリロイロキシエチル）等の多価カルボン酸モノエステル類；等が挙げられる。
Specific examples of the alkali-soluble resin include a copolymer resin of an unsaturated carboxylic acid and an ethylenically unsaturated compound.

The unsaturated carboxylic acid is not particularly limited, but monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and vinyl acetic acid; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, or acid anhydrides thereof And polyvalent carboxylic acid monoesters such as mono (2- (meth) acryloyloxyethyl) phthalate; and the like.

　共重合可能なエチレン性不飽和化合物としては、（メタ）アクリル酸メチル等が挙げられる。また、特開２０１０－９７２１０号公報の段落００２７、及び、特開２０１５－６８８９３号公報の段落００３６～００３７に記載の化合物も使用でき、上記の内容は本明細書に組み込まれる。
Examples of the copolymerizable ethylenically unsaturated compound include methyl (meth) acrylate. Further, the compounds described in paragraph 0027 of JP-A-2010-97210 and paragraphs 0036 to 0037 of JP-A-2015-68893 can also be used, and the above description is incorporated in the present specification.

　また、共重合可能なエチレン性不飽和化合物であって、側鎖にエチレン性不飽和基を含有する化合物を組み合わせて用いてもよい。エチレン性不飽和基としては、（メタ）アクリル酸基が好ましい。側鎖にエチレン性不飽和基を含有するアクリル樹脂は、例えば、カルボン酸基を含有するアクリル樹脂のカルボン酸基に、グリシジル基又は脂環式エポキシ基を含有するエチレン性不飽和化合物を付加反応させて得られる。
Further, a copolymerizable ethylenically unsaturated compound having a side chain containing an ethylenically unsaturated group may be used in combination. As the ethylenically unsaturated group, a (meth) acrylic acid group is preferable. The acrylic resin containing an ethylenically unsaturated group in the side chain is, for example, an addition reaction of an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to a carboxylic acid group of an acrylic resin containing a carboxylic acid group. Obtained.

　アルカリ可溶性樹脂としては、硬化性基を含有するアルカリ可溶性樹脂も好ましい。

　上記硬化性基としては、上述の高分子化合物が含有してもよい硬化性基が同様に挙げられ、好ましい範囲も同様である。

　硬化性基を含有するアルカリ可溶性樹脂としては、硬化性基を側鎖に有するアルカリ可溶性樹脂等が好ましい。硬化性基を含有するアルカリ可溶性樹脂としては、ダイヤナールＮＲシリーズ（三菱レイヨン社製）、Ｐｈｏｔｏｍｅｒ６１７３（ＣＯＯＨ含有　ｐｏｌｙｕｒｅｔｈａｎｅ　ａｃｒｙｌｉｃ　ｏｌｉｇｏｍｅｒ．Ｄｉａｍｏｎｄ　Ｓｈａｍｒｏｃｋ　Ｃｏ．，Ｌｔｄ．製）、ビスコートＲ－２６４、ＫＳレジスト１０６（いずれも大阪有機化学工業社製）、サイクロマーＰシリーズ（例えば、ＡＣＡ２３０ＡＡ）、プラクセル　ＣＦ２００シリーズ（いずれもダイセル社製）、Ｅｂｅｃｒｙｌ３８００（ダイセル・オルネクス社製）、及び、アクリキュアＲＤ－Ｆ８（日本触媒社製）等が挙げられる。
As the alkali-soluble resin, an alkali-soluble resin containing a curable group is also preferable.

Examples of the curable group include curable groups that may be contained in the above-mentioned polymer compound, and the preferable range is also the same.

As the alkali-soluble resin containing a curable group, an alkali-soluble resin having a curable group in a side chain is preferable. Examples of the alkali-soluble resin containing a curable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polythane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264, and KS resist 106 (KS). All are manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Praxel CF200 series (all manufactured by Daicel), Ebecryl3800 (manufactured by Daicel Ornex), and Acrylic RD-F8 (Nippon Shokubai Co., Ltd.) Manufactured).

　アルカリ可溶性樹脂としては、例えば、特開昭５９－４４６１５号公報、特公昭５４－３４３２７号公報、特公昭５８－１２５７７号公報、特公昭５４－２５９５７号公報、特開昭５４－９２７２３号公報、特開昭５９－５３８３６号公報、及び、特開昭５９－７１０４８号公報に記載されている側鎖にカルボン酸基を含有するラジカル重合体；欧州特許第９９３９６６号公報、欧州特許第１２０４０００号明細書、及び、特開２００１－３１８４６３号公報に記載されているアルカリ可溶性基を含有するアセタール変性ポリビニルアルコール系バインダー樹脂；ポリビニルピロリドン；ポリエチレンオキサイド；アルコール可溶性ナイロン、及び、２，２－ビス－（４－ヒドロキシフェニル）－プロパンとエピクロロヒドリンとの反応物であるポリエーテル等；並びに、国際公開第２００８／１２３０９７号パンフレットに記載のポリイミド樹脂；等を使用できる。
Examples of the alkali-soluble resin include, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, and JP-A-54-92723. Radical polymers containing a carboxylic acid group in the side chain described in JP-A-59-53836 and JP-A-59-71048; European Patent No. 939966 and European Patent No. 1204000. And an acetal-modified polyvinyl alcohol-based binder resin containing an alkali-soluble group described in JP-A-2001-318463; polyvinylpyrrolidone; polyethylene oxide; alcohol-soluble nylon and 2,2-bis- (4 -Hydroxyphenyl) -propane and epichlorohydrin And, polyimide resin described in WO 2008/123097 pamphlet; and the like can be used polyethers such as that.

　アルカリ可溶性樹脂としては、例えば、特開２０１６－７５８４５号公報の段落０２２５～０２４５に記載の化合物も使用でき、上記内容は本明細書に組み込まれる。
As the alkali-soluble resin, for example, the compounds described in paragraphs 0225 to 0245 of JP-A-2016-75845 can also be used, and the above description is incorporated herein.

　アルカリ可溶性樹脂としては、ポリイミド前駆体も使用できる。ポリイミド前駆体は、酸無水物基を含有する化合物とジアミン化合物とを４０～１００℃下において付加重合反応して得られる樹脂を意味する。

　ポリイミド前駆体としては、例えば、式（１）で表される繰り返し単位を含有する樹脂が挙げられる。ポリイミド前駆体の構造としては、例えば、下記式（２）で示されるアミック酸構造と、アミック酸構造が一部イミド閉環してなる下記式（３）、及び、全てイミド閉環した下記式（４）で示されるイミド構造を含有するポリイミド前駆体が挙げられる。

　なお、本明細書において、アミック酸構造を有するポリイミド前駆体をポリアミック酸という場合がある。
A polyimide precursor can also be used as the alkali-soluble resin. The polyimide precursor means a resin obtained by subjecting a compound containing an acid anhydride group and a diamine compound to an addition polymerization reaction at 40 to 100 ° C.

Examples of the polyimide precursor include a resin containing a repeating unit represented by the formula (1). Examples of the structure of the polyimide precursor include, for example, an amic acid structure represented by the following formula (2), the following formula (3) in which the amic acid structure is partially imide-closed, and the following formula (4) in which all imides are closed. And the polyimide precursor containing an imide structure represented by the formula (1).

In this specification, a polyimide precursor having an amic acid structure may be referred to as a polyamic acid.

Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011

Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012

Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013

Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014

　上記式（１）～（４）において、Ｒ１は炭素数２～２２の４価の有機基を表し、Ｒ２は炭素数１～２２の２価の有機基を表し、ｎは１又は２を表す。
In the above formulas (1) to (4), R 1 represents a tetravalent organic group having 2 to 22 carbon atoms, R 2 represents a divalent organic group having 1 to 22 carbon atoms, and n is 1 or 2 Represents

　上記ポリイミド前駆体の具体例としては、例えば、特開２００８－１０６２５０号公報の段落００１１～００３１に記載の化合物、特開２０１６－１２２１０１号公報の段落００２２～００３９に記載の化合物、及び、特開２０１６－６８４０１号公報の段落００６１～００９２に記載の化合物等が挙げられ、上記の内容は本明細書に組み込まれる。
Specific examples of the polyimide precursor include, for example, the compounds described in paragraphs 0011 to 0031 of JP-A-2008-106250, the compounds described in paragraphs 0022 to 0039 of JP-A-2016-122101, and Compounds described in paragraphs 0061 to 0092 of 2016-68401 can be mentioned, and the above description is incorporated herein.

　アルカリ可溶性樹脂は、組成物を用いて得られるパターン状の黒色層のパターン形状がより優れる点で、ポリイミド樹脂、及び、ポリイミド前駆体からなる群から選択される少なくとも１種を含有することも好ましい。
The alkali-soluble resin is also preferable to contain at least one selected from the group consisting of a polyimide resin and a polyimide precursor, in that the pattern shape of the patterned black layer obtained using the composition is more excellent. .

　アルカリ可溶性基を含有するポリイミド樹脂としては、特に制限されず、公知のアルカリ可溶性基を含有するポリイミド樹脂を使用できる。上記ポリイミド樹脂としては、例えば、特開２０１４－１３７５２３号公報の段落００５０に記載された樹脂、特開２０１５－１８７６７６号公報の段落００５８に記載された樹脂、及び、特開２０１４－１０６３２６号公報の段落００１２～００１３に記載された樹脂等が挙げられ、上記の内容は本明細書に組み込まれる。
The polyimide resin containing an alkali-soluble group is not particularly limited, and a known polyimide resin containing an alkali-soluble group can be used. Examples of the polyimide resin include a resin described in paragraph 0050 of JP-A-2014-137523, a resin described in paragraph 0058 of JP-A-2015-187676, and a resin described in JP-A-2014-106326. Examples include the resins described in paragraphs 0012 to 0013, and the contents described above are incorporated herein.

　アルカリ可溶性樹脂としては、ポリベンゾオキサゾール前駆体も使用できる。

　ポリベンゾオキサゾール前駆体は、水酸基含有ジアミンとジカルボン酸誘導体とから合成される樹脂である。

　水酸基含有ジアミンとしては、例えば、ビスアミノフェノール化合物等のフェノール系水酸基を有する芳香族ジアミンが挙げられる。水酸基含有ジアミンの具体例としては、３，３－ジヒドロキシベンジジン及び３，３’－ジヒドロキシ－４，４’－ジアミノジフェニルエーテルが挙げられる。

　ジカルボン酸誘導体としては、例えば、ジカルボン酸クロリド、ジカルボン酸エステル等のジカルボン酸誘導体が挙げられ、芳香族ジカルボン酸誘導体が好ましい。ジカルボン酸誘導体の具体例としては、イソフタル酸ジクロリド及びテレフタル酸ジクロリドが挙げられる。

　ポリベンゾオキサゾール前駆体の具体例としては、ポリヒドロキシアミド、ポリアミノアミド、ポリアミド及びポリアミドイミドが挙げられる。
As the alkali-soluble resin, a polybenzoxazole precursor can also be used.

The polybenzoxazole precursor is a resin synthesized from a hydroxyl group-containing diamine and a dicarboxylic acid derivative.

Examples of the hydroxyl group-containing diamine include aromatic diamines having a phenolic hydroxyl group, such as bisaminophenol compounds. Specific examples of the hydroxyl group-containing diamine include 3,3-dihydroxybenzidine and 3,3′-dihydroxy-4,4′-diaminodiphenyl ether.

Examples of the dicarboxylic acid derivative include dicarboxylic acid derivatives such as dicarboxylic acid chloride and dicarboxylic acid ester, and aromatic dicarboxylic acid derivatives are preferable. Specific examples of the dicarboxylic acid derivative include isophthalic acid dichloride and terephthalic acid dichloride.

Specific examples of the polybenzoxazole precursor include polyhydroxyamide, polyaminoamide, polyamide, and polyamideimide.

　ポリベンゾオキサゾール前駆体の具体例としては、例えば、特開２００３－１２１９９７号公報の段落００４９～００６２に記載の化合物、国際公開第２０１７／０５７２８１号明細書の段落００５０～００５７に記載の化合物、国際公開第２０１６／０４３２０３号明細書の段落００１５～００４３に記載の化合物等が挙げられ、上記の内容は本明細書に組み込まれる。
Specific examples of the polybenzoxazole precursor include, for example, the compounds described in paragraphs 0049 to 0062 of JP-A-2003-121997, the compounds described in paragraphs 0050 to 0057 of WO2017 / 057281 and international publications The compounds described in paragraphs 0015 to 0043 of JP-A-2016 / 043203 are exemplified, and the above description is incorporated herein.

　ポリイミド前駆体及びポリベンゾオキサゾール前駆体の共重合体は、ポリアミド酸エステル構造単位及びヒドロキシポリアミド構造単位を有する共重合体であり、例えば、ポリアミド酸エステル構造単位及びヒドロキシポリアミド構造単位の交互共重合構造を有する共重合体が挙げられる。
The copolymer of the polyimide precursor and the polybenzoxazole precursor is a copolymer having a polyamic acid ester structural unit and a hydroxypolyamide structural unit, for example, an alternating copolymer structure of a polyamic acid ester structural unit and a hydroxypolyamide structural unit And a copolymer having the formula:

　アルカリ可溶性樹脂としては、遮光膜の耐光性及び耐熱性がより優れる点から、ポリイミド前駆体、ポリベンゾオキサゾール前駆体及びこれらの共重合体からなる群より選択される少なくとも１種が好ましく、ポリイミド樹脂がより好ましい。
As the alkali-soluble resin, at least one selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a copolymer thereof is preferable because the light resistance and the heat resistance of the light-shielding film are more excellent. Is more preferred.

　また、アルカリ可溶性樹脂としては、〔ベンジル（メタ）アクリレート／（メタ）アクリル酸／必要に応じてその他の付加重合性ビニルモノマー〕共重合体、及び〔アリル（メタ）アクリレート／（メタ）アクリル酸／必要に応じてその他の付加重合性ビニルモノマー〕共重合体は、膜強度、感度、及び、現像性のバランスに優れている点で、好適である。

　上記その他の付加重合性ビニルモノマーには、１種単独でも２種以上でもよい。

　上記共重合体は、黒色層の耐湿性がより優れる点から、硬化性基を有することが好ましく、（メタ）アクリロイル基等のエチレン性不飽和基を含有することがより好ましい。

　例えば、上記その他の付加重合性ビニルモノマーとして硬化性基を有するモノマーを使用して共重合体に硬化性基が導入されていてもよい。また、共重合体中の（メタ）アクリル酸に由来する単位及び／又は上記その他の付加重合性ビニルモノマーに由来する単位の１種以上の、一部又は全部に、硬化性基（好ましくは（メタ）アクリロイル基等のエチレン性不飽和基）が導入されていてもよい。

　上記その他の付加重合性ビニルモノマーとしては、例えば、（メタ）アクリル酸メチル、スチレン系単量体（ヒドロキシスチレン等）、及び、エーテルダイマーが挙げられる。

　上記エーテルダイマーは、例えば、下記一般式（ＥＤ１）で表される化合物、及び、下記一般式（ＥＤ２）で表される化合物が挙げられる。
Examples of the alkali-soluble resin include [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer, and [allyl (meth) acrylate / (meth) acrylic acid]. / If necessary, other addition-polymerizable vinyl monomers] copolymers are suitable because they have an excellent balance of film strength, sensitivity, and developability.

The above-mentioned other addition-polymerizable vinyl monomers may be used alone or in combination of two or more.

The above-mentioned copolymer preferably has a curable group, and more preferably contains an ethylenically unsaturated group such as a (meth) acryloyl group, in that the moisture resistance of the black layer is more excellent.

For example, a curable group may be introduced into the copolymer using a monomer having a curable group as the above-mentioned other addition-polymerizable vinyl monomer. Also, a curable group (preferably ((A) or (B)) may be added to a part or all of one or more of units derived from (meth) acrylic acid and / or units derived from the other addition-polymerizable vinyl monomers in the copolymer. And a (meth) acryloyl group or other ethylenically unsaturated group).

Examples of the other addition-polymerizable vinyl monomers include methyl (meth) acrylate, styrene-based monomers (such as hydroxystyrene), and ether dimers.

Examples of the ether dimer include a compound represented by the following general formula (ED1) and a compound represented by the following general formula (ED2).

Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015

　一般式（ＥＤ１）中、Ｒ１及びＲ２は、それぞれ独立に、水素原子又は炭素数１～２５の炭化水素基を表す。
In the general formula (ED1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms.

Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016

　一般式（ＥＤ２）中、Ｒは、水素原子又は炭素数１～３０の有機基を表す。一般式（ＥＤ２）の具体例としては、特開２０１０－１６８５３９号公報の記載を参酌できる。
In the general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), the description in JP-A-2010-168538 can be referred to.

　エーテルダイマーの具体例としては、例えば、特開２０１３－２９７６０号公報の段落０３１７を参酌することができ、この内容は本明細書に組み込まれる。エーテルダイマーは、１種のみであってもよいし、２種以上であってもよい。
As a specific example of the ether dimer, for example, paragraph 0317 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated herein. The ether dimer may be only one kind or two or more kinds.

　アルカリ可溶性樹脂の酸価としては、特に制限されないが、一般に、３０～５００ｍｇＫＯＨ／ｇが好ましく、５０～２００ｍｇＫＯＨ／ｇ以上がより好ましい。
The acid value of the alkali-soluble resin is not particularly limited, but is generally preferably from 30 to 500 mgKOH / g, and more preferably from 50 to 200 mgKOH / g.

＜重合性化合物＞

　遮光性組成物は、重合性化合物を含有する。

　本明細書において重合性化合物とは、後述する重合開始剤の作用を受けて重合する化合物を意味し、上述の、分散樹脂及びアルカリ可溶性樹脂とは異なる成分を意味する。
<Polymerizable compound>

The light-shielding composition contains a polymerizable compound.

In the present specification, the polymerizable compound means a compound which is polymerized by the action of a polymerization initiator described later, and means a component different from the above-described dispersion resin and alkali-soluble resin.

　組成物中における重合性化合物の含有量としては特に制限されないが、組成物の全固形分に対して、５～３５質量％が好ましく、１０～３０質量％がより好ましく、１５～２５質量％が更に好ましい。重合性化合物は、１種を単独で用いても、２種以上を併用してもよい。２種以上の重合性化合物を併用する場合には、合計含有量が上記範囲内であることが好ましい。

　重合性化合物の分子量（又は、重量平均分子量）は、特に制限されないが、２０００以下が好ましい。
The content of the polymerizable compound in the composition is not particularly limited, but is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, and preferably 15 to 25% by mass based on the total solid content of the composition. More preferred. As the polymerizable compound, one type may be used alone, or two or more types may be used in combination. When two or more polymerizable compounds are used in combination, the total content is preferably within the above range.

The molecular weight (or weight average molecular weight) of the polymerizable compound is not particularly limited, but is preferably 2000 or less.

　重合性化合物としては、エチレン性不飽和基を含有する化合物が好ましい。

　つまり遮光性組成物は、エチレン性不飽和基を含有する低分子化合物を、重合性化合物として含有することが好ましい。

　重合性化合物としては、エチレン性不飽和結合を１個以上含有する化合物が好ましく、２個以上含有する化合物がより好ましく、３個以上含有する化合物が更に好ましく、５個以上含有する化合物が特に好ましい。上限は、例えば、１５個以下である。エチレン性不飽和基としては、例えば、ビニル基、（メタ）アリル基、及び、（メタ）アクリロイル基等が挙げられる。
As the polymerizable compound, a compound containing an ethylenically unsaturated group is preferable.

That is, the light-shielding composition preferably contains a low-molecular compound containing an ethylenically unsaturated group as a polymerizable compound.

As the polymerizable compound, a compound containing one or more ethylenically unsaturated bonds is preferable, a compound containing two or more ethylenically unsaturated bonds is more preferable, a compound containing three or more ethylenically unsaturated bonds is more preferable, and a compound containing five or more ethylenically unsaturated bonds is particularly preferable. . The upper limit is, for example, 15 or less. Examples of the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.

　重合性化合物としては、例えば、特開２００８－２６０９２７号公報の段落００５０、及び、特開２０１５－６８８９３号公報の段落００４０に記載されている化合物を使用でき、上記の内容は本明細書に組み込まれる。
As the polymerizable compound, for example, the compounds described in paragraph 0050 of JP-A-2008-260927 and paragraph 0040 of JP-A-2015-68893 can be used, and the contents described above are incorporated herein. It is.

　重合性化合物は、例えば、モノマー、プレポリマー、オリゴマー、及び、これらの混合物、並びに、これらの多量体等の化学的形態のいずれであってもよい。

　重合性化合物は、３～１５官能の（メタ）アクリレート化合物が好ましく、３～６官能の（メタ）アクリレート化合物がより好ましい。
The polymerizable compound may be in any of chemical forms such as, for example, monomers, prepolymers, oligomers, and mixtures thereof, and multimers thereof.

The polymerizable compound is preferably a 3-15 functional (meth) acrylate compound, more preferably a 3-6 functional (meth) acrylate compound.

　重合性化合物は、エチレン性不飽和基を１個以上含有する、常圧下で１００℃以上の沸点を持つ化合物も好ましい。例えば、特開２０１３－２９７６０号公報の段落０２２７、特開２００８－２９２９７０号公報の段落０２５４～０２５７に記載の化合物を参酌でき、この内容は本明細書に組み込まれる。
As the polymerizable compound, a compound containing at least one ethylenically unsaturated group and having a boiling point of 100 ° C. or more under normal pressure is also preferable. For example, the compounds described in paragraphs 0227 of JP-A-2013-29760 and paragraphs 0254 to 0257 of JP-A-2008-292970 can be referred to, and the contents thereof are incorporated herein.

　重合性化合物は、ジペンタエリスリトールトリアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬株式会社製）、ジペンタエリスリトールテトラアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬株式会社製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬株式会社製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬株式会社製、Ａ－ＤＰＨ－１２Ｅ；新中村化学株式会社製）、及び、これらの（メタ）アクリロイル基がエチレングリコール残基又はプロピレングリコール残基を介している構造（例えば、サートマー社から市販されている、ＳＲ４５４、ＳＲ４９９）が好ましい。これらのオリゴマータイプも使用できる。また、ＮＫエステルＡ－ＴＭＭＴ（ペンタエリスリトールテトラアクリレート、新中村化学株式会社製）、ＫＡＹＡＲＡＤ　ＲＰ－１０４０、ＫＡＹＡＲＡＤ　ＤＰＥＡ－１２ＬＴ、ＫＡＹＡＲＡＤ　ＤＰＨＡ　ＬＴ、ＫＡＹＡＲＡＤ　ＲＰ－３０６０、及び、ＫＡＹＡＲＡＤ　ＤＰＥＡ－１２（いずれも商品名、日本化薬株式会社製）等を使用してもよい。

　以下に好ましい重合性化合物の態様を示す。
Polymerizable compounds include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available product KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acryloyl groups are mediated by an ethylene glycol residue or a propylene glycol residue (for example, commercially available from Sartomer, SR454 , SR499) No. These oligomer types can also be used. Further, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040, KAYARAD DPEA-12LT, KAYARAD DPHA LT, KAYARAD RP-3060, and KAYARAD DPEA-12 (all products) Name, manufactured by Nippon Kayaku Co., Ltd.).

Preferred embodiments of the polymerizable compound are shown below.

　遮光性組成物は、少なくとも２種の重合性化合物を含有することが好ましい。

　中でも、遮光膜の耐熱性及び耐湿性をより優れる点から、類似の構造を有し、エチレン性不飽和基の数が異なる２種以上の重合性化合物を含有し、かつ、エチレン性不飽和基の個数がより少ない化合物が、少なくとも１個以上の水酸基を含有する化合物であることが好ましい。このような２種以上の重合性化合物を使用することにより、遮光膜の耐熱性及び耐湿性が向上する理由は明らかではないが、水酸基を有する重合性化合物を使用することによって、アルカリ可溶性樹脂との相溶性が向上し、重合性化合物が黒色層中に均一に分布され、黒色層全体が均一に硬化するためと推測される。

　このような、類似の構造を有し、エチレン性不飽和基の数が異なる２種以上の化合物の混合物としては、例えば、後述する式（Ｚ－１）、式（Ｚ－４）又は式（Ｚ－５）で表され、末端に有するエチレン性不飽和基（好ましくは（メタ）アクリロイル基）の数が異なる化合物の混合物であって、エチレン性不飽和基の個数がより少ない化合物が、少なくとも１個以上の水酸基を含有する化合物である混合物が挙げられる。
The light-shielding composition preferably contains at least two kinds of polymerizable compounds.

Among them, from the viewpoint of more excellent heat resistance and moisture resistance of the light-shielding film, it has a similar structure, contains two or more polymerizable compounds having different numbers of ethylenically unsaturated groups, and has an ethylenically unsaturated group. Is preferably a compound containing at least one or more hydroxyl groups. By using such two or more polymerizable compounds, the reason why the heat resistance and moisture resistance of the light-shielding film are improved is not clear, but by using a polymerizable compound having a hydroxyl group, an alkali-soluble resin can be obtained. It is presumed that the compatibility of the polymer was improved, the polymerizable compound was uniformly distributed in the black layer, and the entire black layer was uniformly cured.

Examples of such a mixture of two or more compounds having similar structures and different numbers of ethylenically unsaturated groups include, for example, formulas (Z-1), (Z-4), and ( Z-5), a mixture of compounds having different numbers of terminal ethylenically unsaturated groups (preferably (meth) acryloyl groups), wherein the compound having a smaller number of ethylenically unsaturated groups is at least Mixtures that are compounds containing one or more hydroxyl groups are included.

　重合性化合物は、カルボン酸基、スルホン酸基、及び、リン酸基等の酸基を有していてもよい。酸基を含有する重合性化合物としては、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルが好ましく、脂肪族ポリヒドロキシ化合物の未反応の水酸基に非芳香族カルボン酸無水物を反応させて酸基を持たせた重合性化合物がより好ましく、このエステルにおいて、脂肪族ポリヒドロキシ化合物がペンタエリスリトール及び／又はジペンタエリスリトールである化合物が更に好ましい。市販品としては、例えば、東亞合成社製の、アロニックスＴＯ－２３４９、Ｍ－３０５、Ｍ－５１０、及び、Ｍ－５２０等が挙げられる。
The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. As the polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to form an acid. A polymerizable compound having a group is more preferable, and in this ester, a compound in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol is further preferable. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.

　酸基を含有する重合性化合物の酸価としては、０．１～４０ｍｇＫＯＨ／ｇが好ましく、５～３０ｍｇＫＯＨ／ｇがより好ましい。重合性化合物の酸価が０．１ｍｇＫＯＨ／ｇ以上であれば、現像溶解特性が良好であり、４０ｍｇＫＯＨ／ｇ以下であれば、製造及び／又は取扱い上、有利である。更には、光重合性能が良好で、硬化性に優れる。
The acid value of the polymerizable compound having an acid group is preferably from 0.1 to 40 mgKOH / g, more preferably from 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the developing dissolution property is good, and when the acid value is 40 mgKOH / g or less, it is advantageous in production and / or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

　重合性化合物は、カプロラクトン構造を含有する化合物も好ましい態様である。

　カプロラクトン構造を含有する化合物としては、分子内にカプロラクトン構造を含有する限り特に制限されないが、例えば、トリメチロールエタン、ジトリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、グリセリン、ジグリセロール、又は、トリメチロールメラミン等の多価アルコールと、（メタ）アクリル酸及びε－カプロラクトンとをエステル化して得られる、ε－カプロラクトン変性多官能（メタ）アクリレートが挙げられる。中でも下記式（Ｚ－１）で表されるカプロラクトン構造を含有する化合物が好ましい。
In a preferred embodiment, the polymerizable compound is a compound having a caprolactone structure.

The compound having a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule.For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentayl Ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohol such as erythritol, glycerin, diglycerol, or trimethylolmelamine with (meth) acrylic acid and ε-caprolactone. Among them, a compound having a caprolactone structure represented by the following formula (Z-1) is preferable.

Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017

　式（Ｚ－１）中、６個のＲは全てが下記式（Ｚ－２）で表される基であるか、又は６個のＲのうち１～５個が下記式（Ｚ－２）で表される基であり、残余が下記式（Ｚ－３）で表される基である。
In the formula (Z-1), all six Rs are groups represented by the following formula (Z-2), or 1 to 5 of the six Rs are a group represented by the following formula (Z-2) And the remainder is a group represented by the following formula (Z-3).

Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018

　式（Ｚ－２）中、Ｒ１は水素原子又はメチル基を示し、ｍは１又は２の数を示し、「＊」は結合手を示す。
In the formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents the number of 1 or 2, and “*” represents a bond.

Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019

　式（Ｚ－３）中、Ｒ１は水素原子又はメチル基を示し、「＊」は結合手を示す。）
In Formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and “*” represents a bond. )

　カプロラクトン構造を含有する重合性化合物は、例えば、日本化薬からＫＡＹＡＲＡＤ　ＤＰＣＡシリーズとして市販されており、ＤＰＣＡ－２０（上記式（Ｚ－１）～（Ｚ－３）においてｍ＝１、式（Ｚ－２）で表される基の数＝２、Ｒ１が全て水素原子である化合物）、ＤＰＣＡ－３０（同式、ｍ＝１、式（Ｚ－２）で表される基の数＝３、Ｒ１が全て水素原子である化合物）、ＤＰＣＡ－６０（同式、ｍ＝１、式（Ｚ－２）で表される基の数＝６、Ｒ１が全て水素原子である化合物）、及び、ＤＰＣＡ－１２０（同式においてｍ＝２、式（Ｚ－２）で表される基の数＝６、Ｒ１が全て水素原子である化合物）等が挙げられる。また、カプロラクトン構造を含有する重合性化合物の市販品としては、東亞合成株式会社製Ｍ－３５０（商品名）（トリメチロールプロパントリアクリレート）も挙げられる。
A polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku as the KAYARAD DPCA series, for example, DPCA-20 (m = 1 in the above formulas (Z-1) to (Z-3), and the formula (Z -2) = 2, compounds in which all R 1 are hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (Z-2) = 3) compound R 1 are all hydrogen atoms), DPCA-60 (the equation, m = 1, the formula (Z-2) compound number = 6, R 1 of the groups represented by are all hydrogen atoms), And DPCA-120 (a compound in which m = 2, the number of groups represented by the formula (Z-2) = 6, and all R 1 are hydrogen atoms). Commercially available polymerizable compounds having a caprolactone structure include M-350 (trade name) (trimethylolpropane triacrylate) manufactured by Toagosei Co., Ltd.

　重合性化合物は、下記式（Ｚ－４）又は（Ｚ－５）で表される化合物も使用できる。
As the polymerizable compound, a compound represented by the following formula (Z-4) or (Z-5) can also be used.

Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020

　式（Ｚ－４）及び（Ｚ－５）中、Ｅは、－（（ＣＨ２）ｙＣＨ２Ｏ）－、又は（（ＣＨ２）ｙＣＨ（ＣＨ３）Ｏ）－を表し、ｙは、０～１０の整数を表し、Ｘは、（メタ）アクリロイル基、水素原子、又はカルボン酸基を表す。

　式（Ｚ－４）中、（メタ）アクリロイル基の合計は３個又は４個であり、ｍは０～１０の整数を表し、各ｍの合計は０～４０の整数である。

　式（Ｚ－５）中、（メタ）アクリロイル基の合計は５個又は６個であり、ｎは０～１０の整数を表し、各ｎの合計は０～６０の整数である。
In the formulas (Z-4) and (Z-5), E represents — ((CH 2 ) y CH 2 O) — or ((CH 2 ) y CH (CH 3 ) O) —, and y is , 0 to 10, and X represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.

In the formula (Z-4), the total number of the (meth) acryloyl groups is 3 or 4, m represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40.

In the formula (Z-5), the total number of the (meth) acryloyl groups is 5 or 6, and n represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.

　式（Ｚ－４）中、ｍは、０～６の整数が好ましく、０～４の整数がより好ましい。

　また、各ｍの合計は、２～４０の整数が好ましく、２～１６の整数がより好ましく、４～８の整数が更に好ましい。

　式（Ｚ－５）中、ｎは、０～６の整数が好ましく、０～４の整数がより好ましい。

　また、各ｎの合計は、３～６０の整数が好ましく、３～２４の整数がより好ましく、６～１２の整数が更に好ましい。

　また、式（Ｚ－４）又は式（Ｚ－５）中の－（（ＣＨ２）ｙＣＨ２Ｏ）－又は（（ＣＨ２）ｙＣＨ（ＣＨ３）Ｏ）－は、酸素原子側の末端がＸに結合する形態が好ましい。
In the formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.

Further, the sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and further preferably an integer of 4 to 8.

In the formula (Z-5), n is preferably an integer of 0 to 6, more preferably 0 to 4.

Further, the sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and further preferably an integer of 6 to 12.

In the formula (Z-4) or the formula (Z-5),-((CH 2 ) y CH 2 O)-or ((CH 2 ) y CH (CH 3 ) O)- A form in which the terminal is bonded to X is preferred.

　式（Ｚ－４）又は式（Ｚ－５）で表される化合物は１種単独で用いてもよいし、２種以上併用してもよい。特に、式（Ｚ－５）において、６個のＸ全てがアクリロイル基である形態、式（Ｚ－５）において、６個のＸ全てがアクリロイル基である化合物と、６個のＸのうち、少なくとも１個が水素原子である化合物との混合物である態様が好ましい。このような構成により、遮光膜の耐熱性及び耐湿性をより向上できると共に、現像性をより向上できる。
The compound represented by the formula (Z-4) or (Z-5) may be used alone or in combination of two or more. In particular, in Formula (Z-5), a form in which all six Xs are acryloyl groups, in Formula (Z-5), a compound in which all six Xs are acryloyl groups, A preferred embodiment is a mixture with a compound in which at least one is a hydrogen atom. With such a configuration, the heat resistance and the moisture resistance of the light-shielding film can be further improved, and the developability can be further improved.

　また、式（Ｚ－４）又は式（Ｚ－５）で表される化合物の重合性化合物中における全含有量としては、２０質量％以上が好ましく、５０質量％以上がより好ましい。

　式（Ｚ－４）又は式（Ｚ－５）で表される化合物の中でも、ペンタエリスリトール誘導体及び／又はジペンタエリスリトール誘導体がより好ましい。
The total content of the compound represented by the formula (Z-4) or the formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.

Among the compounds represented by the formula (Z-4) or (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.

　また、重合性化合物は、カルド骨格を含有してもよい。

　カルド骨格を含有する重合性化合物としては、９，９－ビスアリールフルオレン骨格を含有する重合性化合物が好ましい。

　カルド骨格を含有する重合性化合物としては、制限されないが、例えば、オンコートＥＸシリーズ（長瀬産業社製）及びオグソール（大阪ガスケミカル社製）等が挙げられる。

　重合性化合物は、イソシアヌル酸骨格を中心核として含有する化合物も好ましい。このような重合性化合物の例としては、例えば、ＮＫエステルＡ－９３００（新中村化学株式会社製）が挙げられる。

　重合性化合物のエチレン性不飽和基の含有量（重合性化合物中のエチレン性不飽和基の数を、重合性化合物の分子量（ｇ／ｍｏｌ）で除した値を意味する）は５．０ｍｍｏｌ／ｇ以上が好ましい。上限は特に制限されないが、一般に、２０．０ｍｍｏｌ／ｇ以下である。
Further, the polymerizable compound may contain a cardo skeleton.

As the polymerizable compound having a cardo skeleton, a polymerizable compound having a 9,9-bisarylfluorene skeleton is preferable.

Examples of the polymerizable compound having a cardo skeleton include, but are not limited to, Oncoat EX series (manufactured by Nagase & Co., Ltd.) and Ogusol (manufactured by Osaka Gas Chemical Company).

As the polymerizable compound, a compound containing an isocyanuric acid skeleton as a central nucleus is also preferable. Examples of such a polymerizable compound include, for example, NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

The content of the ethylenically unsaturated group in the polymerizable compound (meaning the value obtained by dividing the number of ethylenically unsaturated groups in the polymerizable compound by the molecular weight (g / mol) of the polymerizable compound) is 5.0 mmol / g or more is preferable. The upper limit is not particularly limited, but is generally 20.0 mmol / g or less.

＜重合開始剤＞

　遮光性組成物は、重合開始剤を含有することが好ましい。

　重合開始剤としては、特に制限されず、公知の重合開始剤を使用できる。重合開始剤としては、例えば、光重合開始剤、及び、熱重合開始剤等が挙げられ、光重合開始剤が好ましい。なお、重合開始剤としては、いわゆるラジカル重合開始剤が好ましい。

　組成物中における重合開始剤の含有量としては特に制限されないが、組成物の全固形分に対して０．５～２０質量％が好ましく、１．０～１０質量％がより好ましく、１．５～８質量％が更に好ましい。重合開始剤は、１種を単独で用いても、２種以上を併用してもよい。２種以上の重合開始剤を併用する場合には、合計含有量が上記範囲内であることが好ましい。
<Polymerization initiator>

The light-shielding composition preferably contains a polymerization initiator.

The polymerization initiator is not particularly limited, and a known polymerization initiator can be used. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, and a photopolymerization initiator is preferable. In addition, what is called a radical polymerization initiator is preferable as a polymerization initiator.

The content of the polymerization initiator in the composition is not particularly limited, but is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, and more preferably 1.5 to 10% by mass based on the total solid content of the composition. -8% by mass is more preferred. One type of polymerization initiator may be used alone, or two or more types may be used in combination. When two or more polymerization initiators are used in combination, the total content is preferably within the above range.

（熱重合開始剤）

　熱重合開始剤としては、例えば、２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ）、３－カルボキシプロピオニトリル、アゾビスマレノニトリル、及び、ジメチル－（２，２’）－アゾビス（２－メチルプロピオネート）［Ｖ－６０１］等のアゾ化合物、並びに、過酸化ベンゾイル、過酸化ラウロイル、及び、過硫酸カリウム等の有機過酸化物が挙げられる。

　重合開始剤の具体例としては、例えば、加藤清視著「紫外線硬化システム」（株式会社総合技術センター発行：平成元年）の第６５～１４８頁に記載されている重合開始剤等を挙げられる。
(Thermal polymerization initiator)

Examples of the thermal polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalenonitrile, and dimethyl- (2,2 ′)-azobis (2 -Methylpropionate) [V-601], and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.

Specific examples of the polymerization initiator include, for example, polymerization initiators described in “Ultraviolet Curing System” by Kiyomi Kato (published by Sogo Gijutsu Center, pp. 65-148). .

（光重合開始剤）

　上記組成物は光重合開始剤を含有することが好ましい。

　光重合開始剤としては、重合性化合物の重合を開始できれば特に制限されず、公知の光重合開始剤を使用できる。光重合開始剤としては、例えば、紫外線領域から可視光領域に対して感光性を有する光重合開始剤が好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよく、重合性化合物の種類に応じてカチオン重合を開始させるような開始剤であってもよい。

　また、光重合開始剤は、３００～８００ｎｍ（３３０～５００ｎｍがより好ましい。）の範囲内に少なくとも５０のモル吸光係数を有する化合物を、少なくとも１種含有していることが好ましい。
(Photopolymerization initiator)

The composition preferably contains a photopolymerization initiator.

The photopolymerization initiator is not particularly limited as long as the polymerization of the polymerizable compound can be started, and a known photopolymerization initiator can be used. As the photopolymerization initiator, for example, a photopolymerization initiator having photosensitivity from an ultraviolet region to a visible light region is preferable. Further, an activator that generates an active radical by causing some action with the photoexcited sensitizer may be used, or an initiator that starts cationic polymerization depending on the type of the polymerizable compound may be used.

Further, the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least 50 in the range of 300 to 800 nm (more preferably 330 to 500 nm).

　組成物中における光重合開始剤の含有量としては特に制限されないが、組成物の全固形分に対して、０．５～２０質量％が好ましく、１．０～１０質量％がより好ましく、１．５～８質量％が更に好ましい。光重合開始剤は、１種を単独で用いても、２種以上を併用してもよい。２種以上の光重合開始剤を併用する場合には、合計含有量が上記範囲内であることが好ましい。
The content of the photopolymerization initiator in the composition is not particularly limited, but is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, based on the total solid content of the composition. More preferably, it is from 0.5 to 8% by mass. One photopolymerization initiator may be used alone, or two or more photopolymerization initiators may be used in combination. When two or more photopolymerization initiators are used in combination, the total content is preferably within the above range.

　光重合開始剤としては、例えば、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を含有する化合物、オキサジアゾール骨格を含有する化合物、等）、アシルホスフィンオキサイド等のアシルホスフィン化合物、ヘキサアリールビイミダゾール、オキシム誘導体等のオキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、アミノアセトフェノン化合物、及び、ヒドロキシアセトフェノン等が挙げられる。

　光重合開始剤の具体例としては、例えば、特開２０１３－２９７６０号公報の段落０２６５～０２６８を参酌でき、この内容は本明細書に組み込まれる。
Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, Examples include oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenone.

As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated herein.

　光重合開始剤としては、より具体的には、例えば、特開平１０－２９１９６９号公報に記載のアミノアセトフェノン系開始剤、及び特許第４２２５８９８号公報に記載のアシルホスフィンオキシド系開始剤も使用できる。

　ヒドロキシアセトフェノン化合物としては、例えば、ＩＲＧＡＣＵＲＥ－１８４、ＤＡＲＯＣＵＲ－１１７３、ＩＲＧＡＣＵＲＥ－５００、ＩＲＧＡＣＵＲＥ－２９５９、及び、ＩＲＧＡＣＵＲＥ－１２７（商品名、いずれもＢＡＳＦ社製）を使用できる。

　アミノアセトフェノン化合物としては、例えば、市販品であるＩＲＧＡＣＵＲＥ－９０７、ＩＲＧＡＣＵＲＥ－３６９、及び、ＩＲＧＡＣＵＲＥ－３７９ＥＧ（商品名、いずれもＢＡＳＦ社製）を使用できる。アミノアセトフェノン化合物としては、波長３６５ｎｍ又は波長４０５ｎｍ等の長波光源に吸収波長がマッチングされた特開２００９－１９１１７９公報に記載の化合物も使用できる。

　アシルホスフィン化合物としては、市販品であるＩＲＧＡＣＵＲＥ－８１９、及び、ＩＲＧＡＣＵＲＥ－ＴＰＯ（商品名、いずれもＢＡＳＦ社製）を使用できる。
More specifically, as the photopolymerization initiator, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used.

As the hydroxyacetophenone compound, for example, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF) can be used.

As the aminoacetophenone compound, for example, commercially available products IRGACURE-907, IRGACURE-369 and IRGACURE-379EG (trade names, all manufactured by BASF) can be used. As the aminoacetophenone compound, a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long-wavelength light source having a wavelength of 365 nm or 405 nm can also be used.

As the acylphosphine compound, commercially available products IRGACURE-819 and IRGACURE-TPO (trade names, both manufactured by BASF) can be used.

・オキシム化合物

　光重合開始剤として、オキシムエステル系重合開始剤（オキシム化合物）がより好ましい。特にオキシム化合物は高感度で重合効率が高く、組成物中における色材の含有量を高く設計しやすいため好ましい。

　オキシム化合物の具体例としては、特開２００１－２３３８４２号公報に記載の化合物、特開２０００－８００６８号公報に記載の化合物、又は、特開２００６－３４２１６６号公報に記載の化合物を使用できる。

　オキシム化合物としては、例えば、３－ベンゾイロキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイロキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、及び、２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オン等が挙げられる。

　また、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年）ｐｐ．１６５３－１６６０）、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年）ｐｐ．１５６－１６２、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５年）ｐｐ．２０２－２３２、特開２０００－６６３８５号公報に記載の化合物、特開２０００－８００６８号公報、特表２００４－５３４７９７号公報、及び、特開２００６－３４２１６６号公報に記載の化合物等も挙げられる。

　市販品ではＩＲＧＡＣＵＲＥ－ＯＸＥ０１（ＢＡＳＦ社製）、ＩＲＧＡＣＵＲＥ－ＯＸＥ０２（ＢＡＳＦ社製）、ＩＲＧＡＣＵＲＥ－ＯＸＥ０３（ＢＡＳＦ社製）、又は、ＩＲＧＡＣＵＲＥ－ＯＸＥ０４（ＢＡＳＦ社製）も好ましい。また、ＴＲ－ＰＢＧ－３０４（常州強力電子新材料有限公司製）、アデカアークルズＮＣＩ－８３１、アデカアークルズＮＣＩ－９３０（ＡＤＥＫＡ社製）、又は、Ｎ－１９１９（カルバゾール・オキシムエステル骨格含有光開始剤（ＡＤＥＫＡ社製）も使用できる。
・ Oxime compounds

As the photopolymerization initiator, an oxime ester-based polymerization initiator (oxime compound) is more preferable. In particular, oxime compounds are preferable because they have high sensitivity and high polymerization efficiency, and the content of the coloring material in the composition is easy to design.

As specific examples of the oxime compound, compounds described in JP-A-2001-233842, compounds described in JP-A-2000-80068, and compounds described in JP-A-2006-342166 can be used.

Examples of the oxime compound include 3-benzoyloximinobtan-2-one, 3-acetoxyimiminobtan-2-one, 3-propionyloxyimiminobtan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxy Carbonyloxyimino-1-phenylpropan-1-one and the like.

Also, J.I. C. S. Perkin II (1979) pp. 1653-1660); C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A-2000-66385, compounds described in JP-A-2000-80068, JP-T-2004-534797, and JP-A-2006-342166.

Among commercially available products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), or IRGACURE-OXE04 (manufactured by BASF) is also preferable. Also, TR-PBG-304 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), Adeka Aquel's NCI-831, Adeka Aquel's NCI-930 (manufactured by ADEKA) or N-1919 (a carbazole / oxime ester skeleton-containing light) Initiators (ADEKA) can also be used.

　また上記記載以外のオキシム化合物として、カルバゾールＮ位にオキシムが連結した特表２００９－５１９９０４号公報に記載の化合物；ベンゾフェノン部位にヘテロ置換基が導入された米国特許第７６２６９５７号公報に記載の化合物；色素部位にニトロ基が導入された特開２０１０－１５０２５号公報及び米国特許公開２００９－２９２０３９号明細書に記載の化合物；国際公開第２００９－１３１１８９号パンフレットに記載のケトオキシム化合物；及び、トリアジン骨格とオキシム骨格を同一分子内に含有する米国特許７５５６９１０号明細書に記載の化合物；４０５ｎｍに極大吸収を有しｇ線光源に対して良好な感度を有する特開２００９－２２１１１４号公報に記載の化合物；等を用いてもよい。

　例えば、特開２０１３－２９７６０号公報の段落０２７４～０２７５を参酌でき、この内容は本明細書に組み込まれる。

　具体的には、オキシム化合物としては、下記式（ＯＸ－１）で表される化合物が好ましい。なお、オキシム化合物のＮ－Ｏ結合が（Ｅ）体のオキシム化合物であっても、（Ｚ）体のオキシム化合物であっても、（Ｅ）体と（Ｚ）体との混合物であってもよい。
Other oxime compounds other than those described above include compounds described in JP-T-2009-519904 in which an oxime is linked to the carbazole N-position; compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety; Compounds described in JP-A-2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into a dye site; ketoxime compounds described in WO 2009-131189; and a triazine skeleton A compound described in US Pat. No. 7,556,910 containing an oxime skeleton in the same molecule; a compound described in JP-A-2009-221114 having a maximum absorption at 405 nm and having good sensitivity to a g-line light source; Etc. may be used.

For example, paragraphs 0274 to 0275 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated in the present specification.

Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferable. It should be noted that the NO bond of the oxime compound may be an (E) -form oxime compound, a (Z) -form oxime compound, or a mixture of (E) -form and (Z) -form. Good.

Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021

　式（ＯＸ－１）中、Ｒ及びＢはそれぞれ独立に１価の置換基を表し、Ａは２価の有機基を表し、Ａｒはアリール基を表す。

　式（ＯＸ－１）中、Ｒで表される１価の置換基としては、１価の非金属原子団が好ましい。

　１価の非金属原子団としては、アルキル基、アリール基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、複素環基、アルキルチオカルボニル基、及び、アリールチオカルボニル基等が挙げられる。また、これらの基は、１以上の置換基を有していてもよい。また、前述した置換基は、更に他の置換基で置換されていてもよい。

　置換基としてはハロゲン原子、アリールオキシ基、アルコキシカルボニル基又はアリールオキシカルボニル基、アシルオキシ基、アシル基、アルキル基、及び、アリール基等が挙げられる。

　式（ＯＸ－１）中、Ｂで表される１価の置換基としては、アリール基、複素環基、アリールカルボニル基、又は、複素環カルボニル基が好ましく、アリール基、又は、複素環基が好ましい。これらの基は１以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。

　式（ＯＸ－１）中、Ａで表される２価の有機基としては、炭素数１～１２のアルキレン基、シクロアルキレン基、又は、アルキニレン基が好ましい。これらの基は１以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。
In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.

Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Further, these groups may have one or more substituents. Further, the above-mentioned substituent may be further substituted with another substituent.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

In Formula (OX-1), as the monovalent substituent represented by B, an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group is preferable, and an aryl group or a heterocyclic group is preferable. preferable. These groups may have one or more substituents. Examples of the substituent include the substituents described above.

In Formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the substituents described above.

　光重合開始剤として、フッ素原子を含有するオキシム化合物も使用できる。フッ素原子を含有するオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報に記載の化合物；特表２０１４－５００８５２号公報に記載の化合物２４、３６～４０；及び、特開２０１３－１６４４７１号公報に記載の化合物（Ｃ－３）；等が挙げられる。この内容は本明細書に組み込まれる。
Oxime compounds containing a fluorine atom can also be used as the photopolymerization initiator. Specific examples of fluorine-containing oxime compounds include compounds described in JP-A-2010-262028; compounds 24, 36 to 40 described in JP-A-2014-500852; and JP-A-2013-164471. Compound (C-3) described in the gazette; and the like. This content is incorporated herein.

　光重合開始剤として、下記一般式（１）～（４）で表される化合物も使用できる。
As the photopolymerization initiator, compounds represented by the following general formulas (1) to (4) can also be used.

Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022

Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023

　式（１）において、Ｒ１及びＲ２は、それぞれ独立に、炭素数１～２０のアルキル基、炭素数４～２０の脂環式炭化水素基、炭素数６～３０のアリール基、又は、炭素数７～３０のアリールアルキル基を表し、Ｒ１及びＲ２がフェニル基の場合、フェニル基同士が結合してフルオレン基を形成してもよく、Ｒ３及びＲ４は、それぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基又は炭素数４～２０の複素環基を表し、Ｘは、直接結合又はカルボニル基を示す。
In the formula (1), R 1 and R 2 each independently represent an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or When R 1 and R 2 are a phenyl group, the phenyl groups may combine with each other to form a fluorene group, and R 3 and R 4 each independently represent a fluorene group. X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms; Represents a group.

　式（２）において、Ｒ１、Ｒ２、Ｒ３、及び、Ｒ４は、式（１）におけるＲ１、Ｒ２、Ｒ３、及び、Ｒ４と同義であり、Ｒ５は、－Ｒ６、－ＯＲ６、－ＳＲ６、－ＣＯＲ６、－ＣＯＮＲ６Ｒ６、－ＮＲ６ＣＯＲ６、－ＯＣＯＲ６、－ＣＯＯＲ６、－ＳＣＯＲ６、－ＯＣＳＲ６、－ＣＯＳＲ６、－ＣＳＯＲ６、－ＣＮ、ハロゲン原子、又は、水酸基を表し、Ｒ６は、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基、又は、炭素数４～２０の複素環基を表し、Ｘは、直接結合又はカルボニル基を表し、ａは０～４の整数を表す。
In the formula (2), R 1, R 2, R 3 and, R 4 is, R 1, R 2, R 3 in the formula (1), and has the same meaning as R 4, R 5 are, -R 6 , -OR 6 , -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6 , -COSR 6 , -CSOR 6 , —CN represents a halogen atom or a hydroxyl group, and R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a C 4 to C 4 20 represents a heterocyclic group, X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.

　式（３）において、Ｒ１は、炭素数１～２０のアルキル基、炭素数４～２０の脂環式炭化水素基、炭素数６～３０のアリール基、又は、炭素数７～３０のアリールアルキル基を表し、Ｒ３及びＲ４は、それぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基、又は、炭素数４～２０の複素環基を表し、Ｘは、直接結合又はカルボニル基を示す。
In the formula (3), R 1 represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms. R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, Represents a heterocyclic group represented by Formulas 4 to 20, and X represents a direct bond or a carbonyl group.

　式（４）において、Ｒ１、Ｒ３、及び、Ｒ４は、式（３）におけるＲ１、Ｒ３、及び、Ｒ４と同義であり、Ｒ５は、－Ｒ６、－ＯＲ６、－ＳＲ６、－ＣＯＲ６、－ＣＯＮＲ６Ｒ６、－ＮＲ６ＣＯＲ６、－ＯＣＯＲ６、－ＣＯＯＲ６、－ＳＣＯＲ６、－ＯＣＳＲ６、－ＣＯＳＲ６、－ＣＳＯＲ６、－ＣＮ、ハロゲン原子、又は、水酸基を表し、Ｒ６は、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基、又は、炭素数４～２０の複素環基を表し、Ｘは、直接結合又はカルボニル基を表し、ａは０～４の整数を表す。
In the formula (4), R 1, R 3 and, R 4 is, R 1, R 3 in the formula (3), and has the same meaning as R 4, R 5 are, -R 6, -OR 6, -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6 , -COSR 6 , -COR 6 , -CN, halogen atom, Or a hydroxyl group, and R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms. X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.

　上記式（１）及び（２）において、Ｒ１及びＲ２は、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、シクロヘキシル基、又は、フェニル基が好ましい。Ｒ３はメチル基、エチル基、フェニル基、トリル基、又は、キシリル基が好ましい。Ｒ４は炭素数１～６のアルキル基又はフェニル基が好ましい。Ｒ５はメチル基、エチル基、フェニル基、トリル基、又は、ナフチル基が好ましい。Ｘは直接結合が好ましい。

　また、上記式（３）及び（４）において、Ｒ１は、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、シクロヘキシル基、又は、フェニル基が好ましい。Ｒ３はメチル基、エチル基、フェニル基、トリル基、又は、キシリル基が好ましい。Ｒ４は炭素数１～６のアルキル基、又は、フェニル基が好ましい。Ｒ５はメチル基、エチル基、フェニル基、トリル基、又は、ナフチル基が好ましい。Ｘは直接結合が好ましい。

　式（１）及び式（２）で表される化合物の具体例としては、例えば、特開２０１４－１３７４６６号公報の段落００７６～００７９に記載された化合物が挙げられる。この内容は本明細書に組み込まれる。
In the above formulas (1) and (2), R 1 and R 2 are preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xylyl group. R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a naphthyl group. X is preferably a direct bond.

In the above formulas (3) and (4), R 1 is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xylyl group. R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a naphthyl group. X is preferably a direct bond.

Specific examples of the compounds represented by the formulas (1) and (2) include the compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated herein.

　上記組成物に好ましく使用されるオキシム化合物の具体例を以下に示す。以下に示すオキシム化合物の中でも、式（Ｃ－１３）で表されるオキシム化合物がより好ましい。

　また、オキシム化合物としては、国際公開第２０１５－０３６９１０号パンフレットのＴａｂｌｅ１に記載の化合物も使用でき、上記の内容は本明細書に組み込まれる。
Specific examples of the oxime compound preferably used in the above composition are shown below. Among the oxime compounds shown below, the oxime compound represented by the formula (C-13) is more preferable.

Further, as the oxime compound, the compound described in Table 1 of International Publication No. 2015-036910 Pamphlet can also be used, and the above description is incorporated herein.

Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025

　オキシム化合物は、３５０～５００ｎｍの波長領域に極大吸収波長を有することが好ましく、３６０～４８０ｎｍの波長領域に極大吸収波長を有することがより好ましく、３６５ｎｍ及び４０５ｎｍの波長の吸光度が高いことが更に好ましい。

　オキシム化合物の３６５ｎｍ又は４０５ｎｍにおけるモル吸光係数は、感度の点から、１，０００～３００，０００が好ましく、２，０００～３００，０００がより好ましく、５，０００～２００，０００が更に好ましい。

　化合物のモル吸光係数は、公知の方法を使用できるが、例えば、紫外可視分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチルを用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。

　光重合開始剤は、必要に応じて２種以上を組み合わせて使用してもよい。
The oxime compound preferably has a maximum absorption wavelength in a wavelength region of 350 to 500 nm, more preferably has a maximum absorption wavelength in a wavelength region of 360 to 480 nm, and further preferably has high absorbance at wavelengths of 365 nm and 405 nm. .

The molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, and still more preferably from 5,000 to 200,000, from the viewpoint of sensitivity.

The molar extinction coefficient of the compound can be measured by a known method. For example, the molar extinction coefficient is measured at a concentration of 0.01 g / L using ethyl acetate with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian). Is preferred.

Photopolymerization initiators may be used in combination of two or more as necessary.

　また、光重合開始剤としては、特開第２００８－２６０９２７号公報の段落００５２、特開第２０１０－９７２１０号公報の段落００３３～００３７、特開第２０１５－６８８９３号公報の段落００４４に記載の化合物も使用でき、上記の内容は本明細書に組み込まれる。
Examples of the photopolymerization initiator include compounds described in paragraph 0052 of JP-A-2008-260927, paragraphs 0033 to 0037 of JP-A-2010-97210, and paragraph 0044 of JP-A-2015-68893. Can also be used, and the above is incorporated herein.

＜重合禁止剤＞

　組成物は、重合禁止剤を含有してもよい。

　重合禁止剤としては特に制限されず、公知の重合禁止剤を使用できる。重合禁止剤としては、例えば、フェノール系重合禁止剤（例えば、ｐ－メトキシフェノール、２，５－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、２，６－ジｔｅｒｔ－ブチル－４－メチルフェノール、４，４’－チオビス（３－メチル－６－ｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、４－メトキシナフトール等）；ハイドロキノン系重合禁止剤（例えば、ハイドロキノン、２，６－ジ－ｔｅｒｔ－ブチルハイドロキノン等）；キノン系重合禁止剤（例えば、ベンゾキノン等）；フリーラジカル系重合禁止剤（例えば、２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル等）；ニトロベンゼン系重合禁止剤（例えば、ニトロベンゼン、４－ニトロトルエン等）；及び、フェノチアジン系重合禁止剤（例えば、フェノチアジン、２－メトキシフェノチアジン等）；等が挙げられる。

　中でも、組成物がより優れた効果を有する点で、フェノール系重合禁止剤、又は、フリーラジカル系重合禁止剤が好ましい。
<Polymerization inhibitor>

The composition may contain a polymerization inhibitor.

The polymerization inhibitor is not particularly limited, and a known polymerization inhibitor can be used. Examples of the polymerization inhibitor include phenol-based polymerization inhibitors (eg, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-ditert-butyl-4-methylphenol, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4-methoxynaphthol and the like; hydroquinone-based polymerization inhibitors (for example, Quinone-based polymerization inhibitors (eg, benzoquinone); free-radical polymerization inhibitors (eg, 2,2,6,6-tetramethylpiperidine 1-). Oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, etc. ; Nitrobenzene-based polymerization inhibitor (e.g., nitrobenzene, 4-nitrotoluene, etc.); and phenothiazine-based polymerization inhibitor (e.g., phenothiazine, 2-methoxy phenothiazine, etc.), and the like.

Above all, a phenol-based polymerization inhibitor or a free radical-based polymerization inhibitor is preferable in that the composition has a more excellent effect.

　重合禁止剤は、硬化性基を含有する樹脂と共に用いる場合にその効果が顕著である。

　組成物中における重合禁止剤の含有量としては特に制限されないが、組成物の全固形分に対して、０．０００１～０．５質量％が好ましく、０．００１～０．２質量％がより好ましく、０．００８～０．０５質量％が更に好ましい。重合禁止剤は、１種を単独で用いても、２種以上を併用してもよい。２種以上の重合禁止剤を併用する場合には、合計含有量が上記範囲内であることが好ましい。

　また、組成物中の重合性化合物の含有量に対する、重合禁止剤の含有量の比（重合禁止剤の含有量／重合性化合物の含有量（質量比））は、０．０００５超が好ましく、０．０００６～０．０２がより好ましく、０．０００６～０．００５が更に好ましい。
The effect of the polymerization inhibitor is remarkable when it is used together with a resin containing a curable group.

The content of the polymerization inhibitor in the composition is not particularly limited, but is preferably 0.0001 to 0.5% by mass, more preferably 0.001 to 0.2% by mass, based on the total solid content of the composition. It is more preferably 0.008 to 0.05% by mass. As the polymerization inhibitor, one type may be used alone, or two or more types may be used in combination. When two or more polymerization inhibitors are used in combination, the total content is preferably within the above range.

Further, the ratio of the content of the polymerization inhibitor to the content of the polymerizable compound in the composition (content of the polymerization inhibitor / content of the polymerizable compound (mass ratio)) is preferably more than 0.0005, 0.0006 to 0.02 is more preferable, and 0.0006 to 0.005 is still more preferable.

＜紫外線吸収剤＞

　組成物は、紫外線吸収剤を含有してもよい。これにより、黒色層のパターンの形状をより優れた（精細な）形状にできる。

　紫外線吸収剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、及び、トリアジン系の紫外線吸収剤を使用できる。これらの具体例としては、特開２０１２－０６８４１８号公報の段落０１３７～０１４２（対応するＵＳ２０１２／００６８２９２の段落０２５１～０２５４）の化合物が使用でき、これらの内容が援用でき、本明細書に組み込まれる。

　他にジエチルアミノ－フェニルスルホニル系紫外線吸収剤（大東化学社製、商品名、ＵＶ－５０３）等も好適に用いられる。

　紫外線吸収剤としては、特開２０１２－３２５５６号公報の段落０１３４～０１４８に例示される化合物が挙げられる。

　紫外線吸収剤の含有量は、組成物の全固形分に対して、０．００１～１５質量％が好ましく、０．０１～１０質量％がより好ましく、０．１～５質量％が更に好ましい。
<Ultraviolet absorber>

The composition may contain an ultraviolet absorber. Thereby, the shape of the pattern of the black layer can be made more excellent (fine).

As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. As specific examples thereof, compounds described in paragraphs 0137 to 0142 of JP-A-2012-068418 (corresponding to paragraphs 0251 to 0254 of US2012 / 0068292) can be used, and the contents thereof can be referred to and incorporated herein. .

In addition, a diethylamino-phenylsulfonyl-based ultraviolet absorber (trade name, UV-503, manufactured by Daito Chemical Co., Ltd.) and the like are also preferably used.

Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP-A-2012-32556.

The content of the ultraviolet absorbent is preferably from 0.001 to 15% by mass, more preferably from 0.01 to 10% by mass, even more preferably from 0.1 to 5% by mass, based on the total solid content of the composition.

＜シランカップリング剤（密着剤）＞

　組成物はシランカップリング剤を含有してもよい。シランカップリング剤は、基板上に黒色層を形成する際に、基板と黒色層間の密着性を向上させる密着剤として機能する。

　シランカップリング剤とは、分子中に加水分解性基とそれ以外の官能基とを含有する化合物である。なお、アルコキシ基等の加水分解性基は、珪素原子に結合している。

　加水分解性基とは、珪素原子に直結し、加水分解反応及び／又は縮合反応によってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基、及び、アルケニルオキシ基が挙げられる。加水分解性基が炭素原子を含有する場合、その炭素数は６以下が好ましく、４以下がより好ましい。特に、炭素数４以下のアルコキシ基又は炭素数４以下のアルケニルオキシ基が好ましい。
<Silane coupling agent (adhesive)>

The composition may contain a silane coupling agent. The silane coupling agent functions as an adhesive for improving the adhesion between the substrate and the black layer when forming the black layer on the substrate.

The silane coupling agent is a compound containing a hydrolyzable group and other functional groups in the molecule. Note that a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.

The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group contains a carbon atom, the number of carbon atoms is preferably 6 or less, more preferably 4 or less. Particularly, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.

　また、基板上に黒色層を形成する場合に、シランカップリング剤は基板と黒色層間の密着性を向上させるため、フッ素原子及び珪素原子（ただし、加水分解性基が結合した珪素原子は除く）を含まないことが好ましく、フッ素原子、珪素原子（ただし、加水分解性基が結合した珪素原子は除く）、珪素原子で置換されたアルキレン基、炭素数８以上の直鎖状アルキル基、及び、炭素数３以上の分岐鎖状アルキル基は含まないことが望ましい。

　シランカップリング剤は、（メタ）アクリロイル基等のエチレン性不飽和基を含有してもよい。エチレン性不飽和基を含有する場合、その数は１～１０個が好ましく、４～８個がより好ましい。なお、エチレン性不飽和基を含有するシランカップリング剤（例えば、加水分解性基とエチレン性不飽和基とを含有する、分子量２０００以下の化合物）は、上述の重合性化合物に該当しない。
When a black layer is formed on the substrate, the silane coupling agent improves the adhesion between the substrate and the black layer, so that a fluorine atom and a silicon atom (excluding a silicon atom to which a hydrolyzable group is bonded) are used. It is preferable not to contain a fluorine atom, a silicon atom (however, a silicon atom to which a hydrolyzable group is bonded), an alkylene group substituted by a silicon atom, a linear alkyl group having 8 or more carbon atoms, and It is desirable not to include a branched alkyl group having 3 or more carbon atoms.

The silane coupling agent may contain an ethylenically unsaturated group such as a (meth) acryloyl group. When an ethylenically unsaturated group is contained, the number is preferably 1 to 10, more preferably 4 to 8. Note that a silane coupling agent containing an ethylenically unsaturated group (for example, a compound containing a hydrolyzable group and an ethylenically unsaturated group and having a molecular weight of 2000 or less) does not correspond to the above-described polymerizable compound.

　上記組成物中におけるシランカップリング剤の含有量は、組成物中の全固形分に対して、０．１～１０質量％が好ましく、０．５～８質量％がより好ましく、１．０～６質量％が更に好ましい。

　上記組成物は、シランカップリング剤を１種単独で含んでいてもよく、２種以上を含んでいてもよい。組成物がシランカップリング剤を２種以上含有する場合は、その合計が上記範囲内であればよい。
The content of the silane coupling agent in the composition is preferably from 0.1 to 10% by mass, more preferably from 0.5 to 8% by mass, and more preferably from 1.0 to 10% by mass, based on the total solids in the composition. 6% by mass is more preferred.

The composition may contain one kind of the silane coupling agent alone, or may contain two or more kinds. When the composition contains two or more silane coupling agents, the total may be within the above range.

　シランカップリング剤としては、例えば、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、ビニルトリメトキシシラン、及び、ビニルトリエトキシシラン等が挙げられる。
Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, Vinyl trimethoxy silane, vinyl triethoxy silane and the like can be mentioned.

＜界面活性剤＞

　組成物は、界面活性剤を含有してもよい。界面活性剤は、組成物の塗布性向上に寄与する。

　上記組成物が、界面活性剤を含有する場合、界面活性剤の含有量としては、組成物の全固形分に対して、０．００１～２．０質量％が好ましく、０．００５～０．５質量％がより好ましく、０．０１～０．１質量％が更に好ましい。

　界面活性剤は、１種を単独で用いても、２種以上を併用してもよい。界面活性剤を２種以上併用する場合は、合計量が上記範囲内であることが好ましい。
<Surfactant>

The composition may contain a surfactant. The surfactant contributes to improving the coatability of the composition.

When the composition contains a surfactant, the content of the surfactant is preferably from 0.001 to 2.0% by mass, and more preferably from 0.005 to 0. 5 mass% is more preferable, and 0.01 to 0.1 mass% is further preferable.

One type of surfactant may be used alone, or two or more types may be used in combination. When two or more surfactants are used in combination, the total amount is preferably within the above range.

　界面活性剤としては、例えば、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、及び、シリコーン系界面活性剤等が挙げられる。
Examples of the surfactant include a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant.

　例えば、組成物がフッ素系界面活性剤を含有すれば、組成物の液特性（特に、流動性）がより向上する。即ち、フッ素系界面活性剤を含有する組成物を用いて膜形成する場合においては、被塗布面と塗布液との界面張力を低下させて、被塗布面への濡れ性が改善され、被塗布面への塗布性が向上する。このため、少量の液量で数μｍ程度の薄膜を形成した場合であっても、厚さムラの小さい均一厚の膜形成をより好適に行える点で有効である。
For example, when the composition contains a fluorine-based surfactant, the liquid properties (particularly, fluidity) of the composition are further improved. That is, when a film is formed using a composition containing a fluorine-based surfactant, the interfacial tension between the surface to be coated and the coating solution is reduced, the wettability to the surface to be coated is improved, and The applicability to the surface is improved. For this reason, even when a thin film having a thickness of about several μm is formed with a small amount of liquid, it is effective in that a uniform thickness film having small thickness unevenness can be more suitably formed.

　フッ素系界面活性剤中のフッ素含有率は、３～４０質量％が好ましく、５～３０質量％がより好ましく、７～２５質量％が更に好ましい。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性及び／又は省液性の点で効果的であり、組成物中における溶解性も良好である。
The fluorine content in the fluorinated surfactant is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, even more preferably from 7 to 25% by mass. A fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of the thickness of the coating film and / or liquid saving properties, and has good solubility in the composition.

　フッ素系界面活性剤としては、例えば、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７６、同Ｆ１７７、同Ｆ１４１、同Ｆ１４２、同Ｆ１４３、同Ｆ１４４、同Ｒ３０、同Ｆ４３７、同Ｆ４７５、同Ｆ４７９、同Ｆ４８２、同Ｆ５５４、及び、同Ｆ７８０（以上、ＤＩＣ株式会社製）；フロラードＦＣ４３０、同ＦＣ４３１、及び、同ＦＣ１７１（以上、住友スリーエム株式会社製）；サーフロンＳ－３８２、同ＳＣ－１０１、同ＳＣ－１０３、同ＳＣ－１０４、同ＳＣ－１０５、同ＳＣ－１０６８、同ＳＣ－３８１、同ＳＣ－３８３、同Ｓ－３９３、及び、同ＫＨ－４０（以上、旭硝子株式会社製）；並びに、ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、及び、ＰＦ７００２（ＯＭＮＯＶＡ社製）等が挙げられる。

　フッ素系界面活性剤としてブロックポリマーも使用でき、具体例としては、例えば特開第２０１１－８９０９０号公報に記載されたが化合物が挙げられる。
Examples of the fluorine-based surfactant include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479. F482, F554, and F780 (all made by DIC Corporation); Florado FC430, FC431, and FC171 (all made by Sumitomo 3M Limited); Surflon S-382, SC-101, same SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by Asahi Glass Co., Ltd.); , PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA).

A block polymer can also be used as the fluorinated surfactant, and specific examples thereof include compounds described in JP-A-2011-89090.

＜溶剤＞

　組成物は、溶剤を含有することが好ましい。

　溶剤としては特に制限されず公知の溶剤を使用できる。

　組成物中における溶剤の含有量としては特に制限されないが、組成物の固形分が１０～９０質量％となる量が好ましく、１０～４０質量％となる量がより好ましく、１５～３５質量％となる量が更に好ましい。

　溶剤は１種を単独で用いても、２種以上を併用してもよい。２種以上の溶剤を併用する場合には、組成物の全固形分が上記範囲内となるように調整されることが好ましい。
<Solvent>

The composition preferably contains a solvent.

The solvent is not particularly limited, and a known solvent can be used.

The content of the solvent in the composition is not particularly limited, but is preferably an amount such that the solid content of the composition is 10 to 90% by mass, more preferably 10 to 40% by mass, and more preferably 15 to 35% by mass. Is more preferred.

One type of solvent may be used alone, or two or more types may be used in combination. When two or more solvents are used in combination, the composition is preferably adjusted so that the total solid content of the composition falls within the above range.

　溶剤としては、例えば、水、及び、有機溶剤が挙げられる。
Examples of the solvent include water and an organic solvent.

（有機溶剤）

　有機溶剤としては、例えば、アセトン、メチルエチルケトン、シクロヘキサン、酢酸エチル、エチレンジクロライド、テトラヒドロフラン、トルエン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、アセチルアセトン、シクロヘキサノン、シクロペンタノン、ジアセトンアルコール、エチレングリコールモノメチルエーテルアセテート、エチレングリコールエチルエーテルアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテルアセテート、３－メトキシプロパノール、メトキシメトキシエタノール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、３－メトキシプロピルアセテート、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、γ－ブチロラクトン、酢酸エチル、酢酸ブチル、乳酸メチル、Ｎ－メチル－２－ピロリドン、及び、乳酸エチル等が挙げられるが、これらに制限されない。
(Organic solvent)

Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and acetylacetone. , Cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol mono Butyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, Examples include, but are not limited to, butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, and ethyl lactate.

（水）

　組成物が、水を含有する場合、その含有量は、組成物の全質量に対して、０．００１～５．０質量％が好ましく、０．０１～３．０質量％がより好ましく、０．１～１．０質量％が更に好ましい。

　中でも、水の含有量が、組成物の全質量に対して、３．０質量％以下（より好ましくは１．０質量％以下）であれば、組成物中の成分の加水分解等による経時粘度安定性の劣化を抑制しやすく、０．０１質量％以上（好ましくは０．１質量％以上）であれば、経時沈降安定性を改善しやすい。
(water)

When the composition contains water, its content is preferably from 0.001 to 5.0% by mass, more preferably from 0.01 to 3.0% by mass, based on the total mass of the composition. More preferably, the amount is from 1 to 1.0% by mass.

Above all, if the content of water is 3.0% by mass or less (more preferably 1.0% by mass or less) with respect to the total mass of the composition, the viscosity over time due to hydrolysis of the components in the composition and the like. It is easy to suppress the deterioration of stability, and if it is 0.01% by mass or more (preferably 0.1% by mass or more), the sedimentation stability over time is easily improved.

＜その他の任意成分＞

　組成物は、上述した成分以外のその他の任意成分を更に含有してもよい。例えば、増感剤、共増感剤、架橋剤、硬化促進剤、熱硬化促進剤、フィラー、可塑剤、希釈剤、及び、感脂化剤等が挙げられ、更に、基板表面への密着促進剤及びその他の助剤類（例えば、導電性粒子、充填剤、消泡剤、難燃剤、レベリング剤、剥離促進剤、酸化防止剤、香料、表面張力調整剤、及び、連鎖移動剤等）等の公知の添加剤を必要に応じて加えてもよい。

　これらの成分は、例えば、特開２０１２－００３２２５号公報の段落０１８３～０２２８（対応する米国特許出願公開第２０１３／００３４８１２号明細書の段落０２３７～０３０９）、特開２００８－２５００７４号公報の段落０１０１～０１０２、段落０１０３～０１０４、段落０１０７～０１０９、及び特開２０１３－１９５４８０号公報の段落０１５９～０１８４等の記載を参酌でき、これらの内容は本願明細書に組み込まれる。
<Other optional ingredients>

The composition may further contain other optional components other than the components described above. For example, a sensitizer, a co-sensitizer, a cross-linking agent, a curing accelerator, a thermosetting accelerator, a filler, a plasticizer, a diluent, and a sensitizer may be used. Agents and other auxiliaries (eg, conductive particles, fillers, defoamers, flame retardants, leveling agents, release accelerators, antioxidants, fragrances, surface tension regulators, chain transfer agents, etc.), etc. May be added as necessary.

These components are described in, for example, paragraphs 0183 to 0228 of JP-A-2012-003225 (paragraphs 0237 to 0309 of US Patent Application Publication No. 2013/0034812) and paragraph 0101 of JP-A-2008-250074. To 0102, paragraphs 0103 to 0104, paragraphs 0107 to 0109, and paragraphs 0159 to 0184 of JP-A-2013-195480 can be referred to, and the contents thereof are incorporated in the specification of the present application.

＜遮光性組成物の製造方法＞

　組成物は、まず、黒色色材を含有する色材組成物を製造し、得られた色材組成物を更にその他の成分と混合して組成物とすることが好ましい。

　色材組成物は、黒色色材、樹脂（好ましくは分散樹脂）、及び、溶剤を混合して調製することが好ましい。また、色材組成物に重合禁止剤を含有させることも好ましい。
<Method for producing light-shielding composition>

The composition is preferably prepared by first producing a coloring material composition containing a black coloring material, and further mixing the obtained coloring material composition with other components.

The coloring material composition is preferably prepared by mixing a black coloring material, a resin (preferably, a dispersing resin), and a solvent. It is also preferable to include a polymerization inhibitor in the coloring material composition.

　上記色材組成物は、上記の各成分を公知の混合方法（例えば、撹拌機、ホモジナイザー、高圧乳化装置、湿式粉砕機、又は、湿式分散機等を用いた混合方法）により混合して調製できる。
The coloring material composition can be prepared by mixing the above-mentioned components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, or a wet disperser). .

　遮光性組成物の調製に際しては、各成分を一括配合してもよいし、各成分をそれぞれ、溶剤に溶解又は分散した後に逐次配合してもよい。また、配合する際の投入順序及び作業条件は特に制限されない。
In preparing the light-shielding composition, the components may be blended together, or the components may be dissolved or dispersed in a solvent and then blended sequentially. In addition, the order of charging and the working conditions for mixing are not particularly limited.

　遮光性組成物は、異物の除去及び欠陥の低減等の目的で、フィルタで濾過することが好ましい。フィルタとしては、従来からろ過用途等に用いられているフィルタであれば特に制限されずに使用できる。例えば、ＰＴＦＥ（ポリテトラフルオロエチレン）等のフッ素樹脂、ナイロン等のポリアミド系樹脂、並びに、ポリエチレン及びポリプロピレン（ＰＰ）等のポリオレフィン系樹脂（高密度、超高分子量を含む）等によるフィルタが挙げられる。これら素材の中でもポリプロピレン（高密度ポリプロピレンを含む）、ナイロンが好ましい。

　フィルタの孔径は、０．１～７．０μｍが好ましく、０．２～２．５μｍがより好ましく、０．２～１．５μｍが更に好ましく、０．３～０．７μｍが特に好ましい。この範囲とすれば、顔料（黒色顔料を含む）のろ過詰まりを抑えつつ、顔料に含まれる不純物及び凝集物等、微細な異物を確実に除去できるようになる。

　フィルタを使用する際、異なるフィルタを組み合わせてもよい。その際、第１のフィルタでのフィルタリングは、１回のみでもよいし、２回以上行ってもよい。異なるフィルタを組み合わせて２回以上フィルタリングを行う場合は１回目のフィルタリングの孔径より２回目以降の孔径が同じ、又は、大きい方が好ましい。また、上述した範囲内で異なる孔径の第１のフィルタを組み合わせてもよい。ここでの孔径は、フィルタメーカーの公称値を参照できる。市販のフィルタとしては、例えば、日本ポール株式会社、アドバンテック東洋株式会社、日本インテグリス株式会社（旧日本マイクロリス株式会社）、及び、株式会社キッツマイクロフィルタ等が提供する各種フィルタの中から選択できる。

　第２のフィルタは、上述した第１のフィルタと同様の材料等で形成されたフィルタを使用できる。第２のフィルタの孔径は、０．２～１０．０μｍが好ましく、０．２～７．０μｍがより好ましく、０．３～６．０μｍが更に好ましい。

　組成物は、金属、ハロゲンを含有する金属塩、酸、アルカリ等の不純物を含まないことが好ましい。これら材料に含まれる不純物の含有量としては、１質量ｐｐｍ以下が好ましく、１質量ｐｐｂ以下がより好ましく、１００質量ｐｐｔ以下が更に好ましく、１０質量ｐｐｔ以下が特に好ましく、実質的に含まないこと（測定装置の検出限界以下であること）が最も好ましい。

　なお、上記不純物は、誘導結合プラズマ質量分析装置（横河アナリティカルシステムズ製、Ａｇｉｌｅｎｔ　７５００ｃｓ型）により測定できる。
The light-shielding composition is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects. The filter can be used without any particular limitation as long as it is a filter conventionally used for filtration or the like. For example, a filter made of a fluorine resin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, and a polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP) can be used. . Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.

The pore size of the filter is preferably from 0.1 to 7.0 μm, more preferably from 0.2 to 2.5 μm, even more preferably from 0.2 to 1.5 μm, and particularly preferably from 0.3 to 0.7 μm. Within this range, fine foreign substances such as impurities and agglomerates contained in the pigment can be reliably removed while suppressing clogging of the pigment (including the black pigment) by filtration.

When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed two or more times. When filtering is performed two or more times by combining different filters, it is preferable that the diameters of the holes after the second filtering are the same as or larger than the diameters of the holes after the first filtering. Further, first filters having different hole diameters within the above-described range may be combined. The pore diameter here can refer to the nominal value of the filter manufacturer. Commercially available filters can be selected from various filters provided by, for example, Nippon Pall Co., Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (former Nippon Microlith Co., Ltd.), and Kitz Micro Filter Co., Ltd.

As the second filter, a filter formed of the same material as the first filter described above can be used. The pore size of the second filter is preferably from 0.2 to 10.0 μm, more preferably from 0.2 to 7.0 μm, even more preferably from 0.3 to 6.0 μm.

The composition preferably does not contain impurities such as metals, metal salts containing halogens, acids, and alkalis. The content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 1 mass ppb or less, still more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and it is substantially free of ( Below the detection limit of the measuring device).

The impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).

〔黒色層の形成〕

　黒色層の形成方法は特に制限されず、支持体上に、本発明の遮光性組成物を塗布し、得られた塗膜を硬化して、黒色層（パターン状の黒色層を含む）が形成される。
(Formation of black layer)

The method for forming the black layer is not particularly limited, and the light-shielding composition of the present invention is applied on a support, and the obtained coating film is cured to form a black layer (including a patterned black layer). Is done.

　黒色層の形成方法は、以下の工程を含有することが好ましい。

・塗膜形成工程

・硬化工程

・現像工程

　以下、各工程について説明する。
The method for forming a black layer preferably includes the following steps.

・ Film formation process

・ Curing process

・ Development process

Hereinafter, each step will be described.

＜塗膜形成工程＞

　塗膜形成工程においては、硬化（露光）に先立ち、支持体上に、遮光性組成物を塗布して塗膜（組成物層）を形成する。支持体としては、例えば、基板（例えば、シリコン基板）上にＣＣＤ（Ｃｈａｒｇｅ　Ｃｏｕｐｌｅｄ　Ｄｅｖｉｃｅ）又はＣＭＯＳ（Ｃｏｍｐｌｅｍｅｎｔａｒｙ　Ｍｅｔａｌ－Ｏｘｉｄｅ　Ｓｅｍｉｃｏｎｄｕｃｔｏｒ）等の撮像素子（受光素子）が設けられた固体撮像素子用基板を使用できる。また、支持体上には、必要により、上部の層との密着改良、物質の拡散防止及び基板表面の平坦化等のために下塗り層を設けてもよい。
<Coating process>

In the coating film forming step, prior to curing (exposure), a light-shielding composition is applied on a support to form a coating film (composition layer). As the support, for example, a substrate for a solid-state imaging device in which an imaging device (light-receiving device) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (eg, a silicon substrate). it can. If necessary, an undercoat layer may be provided on the support for improving adhesion to an upper layer, preventing diffusion of a substance, and flattening the surface of the substrate.

　支持体上への組成物の塗布方法としては、スリット塗布法、インクジェット法、回転塗布法、流延塗布法、ロール塗布法、及び、スクリーン印刷法等の各種の塗布方法を適用できる。塗膜の膜厚としては、０．１～１０μｍが好ましく、０．２～５μｍがより好ましく、０．２～３μｍが更に好ましい。支持体上に塗布された塗膜の乾燥（プリベーク）は、例えば、ホットプレート、オーブン等で５０～１４０℃の温度で１０～３００秒間で行える。
As a method of applying the composition on the support, various application methods such as a slit coating method, an ink jet method, a spin coating method, a casting coating method, a roll coating method, and a screen printing method can be applied. The thickness of the coating film is preferably from 0.1 to 10 μm, more preferably from 0.2 to 5 μm, even more preferably from 0.2 to 3 μm. Drying (prebaking) of the coating film applied on the support can be performed, for example, on a hot plate or an oven at a temperature of 50 to 140 ° C. for 10 to 300 seconds.

＜硬化工程＞

　硬化工程では、塗膜形成工程において形成された塗膜に活性光線又は放射線を照射して露光し、光照射された塗膜を硬化させる。

　光照射の方法としては特に制限されないが、パターン状の開口部を有するフォトマスクを介して光照射することが好ましい。

　露光は放射線の照射により行うことが好ましい。露光に際して使用できる放射線としては、特に、ｇ線、ｈ線、及び、ｉ線等の紫外線が好ましく、光源としては高圧水銀灯が好まれる。照射強度は５～１５００ｍＪ／ｃｍ２が好ましく、１０～１０００ｍＪ／ｃｍ２がより好ましい。

　なお、組成物が熱重合開始剤を含有する場合、上記硬化工程において、塗膜を加熱してもよい。加熱の温度として特に制限されないが、８０～２５０℃が好ましい。また、加熱の時間としては特に制限されないが、３０～３００秒間が好ましい。

　なお、硬化工程において、塗膜を加熱する場合、後述するポストベークを兼ねてもよい。言い換えれば、硬化工程において、塗膜を加熱する場合、黒色層の製造方法はポストベーク工程を含有しなくてもよい。
<Curing process>

In the curing step, the coating film formed in the coating film forming step is exposed to actinic rays or radiation and exposed to cure the light-irradiated coating film.

The method of light irradiation is not particularly limited, but light irradiation is preferably performed through a photomask having a pattern-shaped opening.

Exposure is preferably performed by irradiation with radiation. As radiation that can be used for exposure, ultraviolet rays such as g-rays, h-rays and i-rays are particularly preferred, and a high-pressure mercury lamp is preferred as a light source. The irradiation intensity is preferably 5 ~ 1500mJ / cm 2, more preferably 10 ~ 1000mJ / cm 2.

In addition, when a composition contains a thermal-polymerization initiator, you may heat a coating film in the said hardening process. The heating temperature is not particularly limited, but is preferably from 80 to 250 ° C. The heating time is not particularly limited, but is preferably 30 to 300 seconds.

In addition, when heating a coating film in a hardening process, you may also serve as post bake mentioned later. In other words, when the coating film is heated in the curing step, the method for producing the black layer may not include the post-baking step.

＜現像工程＞

　現像工程は、露光後の上記塗膜を現像する工程である。本工程により、硬化工程における光未照射部分の塗膜が溶出し、光硬化した部分だけが残り、パターン状の黒色層が得られる。

　現像工程で使用される現像液の種類は特に制限されないが、下地の撮像素子及び回路等にダメージを起こさない、アルカリ現像液が望ましい。

　現像温度としては、例えば、２０～３０℃である。

　現像時間は、例えば、２０～９０秒間である。残渣をよりよく除去するため、近年では１２０～１８０秒間実施する場合もある。更には、残渣除去性をより向上するため、現像液を６０秒ごとに振り切り、更に新たに現像液を供給する工程を数回繰り返す場合もある。
<Development process>

The developing step is a step of developing the exposed coating film. By this step, the coating film in the unirradiated portion in the curing step elutes, leaving only the photocured portion, and a patterned black layer is obtained.

The type of the developing solution used in the developing step is not particularly limited, but an alkali developing solution that does not cause damage to the underlying image pickup device, circuits, and the like is preferable.

The development temperature is, for example, 20 to 30 ° C.

The development time is, for example, 20 to 90 seconds. In order to remove the residue better, in recent years, it may be performed for 120 to 180 seconds. Further, in order to further improve the residue removal property, the step of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

　アルカリ現像液としては、アルカリ性化合物を濃度が０．００１～１０質量％（好ましくは０．０１～５質量％）となるように水に溶解して調製されたアルカリ性水溶液が好ましい。

　アルカリ性化合物は、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム，硅酸ナトリウム、メタ硅酸ナトリウム、アンモニア水、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシ、ベンジルトリメチルアンモニウムヒドロキシド、コリン、ピロール、ピペリジン、及び、１，８－ジアザビシクロ［５．４．０］－７－ウンデセン等が挙げられる（このうち、有機アルカリが好ましい。）。

　なお、アルカリ現像液として用いた場合は、一般に現像後に水で洗浄処理が施される。
As the alkali developer, an alkaline aqueous solution prepared by dissolving an alkaline compound in water so as to have a concentration of 0.001 to 10% by mass (preferably 0.01 to 5% by mass) is preferable.

Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropyl. Ammonium hydroxide, tetrabutylammonium hydroxy, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like. preferable.).

When used as an alkaline developer, a washing treatment with water is generally performed after development.

＜ポストベーク＞

　硬化工程の後、後加熱処理（ポストベーク）を行うことが好ましい。ポストベークは、硬化を完全にするための現像後の加熱処理である。その加熱温度は、２４０℃以下が好ましく、２２０℃以下がより好ましい。下限は特にないが、効率的かつ効果的な処理を考慮すると、５０℃以上が好ましく、１００℃以上がより好ましい。

　ポストベークは、ホットプレート、コンベークションオーブン（熱風循環式乾燥機）、又は、高周波加熱機等の加熱手段を用いて、連続式又はバッチ式で行える。
<Post bake>

After the curing step, a post-heating treatment (post-bake) is preferably performed. Post baking is a heat treatment after development to complete curing. The heating temperature is preferably 240 ° C. or lower, more preferably 220 ° C. or lower. There is no particular lower limit, but in consideration of efficient and effective treatment, the temperature is preferably 50 ° C or higher, more preferably 100 ° C or higher.

Post-baking can be performed in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater.

　上記のポストベークは、低酸素濃度の雰囲気下で行うことが好ましい。その酸素濃度は、１９体積％以下が好ましく、１５体積％以下がより好ましく、１０体積％以下が更に好ましく、７体積％以下が特に好ましく、３体積％以下が最も好ましい。下限は特にないが、１０体積ｐｐｍ以上が実際的である。
The post-baking is preferably performed in an atmosphere having a low oxygen concentration. The oxygen concentration is preferably 19% by volume or less, more preferably 15% by volume or less, still more preferably 10% by volume or less, particularly preferably 7% by volume or less, and most preferably 3% by volume or less. There is no particular lower limit, but 10 ppm by volume or more is practical.

　また、上記の加熱によるポストベークに変え、ＵＶ（紫外線）照射によって硬化を完遂させてもよい。

　この場合、上述した組成物は、更にＵＶ硬化剤を含有することが好ましい。ＵＶ硬化剤は、通常のｉ線露光によるリソグラフィー工程のために添加する重合開始剤の露光波長である３６５ｎｍより短波の波長で硬化できるＵＶ硬化剤が好ましい。ＵＶ硬化剤としては、例えば、チバ　イルガキュア　２９５９（商品名）が挙げられる。ＵＶ照射を行う場合においては、塗膜が波長３４０ｎｍ以下で硬化する材料であることが好ましい。波長の下限値は特にないが、２２０ｎｍ以上が一般的である。またＵＶ照射の露光量は１００～５０００ｍＪが好ましく、３００～４０００ｍＪがより好ましく、８００～３５００ｍＪが更に好ましい。このＵＶ硬化工程は、硬化工程の後に行うことが、低温硬化をより効果的に行うために、好ましい。露光光源はオゾンレス水銀ランプを使用することが好ましい。
The curing may be completed by UV (ultraviolet) irradiation instead of the post-baking by heating.

In this case, the above-mentioned composition preferably further contains a UV curing agent. The UV curing agent is preferably a UV curing agent that can be cured at a wavelength shorter than 365 nm, which is the exposure wavelength of the polymerization initiator added for the lithography process using ordinary i-ray exposure. As the UV curing agent, for example, Chibile Gacure 2959 (trade name) can be mentioned. When performing UV irradiation, it is preferable that the coating film is a material that cures at a wavelength of 340 nm or less. Although there is no particular lower limit for the wavelength, it is generally 220 nm or more. The exposure amount of UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, and further preferably 800 to 3500 mJ. This UV curing step is preferably performed after the curing step in order to more effectively perform low-temperature curing. The exposure light source preferably uses an ozone-less mercury lamp.

〔黒色層の物性〕

　黒色層は、優れた遮光性を有する点で、４００～１２００ｎｍの波長領域における厚さ１．０μｍあたりの光学濃度（ＯＤ：Ｏｐｔｉｃａｌ　Ｄｅｎｓｉｔｙ）が、１．７以上が好ましく、２．０以上がより好ましく、２．１以上が更に好ましい。なお、上限値は特に制限されないが、一般に１０以下が好ましい。

　なお、本明細書において、４００～１２００ｎｍの波長領域における厚さ１．０μｍあたりの光学濃度が２．０以上であるとは、波長４００～１２００ｎｍの全域において、厚さ１．０μｍあたりの光学濃度が２．０以上であることを意味する。

　なお、黒色層（遮光膜）の光学濃度は、まず、ガラス基板上に黒色層（遮光膜）を形成して、分光光度計Ｕ－４１００（商品名、日立ハイテクノロジーズ社製）積分球型受光ユニットを用いて測定し、測定箇所の厚さも測定し、所定の厚さあたりの光学濃度を算出することにより、測定できる。
(Physical properties of black layer)

Since the black layer has excellent light-shielding properties, the optical density (OD: Optical Density) per 1.0 μm in the wavelength region of 400 to 1200 nm is preferably 1.7 or more, more preferably 2.0 or more. Preferably, 2.1 or more is more preferable. The upper limit is not particularly limited, but is generally preferably 10 or less.

In this specification, the expression that the optical density per 1.0 μm thickness in the wavelength region of 400 to 1200 nm is 2.0 or more means that the optical density per 1.0 μm thickness in the entire wavelength range of 400 to 1200 nm. Is 2.0 or more.

The optical density of the black layer (light-shielding film) is determined by first forming a black layer (light-shielding film) on a glass substrate and using a spectrophotometer U-4100 (trade name, manufactured by Hitachi High-Technologies Corp.) It can be measured by measuring using a unit, measuring the thickness of the measurement location, and calculating the optical density per predetermined thickness.

　黒色層の厚さは、例えば、０．１～４．０μｍが好ましく、１．０～２．５μｍがより好ましい。また、黒色層は、用途にあわせてこの範囲よりも薄膜としてもよいし、厚膜としてもよい。

　また、黒色層を光減衰膜として使用する場合、上記範囲よりも薄膜（例えば、０．１～０．５μｍ）として遮光性を調整してもよい。この場合、４００～１２００ｎｍの波長領域における厚さ１．０μｍあたりの光学濃度は、０．１～１．５が好ましく、０．２～１．０がより好ましい。
The thickness of the black layer is, for example, preferably from 0.1 to 4.0 μm, more preferably from 1.0 to 2.5 μm. The black layer may be thinner or thicker than this range depending on the application.

When the black layer is used as a light attenuating film, the light-shielding property may be adjusted by making the black layer thinner (for example, 0.1 to 0.5 μm) than the above range. In this case, the optical density per 1.0 μm thickness in the wavelength region of 400 to 1200 nm is preferably 0.1 to 1.5, and more preferably 0.2 to 1.0.

［酸素遮断層］

　酸素遮断層は、黒色層上に形成された層であり、黒色層との接面とは反対側の面から黒色層へと通過する酸素を遮断する機能を有する層である。

　酸素遮断層としては、厚さ方向の酸素透過率（以下、単に「酸素透過率」とも記載する）が５０ｍｌ／（ｍ２・ｄａｙ・ａｔｍ）以下である層が挙げられ、酸素透過率が１０ｍｌ／（ｍ２・ｄａｙ・ａｔｍ）以下である層が好ましく、１．５ｍｌ／（ｍ２・ｄａｙ・ａｔｍ）以下である層がより好ましく、１．０ｍｌ／（ｍ２・ｄａｙ・ａｔｍ）以下である層が更に好ましい。酸素透過率の下限は０．００１ｍｌ／（ｍ２・ｄａｙ・ａｔｍ）が好ましい。

　酸素透過率は、例えば、酸素透過測定装置（Ｍｏｄｅｌ８００１、イリノイ株式会社製）を用いて測定することができる。
[Oxygen barrier layer]

The oxygen blocking layer is a layer formed on the black layer, and has a function of blocking oxygen passing from the surface opposite to the surface in contact with the black layer to the black layer.

Examples of the oxygen barrier layer include a layer having an oxygen permeability in the thickness direction (hereinafter, also simply referred to as “oxygen permeability”) of 50 ml / (m 2 · day · atm) or less, and an oxygen permeability of 10 ml. / (m 2 · day · atm ) layers preferably not more than, 1.5 ml / more preferably the layer is (m 2 · day · atm) or less, 1.0ml / (m 2 · day · atm) or less Certain layers are more preferred. The lower limit of the oxygen permeability is preferably 0.001 ml / (m 2 · day · atm).

The oxygen transmission rate can be measured using, for example, an oxygen transmission measurement apparatus (Model 8001, manufactured by Illinois Co., Ltd.).

　酸素遮断層は、無機材料からなる単層である。

　本明細書において、「単層」とは、層を構成する材料の組成が厚さ方向及び面内の方向に沿って均一である層を意味する。よって、例えば、無機材料ａからなる層Ａと、無機材料ａとは組成が異なる無機材料ｂからなる層Ｂとの積層体は、層Ａ及び層Ｂがいずれも酸素を遮断する機能を有していたとしても、本明細書で規定する酸素遮断層には含まれない。

　また、「無機材料からなる」とは、酸素遮断層を構成する材料中の炭素原子の含有量が、酸素遮断層の総質量に対して５質量％以下であることを意味する。上記炭素原子の含有量は、酸素遮断層の総質量に対して２．５質量％以下が好ましい。また、上記炭素原子の含有量の下限は特に制限されず、検出限界以下であってよい。

　酸素遮断層を構成する材料中の炭素原子の含有量は、研磨又は切削等により酸素遮断層に平滑な面を形成した後、形成した平滑面を電子線マイクロアナライザー（ＥＰＭＡ：Electron Probe Micro Analyzer）（例えば、日本電子株式会社社製「ＪＸＡ－８５３０Ｆ」（商品名））を用いて分析することにより、測定される。
The oxygen barrier layer is a single layer made of an inorganic material.

In the present specification, “single layer” means a layer in which the composition of the material constituting the layer is uniform along the thickness direction and the in-plane direction. Thus, for example, a laminate of the layer A made of the inorganic material a and the layer B made of the inorganic material b having a different composition from the inorganic material a has a function of blocking oxygen in both the layer A and the layer B. If it does, it is not included in the oxygen barrier layer as defined herein.

Further, “comprising an inorganic material” means that the content of carbon atoms in the material constituting the oxygen barrier layer is 5% by mass or less based on the total mass of the oxygen barrier layer. The content of the carbon atoms is preferably 2.5% by mass or less based on the total mass of the oxygen barrier layer. The lower limit of the content of the carbon atom is not particularly limited, and may be lower than the detection limit.

The content of carbon atoms in the material constituting the oxygen-blocking layer is determined by forming a smooth surface on the oxygen-blocking layer by polishing or cutting, and then forming the formed smooth surface on an electron beam microanalyzer (EPMA). (Eg, “JXA-8530F” (trade name) manufactured by JEOL Ltd.) and analyzed.

　酸素遮断層の厚さは、１０～５００ｎｍである。

　酸素遮断層の厚さが上記の範囲にあることにより、耐光性と耐湿性のバランスがより優れた遮光膜を製造できる。より詳しくは、酸素遮断層の厚さが１０ｎｍ以上であると、耐光試験後における遮光膜の膜厚の変動及び光学特性（透過率及び反射率）の変動を抑制する効果が向上し、酸素遮断層の厚さが５００ｎｍ以下であると、耐湿試験後の基板からの黒色層の剥がれを抑制する効果が向上する。

　酸素遮断層の厚さが５００ｎｍ以下であると耐湿性が向上する理由は明らかではないが、酸素遮断層の厚さが５００ｎｍ超であると、耐湿試験後、酸素遮断層付きの黒色層と基板との間の収縮率の差によって生じる応力が強くなり、基板からの黒色層の剥がれが引き起こされるためであると推測される。

　また、酸素遮断層の厚さが５００ｎｍ以下である場合、黒色層及び酸素遮断層からなる遮光膜をデバイス上に設けたときの、黒色層表面での反射光と酸素遮断層表面での反射光の干渉を低減し、デバイス性能の低下を防止できる。
The thickness of the oxygen barrier layer is 10 to 500 nm.

When the thickness of the oxygen barrier layer is in the above range, a light-shielding film having a more excellent balance between light resistance and moisture resistance can be manufactured. More specifically, when the thickness of the oxygen barrier layer is 10 nm or more, the effect of suppressing the variation in the thickness of the light-shielding film and the variation in optical characteristics (transmittance and reflectance) after the light resistance test is improved. When the thickness of the layer is 500 nm or less, the effect of suppressing peeling of the black layer from the substrate after the moisture resistance test is improved.

Although the reason why the moisture resistance is improved when the thickness of the oxygen barrier layer is 500 nm or less is not clear, when the thickness of the oxygen barrier layer is more than 500 nm, the black layer with the oxygen barrier layer and the substrate after the moisture resistance test are performed. This is presumed to be due to the fact that the stress generated due to the difference in the shrinkage ratio between the substrate and the substrate increases, causing the black layer to peel off from the substrate.

When the thickness of the oxygen blocking layer is 500 nm or less, the light reflected on the surface of the black layer and the light reflected on the surface of the oxygen blocking layer when a light-shielding film composed of the black layer and the oxygen blocking layer are provided on the device. Can be reduced, and a decrease in device performance can be prevented.

　酸素遮断層の厚さは、遮光膜の耐湿性及び耐熱性がより優れる点から、５０ｎｍ超２５０ｎｍ未満が好ましく、７０～２００ｎｍがより好ましい。

　また、酸素遮断層の厚さに対する黒色層の厚さの比率（黒色層の厚さ／酸素遮断層の厚さ）は、２～１００であってよく、遮光膜の耐湿性及び耐熱性がより優れる点から、７～３０が好ましく、１０～２５がより好ましい。
The thickness of the oxygen barrier layer is preferably more than 50 nm and less than 250 nm, more preferably 70 to 200 nm, from the viewpoint that the moisture resistance and heat resistance of the light shielding film are more excellent.

The ratio of the thickness of the black layer to the thickness of the oxygen blocking layer (the thickness of the black layer / the thickness of the oxygen blocking layer) may be 2 to 100, and the moisture resistance and the heat resistance of the light-shielding film are more improved. From the viewpoint of superiority, 7 to 30 is preferable, and 10 to 25 is more preferable.

　酸素遮断層を構成する無機材料としては、特に制限されず、金属酸化物、金属窒化物及び金属酸窒化物が挙げられる。

　無機材料に含まれる金属としては、ケイ素、チタン、アルミニウム、インジウム、スズ、ニオブ、ジルコニウム、セリウム、タンタル及び亜鉛が挙げられ、ケイ素、チタン又はアルミニウムが好ましく、ケイ素がより好ましい。
The inorganic material constituting the oxygen barrier layer is not particularly limited, and includes a metal oxide, a metal nitride, and a metal oxynitride.

Examples of the metal contained in the inorganic material include silicon, titanium, aluminum, indium, tin, niobium, zirconium, cerium, tantalum, and zinc, with silicon, titanium or aluminum being preferred, and silicon being more preferred.

　酸素遮断層を構成する無機材料の具体例としては、酸化ケイ素、窒化ケイ素、酸化インジウム、酸化スズ、酸化ニオブ、酸化チタン、酸化ジルコニウム、酸化セリウム、酸化タンタル、酸化アルミニウム及び酸化亜鉛が挙げられ、酸化ケイ素及び窒化ケイ素が好ましく、遮光膜の耐光性及び耐湿性がより優れる点から、酸化ケイ素がより好ましい。
Specific examples of the inorganic material constituting the oxygen barrier layer, silicon oxide, silicon nitride, indium oxide, tin oxide, niobium oxide, titanium oxide, zirconium oxide, cerium oxide, tantalum oxide, aluminum oxide and zinc oxide, Silicon oxide and silicon nitride are preferred, and silicon oxide is more preferred because the light-shielding film has better light resistance and moisture resistance.

　また、本発明の酸素遮断層は、無機材料からなる単層であり、有機成分を実質的に含有しない。

　酸素遮断層が有機成分を含有する場合、酸素遮断層への光照射により内部に含まれる有機成分が分解され、酸素遮断能が低下する。それに対して、無機材料からなる単層である本発明の酸素遮断層は、このような酸素遮断能の低下を防止できる。

　なお、本明細書において酸素遮断層が「有機成分を実質的に含有しない」とは、酸素遮断層を構成する材料中の炭素原子の含有量が、酸素遮断層の総質量に対して５質量％以下であることを意味する。酸素遮断層を構成する材料中の炭素原子の含有量は、上述の方法により、電子線マイクロアナライザーを用いて測定される。
The oxygen barrier layer of the present invention is a single layer made of an inorganic material, and does not substantially contain an organic component.

When the oxygen barrier layer contains an organic component, the organic component contained therein is decomposed by light irradiation on the oxygen barrier layer, and the oxygen barrier ability is reduced. In contrast, the oxygen barrier layer of the present invention, which is a single layer made of an inorganic material, can prevent such a decrease in oxygen barrier ability.

In addition, in this specification, the oxygen-barrier layer "contains substantially no organic component" means that the content of carbon atoms in the material constituting the oxygen-barrier layer is 5 mass% with respect to the total mass of the oxygen-barrier layer. % Or less. The content of carbon atoms in the material constituting the oxygen barrier layer is measured by the above-described method using an electron beam microanalyzer.

　酸素遮断層は、耐熱性がより優れる点から、実質的に粒子を含有しないことが好ましい。酸素遮断層が粒子を含有する場合、層を構成する材料の組成が均一でなくなり、熱に対する収縮性が異なる領域が生じることにより、高温環境下で酸素遮断層が大きく歪み、耐熱性が低下することがあるためである。

　また、酸素遮断層は、表面がより平滑になり、反射率の面内均一性がより優れる点から実質的に粒子を含有しないことが好ましい。

　なお、上記の「粒子」とは、酸素遮断層を構成する無機材料とは組成が異なる物質の粒子であって、その粒径が１０ｎｍ以上である粒子を意味する。
It is preferable that the oxygen barrier layer does not substantially contain particles from the viewpoint of more excellent heat resistance. When the oxygen barrier layer contains particles, the composition of the material constituting the layer is not uniform, and a region having different heat shrinkage is generated, so that the oxygen barrier layer is greatly distorted in a high temperature environment, and the heat resistance is reduced. This is because there are times.

Further, it is preferable that the oxygen barrier layer contains substantially no particles from the viewpoint that the surface becomes smoother and the in-plane uniformity of the reflectance is more excellent.

The “particles” described above are particles of a substance having a different composition from the inorganic material forming the oxygen barrier layer, and mean particles having a particle size of 10 nm or more.

　酸素遮断層中の粒子の含有量は、電子線マイクロアナライザー（ＥＰＭＡ）（例えば、日本電子株式会社社製「ＪＸＡ－８５３０Ｆ」（商品名））を用いる以下の方法により、測定できる。まず、酸素遮断層を研磨又は切削して平滑な面を形成する。その後、形成した平滑面における元素組成の分布を、電子線マイクロアナライザーを用いて測定し、元素組成のマッピング画像を得る。得られたマッピング画像において、連続相との元素組成の違いに基づいて、粒子が存在する領域を特定する。次いで、粒子領域の面積の総和を観察面積で除することによって、観察面における粒子の占める面積比率を得る。次いで、その面積比率を体積比率に換算（面積比率の３／２乗）し、更に元素組成に基づいて質量比率に換算することにより、酸素遮断層の総量に対する粒子の含有量が得られる。

　例えば、酸化ケイ素（ＳｉＯ２）からなる酸素遮断層中に酸化ケイ素粒子が存在する場合、酸化ケイ素粒子の表面に存在するシラノール基（ＳｉＯＨ）により、酸化ケイ素粒子の輪郭がマッピング画像に表示されるため、粒子の存在を確認できる。このように、上記の方法によれば、酸素遮断層中の連続相と粒子との組成の違いに基づいて、粒子の含有量を測定できる。

　なお、本明細書において酸素遮断層が「実質的に粒子を含有しない」とは、また、上記方法により測定される酸素遮断層中の粒子の含有量が、酸素遮断層の総質量に対して５質量％以下であるか、又は検出限界以下であることを意味する。
The content of the particles in the oxygen barrier layer can be measured by the following method using an electron beam microanalyzer (EPMA) (for example, “JXA-8530F” (trade name) manufactured by JEOL Ltd.). First, the oxygen barrier layer is polished or cut to form a smooth surface. After that, the distribution of the element composition on the formed smooth surface is measured using an electron beam microanalyzer to obtain a mapping image of the element composition. In the obtained mapping image, a region where the particles exist is specified based on a difference in element composition from the continuous phase. Next, the area ratio of the particles on the observation surface is obtained by dividing the total area of the particle regions by the observation area. Next, the area ratio is converted into a volume ratio (3/2 power of the area ratio), and further converted into a mass ratio based on the elemental composition, thereby obtaining the content of the particles with respect to the total amount of the oxygen barrier layer.

For example, when silicon oxide particles are present in an oxygen barrier layer made of silicon oxide (SiO 2 ), the outline of the silicon oxide particles is displayed on a mapping image due to silanol groups (SiOH) present on the surface of the silicon oxide particles. Therefore, the presence of particles can be confirmed. As described above, according to the above method, the content of the particles can be measured based on the difference in the composition between the continuous phase and the particles in the oxygen barrier layer.

In the present specification, the oxygen barrier layer "substantially contains no particles" means that the content of the particles in the oxygen barrier layer measured by the above method is based on the total mass of the oxygen barrier layer. 5% by mass or less, or below the detection limit.

〔酸素遮断層の形成〕

　酸素遮断層を形成する方法は特に制限されず、公知の無機材料の成膜方法を用いることができる。

　成膜方法としては、スパッタリング法、真空蒸着法、イオンビームアシスト蒸着法、イオンプレート法、及び、プラズマＣＶＤ（化学蒸着）法等の蒸着による形成方法、並びに、スピンコート法、ディップコート法、キャスト法、スリットコート法、及び、スプレー法等の湿式法が挙げられる。
(Formation of oxygen barrier layer)

The method for forming the oxygen barrier layer is not particularly limited, and a known method for forming a film of an inorganic material can be used.

As a film forming method, a sputtering method, a vacuum deposition method, an ion beam assisted deposition method, an ion plate method, a deposition method such as a plasma CVD (chemical vapor deposition) method, a spin coating method, a dip coating method, and a casting method Method, a slit coating method, and a wet method such as a spray method.

　中でも、薄膜の形成がより容易であることから、蒸着により酸素遮断層を形成することが好ましく、厚さの制御がより容易であり、対象物である黒色層との密着力がより優れる点から、スパッタリング法により酸素遮断層を形成することがより好ましい。

　スパッタリング法としては、特に制限されず、パルススパッタリング法、ＡＣスパッタリング法、及び、デジタルスパッタリング法等の公知の方法であってよい。
Above all, it is preferable to form an oxygen barrier layer by vapor deposition because it is easier to form a thin film, it is easier to control the thickness, and the adhesion to the black layer that is the object is more excellent. It is more preferable to form an oxygen barrier layer by a sputtering method.

The sputtering method is not particularly limited, and may be a known method such as a pulse sputtering method, an AC sputtering method, and a digital sputtering method.

　例えば、スパッタリング法により酸素遮断層を形成する場合、不活性ガスと反応性ガス（例えば酸素又は窒素等）との混合ガス雰囲気のチャンバ内に、黒色層が表面に形成された基板を配置し、所望の組成となるようにターゲットを選択して酸素遮断層を成膜する。

　なお、不活性ガスの種類は特に制限されず、アルゴン又はヘリウム等の不活性ガスが使用できる。また、反応性ガスは、形成する酸素遮断層の組成に応じて選択すればよい。
For example, when an oxygen barrier layer is formed by a sputtering method, a substrate having a black layer formed on a surface thereof is disposed in a chamber in a mixed gas atmosphere of an inert gas and a reactive gas (eg, oxygen or nitrogen), A target is selected so as to have a desired composition, and an oxygen barrier layer is formed.

The type of the inert gas is not particularly limited, and an inert gas such as argon or helium can be used. The reactive gas may be selected according to the composition of the oxygen barrier layer to be formed.

　不活性ガスと反応性ガスとの混合ガスによるチャンバ内の圧力は、特に制限されず、１．０Ｐａ以下であればよく、０．５Ｐａ以下が好ましい。不活性ガスと反応性ガスとの混合ガスによるチャンバ内の圧力の下限値は、特に制限されるものではないが、例えば、０．１Ｐａ以上であることが好ましい。

　また、スパッタリング法により酸素遮断層を形成する場合、放電電力、又は、成膜時間を調整することにより、酸素遮断層の厚さを調整できる。
The pressure in the chamber by the mixed gas of the inert gas and the reactive gas is not particularly limited, and may be 1.0 Pa or less, preferably 0.5 Pa or less. The lower limit of the pressure in the chamber due to the mixed gas of the inert gas and the reactive gas is not particularly limited, but is preferably, for example, 0.1 Pa or more.

In the case where the oxygen barrier layer is formed by a sputtering method, the thickness of the oxygen barrier layer can be adjusted by adjusting the discharge power or the deposition time.

［遮光膜の製造］

　本発明の遮光膜の製造方法は、特に制限されない。

　本発明の遮光膜は、支持体上に、黒色色材、樹脂、重合性化合物、及び、重合開始剤を含有する遮光性組成物を塗布し、得られた塗布膜を硬化して、黒色層を形成する工程と、上記黒色層上に、酸素遮断層を形成する工程と、を備える製造方法により、製造できる。

　上記「黒色層を形成する工程」としては、上記「黒色層の形成」にて説明した方法を適用すればよく、上記「酸素遮断層を形成する工程」としては、上記「酸素遮断層の形成」にて説明した方法を適用すればよい。
[Manufacture of light-shielding film]

The method for producing the light-shielding film of the present invention is not particularly limited.

The light-shielding film of the present invention, on a support, a black colorant, a resin, a polymerizable compound, and a light-shielding composition containing a polymerization initiator is applied, and the obtained coating film is cured to form a black layer. And a step of forming an oxygen barrier layer on the black layer.

As the "step of forming a black layer", the method described in the above "formation of a black layer" may be applied, and as the "step of forming an oxygen barrier layer", the "step of forming an oxygen barrier layer" May be applied.

［遮光膜の物性及び用途］

　遮光膜の厚さは、例えば、０．１～６．０μｍが好ましく、１．０～３．５μｍがより好ましい。また、遮光膜は、用途にあわせてこの範囲よりも薄膜としてもよいし、厚膜としてもよい。

　遮光膜の反射率は、５％未満が好ましく、３％未満がより好ましく、２％未満が更に好ましい。
[Physical properties and uses of light-shielding film]

The thickness of the light-shielding film is, for example, preferably from 0.1 to 6.0 μm, more preferably from 1.0 to 3.5 μm. The light-shielding film may be thinner or thicker than this range depending on the application.

The reflectance of the light-shielding film is preferably less than 5%, more preferably less than 3%, even more preferably less than 2%.

　また、上記遮光膜は、パーソナルコンピュータ、タブレット、携帯電話、スマートフォン、及び、デジタルカメラ等のポータブル機器；プリンタ複合機、及び、スキャナ等のＯＡ（Ｏｆｆｉｃｅ　Ａｕｔｏｍａｔｉｏｎ）機器；監視カメラ、バーコードリーダ、現金自動預け払い機（ＡＴＭ：ａｕｔｏｍａｔｅｄ　ｔｅｌｌｅｒ　ｍａｃｈｉｎｅ）、ハイスピードカメラ、及び、顔画像認証又は生体認証を使用した本人認証機能を有する機器等の産業用機器；車載用カメラ機器；内視鏡、カプセル内視鏡、及び、カテーテル等の医療用カメラ機器；並びに、生体センサ、バイオセンサ、軍事偵察用カメラ、立体地図用カメラ、気象及び海洋観測カメラ、陸地資源探査カメラ、及び、宇宙の天文及び深宇宙ターゲット用の探査カメラ等の宇宙用機器；等に使用される光学フィルタ及びモジュールの遮光部材及び遮光膜、更には反射防止部材及び反射防止膜に好適である。
In addition, the light-shielding film may be a portable device such as a personal computer, a tablet, a mobile phone, a smartphone, and a digital camera; an OA (Office Automation) device such as a multifunction printer and a scanner; a monitoring camera, a barcode reader, and cash Industrial equipment such as an automated teller machine (ATM), a high-speed camera, and a device having a personal authentication function using face image authentication or biometric authentication; a vehicle-mounted camera device; an endoscope, in a capsule Medical camera equipment such as endoscopes and catheters; and biometric sensors, biosensors, military reconnaissance cameras, stereo map cameras, weather and ocean observation cameras, land resources exploration cameras, and astronomical and deep space astronomy Space equipment such as exploration cameras for targets Light blocking member and the light-shielding film of the optical filter and module used etc., and further is suitable for anti-reflection member and the antireflection film.

　上記遮光膜は、マイクロＬＥＤ（Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）及びマイクロＯＬＥＤ（Ｏｒｇａｎｉｃ　Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）等の用途にも使用できる。上記遮光膜は、マイクロＬＥＤ及びマイクロＯＬＥＤに使用される光学フィルタ及び光学フィルムのほか、遮光機能又は反射防止機能を付与する部材に対して好適である。

　マイクロＬＥＤ及びマイクロＯＬＥＤの例としては、特表２０１５－５００５６２号公報及び特表２０１４－５３３８９０号公報に記載された例が挙げられる。
The light-shielding film can also be used for applications such as a micro LED (Light Emitting Diode) and a micro OLED (Organic Light Emitting Diode). The light-shielding film is suitable for a member having a light-shielding function or an anti-reflection function, in addition to an optical filter and an optical film used for a micro LED and a micro OLED.

Examples of the micro LED and the micro OLED include the examples described in JP-T-2015-500562 and JP-T-2014-533890.

　上記遮光膜は、量子ドットセンサー及び量子ドット固体撮像素子に使用される光学フィルタ及び光学フィルムとしても好適である。また、遮光機能及び反射防止機能を付与する部材として好適である。量子ドットセンサー及び量子ドット固体撮像素子の例としては、米国特許出願公開第２０１２／３７７８９号明細書及び国際公開第２００８／１３１３１３号パンフレットに記載された例が挙げられる。
The light-shielding film is also suitable as an optical filter and an optical film used for a quantum dot sensor and a quantum dot solid-state imaging device. Further, it is suitable as a member for providing a light blocking function and an anti-reflection function. Examples of the quantum dot sensor and the quantum dot solid-state imaging device include those described in U.S. Patent Application Publication No. 2012/37789 and WO 2008/131313.

〔光学素子、並びに、固体撮像素子及び固体撮像装置〕

　本発明の遮光膜は、固体撮像素子に使用することも好ましい。

　本発明の遮光膜は、上述の通り、耐光性及び耐湿性に優れる。また、本発明の遮光膜は、優れた耐熱性を備える。
[Optical element, and solid-state imaging device and solid-state imaging device]

The light-shielding film of the present invention is also preferably used for a solid-state imaging device.

As described above, the light-shielding film of the present invention is excellent in light resistance and moisture resistance. Further, the light-shielding film of the present invention has excellent heat resistance.

　本発明は、光学素子の発明をも含有する。本発明の光学素子は、上記遮光膜を有する光学素子である。光学素子としては、例えば、カメラ、双眼鏡、顕微鏡、及び、半導体露光装置等の光学機器に使用される光学素子が挙げられる。

　中でも、上記光学素子としては、例えば、カメラ等に搭載される固体撮像素子が好ましい。
The present invention also includes the invention of an optical element. The optical element of the present invention is an optical element having the above-mentioned light shielding film. Examples of the optical element include an optical element used for an optical device such as a camera, binoculars, a microscope, and a semiconductor exposure apparatus.

Above all, as the optical element, for example, a solid-state imaging element mounted on a camera or the like is preferable.

　また、本発明の固体撮像素子は、上記遮光膜を有する固体撮像素子である。

　固体撮像素子が遮光膜を含有する形態としては特に制限されず、例えば、基板上に、固体撮像素子（ＣＣＤイメージセンサ、ＣＭＯＳイメージセンサ等）の受光エリアを構成する複数のフォトダイオード及びポリシリコン等からなる受光素子を有し、支持体の受光素子形成面側（例えば、受光部以外の部分及び／又は色調整用画素等）又は形成面の反対側に遮光膜を有する形態が挙げられる。

　また、遮光膜を光減衰膜として使用する場合、例えば、一部の光が光減衰膜を通過した上で受光素子に入射するように、光減衰膜を配置すれば、固体撮像素子のダイナミックレンジを改善できる。

　固体撮像装置は、上記固体撮像素子を具備する。
Further, a solid-state imaging device according to the present invention is a solid-state imaging device having the light-shielding film.

The form in which the solid-state imaging device includes the light-shielding film is not particularly limited. For example, a plurality of photodiodes, polysilicon, and the like, which form a light receiving area of the solid-state imaging device (CCD image sensor, CMOS image sensor, and the like) on the substrate And a light-shielding film on the side of the support on which the light-receiving element is formed (for example, a portion other than the light-receiving portion and / or the pixel for color adjustment) or on the side opposite to the formation surface.

When the light-shielding film is used as a light-attenuating film, for example, if the light-attenuating film is arranged so that a part of the light passes through the light-attenuating film and then enters the light-receiving element, the dynamic range of the solid-state imaging device can be improved. Can be improved.

The solid-state imaging device includes the solid-state imaging device.

　固体撮像装置、及び、固体撮像素子の構成例を図１～２を参照して説明する。なお、図１～２では、各部を明確にするため、相互の厚さ及び／又は幅の比率は無視して一部誇張して表示している。

　図１は、本発明の固体撮像素子を含有する固体撮像装置の構成例を示す概略断面図である。

　図１に示すように、固体撮像装置１００は、矩形状の固体撮像素子１０１と、固体撮像素子１０１の上方に保持され、この固体撮像素子１０１を封止する透明なカバーガラス１０３とを備えている。更に、このカバーガラス１０３上には、スペーサー１０４を介してレンズ層１１１が重ねて設けられている。レンズ層１１１は、支持体１１３とレンズ材１１２とで構成されている。レンズ層１１１は、支持体１１３とレンズ材１１２とが一体成形された構成でもよい。レンズ層１１１の周縁領域に迷光が入射すると光の拡散によりレンズ材１１２での集光の効果が弱くなり、撮像部１０２に届く光が低減する。また、迷光によるノイズの発生も生じる。そのため、このレンズ層１１１の周縁領域は、遮光膜１１４が設けられて遮光されている。本発明の遮光膜は上記遮光膜１１４として使用できる。
Configuration examples of the solid-state imaging device and the solid-state imaging device will be described with reference to FIGS. In FIG. 1 and FIG. 2, in order to clarify each part, the ratio of the thickness and / or width is neglected, and some parts are exaggerated.

FIG. 1 is a schematic sectional view showing a configuration example of a solid-state imaging device including the solid-state imaging device of the present invention.

As shown in FIG. 1, the solid-state imaging device 100 includes a rectangular solid-state imaging device 101, and a transparent cover glass 103 that is held above the solid-state imaging device 101 and seals the solid-state imaging device 101. I have. Further, a lens layer 111 is provided on the cover glass 103 with a spacer 104 interposed therebetween. The lens layer 111 includes a support 113 and a lens material 112. The lens layer 111 may have a configuration in which the support 113 and the lens material 112 are integrally formed. When stray light enters the peripheral region of the lens layer 111, the effect of light condensing by the lens material 112 is weakened by diffusion of light, and light reaching the imaging unit 102 is reduced. Also, noise is generated due to stray light. Therefore, the peripheral area of the lens layer 111 is shielded from light by providing the light shielding film 114. The light shielding film of the present invention can be used as the light shielding film 114.

　固体撮像素子１０１は、その受光面となる撮像部１０２で結像した光学像を光電変換して、画像信号として出力する。この固体撮像素子１０１は、２枚の基板を積層した積層基板１０５を備えている。積層基板１０５は、同サイズの矩形状のチップ基板１０６及び回路基板１０７からなり、チップ基板１０６の裏面に回路基板１０７が積層されている。
The solid-state imaging device 101 photoelectrically converts an optical image formed by the imaging unit 102, which is a light receiving surface, and outputs an image signal. The solid-state imaging device 101 includes a laminated substrate 105 in which two substrates are laminated. The laminated substrate 105 includes a rectangular chip substrate 106 and a circuit substrate 107 having the same size, and the circuit substrate 107 is laminated on the back surface of the chip substrate 106.

　チップ基板１０６として用いられる基板の材料としては特に制限されず、公知の材料を使用できる。
The material of the substrate used as the chip substrate 106 is not particularly limited, and a known material can be used.

　チップ基板１０６の表面中央部には、撮像部１０２が設けられている。また、撮像部１０２の周縁領域には遮光膜１１５が設けられている。この周縁領域に入射する迷光を遮光膜１１５が遮光することにより、この周縁領域内の回路からの暗電流（ノイズ）の発生を防ぐことができる。本発明の遮光膜を遮光膜１１５として用いることが好ましい。
The imaging unit 102 is provided at the center of the surface of the chip substrate 106. Further, a light-shielding film 115 is provided in a peripheral area of the imaging unit 102. Since the light shielding film 115 shields the stray light incident on the peripheral region, generation of dark current (noise) from circuits in the peripheral region can be prevented. It is preferable to use the light-shielding film of the present invention as the light-shielding film 115.

　チップ基板１０６の表面縁部には、複数の電極パッド１０８が設けられている。電極パッド１０８は、チップ基板１０６の表面に設けられた図示しない信号線（ボンディングワイヤでも可）を介して、撮像部１０２に電気的に接続されている。
A plurality of electrode pads 108 are provided on the surface edge of the chip substrate 106. The electrode pad 108 is electrically connected to the imaging unit 102 via a signal line (not shown) (not shown) provided on the surface of the chip substrate 106.

　回路基板１０７の裏面には、各電極パッド１０８の略下方位置にそれぞれ外部接続端子１０９が設けられている。各外部接続端子１０９は、積層基板１０５を垂直に貫通する貫通電極１１０を介して、それぞれ電極パッド１０８に接続されている。また、各外部接続端子１０９は、図示しない配線を介して、固体撮像素子１０１の駆動を制御する制御回路、及び固体撮像素子１０１から出力される撮像信号に画像処理を施す画像処理回路等に接続されている。
External connection terminals 109 are provided on the rear surface of the circuit board 107 at positions substantially below the electrode pads 108, respectively. Each external connection terminal 109 is connected to an electrode pad 108 via a through electrode 110 vertically penetrating the laminated substrate 105. In addition, each external connection terminal 109 is connected to a control circuit that controls driving of the solid-state imaging device 101, an image processing circuit that performs image processing on an imaging signal output from the solid-state imaging device 101, and the like via wiring (not shown). Have been.

　図２に、撮像部１０２の概略断面図を示す。図２に示すように、撮像部１０２は、受光素子２０１、カラーフィルタ２０２、マイクロレンズ２０３等の基板２０４上に設けられた各部から構成される。カラーフィルタ２０２は、青色画素２０５ｂ、赤色画素２０５ｒ、緑色画素２０５ｇ、及び、ブラックマトリクス２０５ｂｍを有している。本発明の遮光膜は、ブラックマトリクス２０５ｂｍとして用いてもよい。
FIG. 2 is a schematic cross-sectional view of the imaging unit 102. As illustrated in FIG. 2, the imaging unit 102 includes various units provided on a substrate 204 such as a light receiving element 201, a color filter 202, and a micro lens 203. The color filter 202 has a blue pixel 205b, a red pixel 205r, a green pixel 205g, and a black matrix 205bm. The light shielding film of the present invention may be used as the black matrix 205bm.

　基板２０４の材料としては、前述のチップ基板１０６と同様の材料を使用できる。基板２０４の表層にはｐウェル層２０６が形成されている。このｐウェル層２０６内には、ｎ型層からなり光電変換により信号電荷を生成して蓄積する受光素子２０１が正方格子状に配列形成されている。
As the material of the substrate 204, the same material as that of the above-described chip substrate 106 can be used. A p-well layer 206 is formed on the surface of the substrate 204. In the p-well layer 206, light receiving elements 201 which are made of an n-type layer and generate and accumulate signal charges by photoelectric conversion are arranged in a square lattice.

　受光素子２０１の一方の側方には、ｐウェル層２０６の表層の読み出しゲート部２０７を介して、ｎ型層からなる垂直転送路２０８が形成されている。また、受光素子２０１の他方の側方には、ｐ型層からなる素子分離領域２０９を介して、隣接画素に属する垂直転送路２０８が形成されている。読み出しゲート部２０７は、受光素子２０１に蓄積された信号電荷を垂直転送路２０８に読み出すためのチャネル領域である。
On one side of the light receiving element 201, a vertical transfer path 208 made of an n-type layer is formed via a readout gate 207 on the surface of the p-well layer 206. On the other side of the light receiving element 201, a vertical transfer path 208 belonging to an adjacent pixel is formed via an element isolation region 209 made of a p-type layer. The read gate unit 207 is a channel region for reading signal charges accumulated in the light receiving element 201 to the vertical transfer path 208.

　基板２０４の表面上には、ＯＮＯ（Ｏｘｉｄｅ－Ｎｉｔｒｉｄｅ－Ｏｘｉｄｅ）膜からなるゲート絶縁膜２１０が形成されている。このゲート絶縁膜２１０上には、垂直転送路２０８、読み出しゲート部２０７、及び、素子分離領域２０９の略直上を覆うように、ポリシリコン又はアモルファスシリコンからなる垂直転送電極２１１が形成されている。垂直転送電極２１１は、垂直転送路２０８を駆動して電荷転送を行わせる駆動電極と、読み出しゲート部２０７を駆動して信号電荷の読み出しを行わせる読み出し電極として機能する。信号電荷は、垂直転送路２０８から図示しない水平転送路及び出力部（フローティングディフュージョンアンプ）に順に転送された後、電圧信号として出力される。
On the surface of the substrate 204, a gate insulating film 210 made of an ONO (Oxide-Nitride-Oxide) film is formed. On the gate insulating film 210, a vertical transfer electrode 211 made of polysilicon or amorphous silicon is formed so as to cover the vertical transfer path 208, the read gate unit 207, and almost immediately above the element isolation region 209. The vertical transfer electrode 211 functions as a drive electrode that drives the vertical transfer path 208 to transfer charges and a read electrode that drives the read gate unit 207 to read signal charges. The signal charges are sequentially transferred from the vertical transfer path 208 to a horizontal transfer path (not shown) and an output unit (floating diffusion amplifier), and then output as a voltage signal.

　垂直転送電極２１１上には、その表面を覆うように遮光膜２１２が形成されている。遮光膜２１２は、受光素子２０１の直上位置に開口部を有し、それ以外の領域を遮光している。本発明の遮光膜は、遮光膜２１２として用いてもよい。

　遮光膜２１２上には、ＢＰＳＧ（ｂｏｒｏｐｈｏｓｐｈｏ　ｓｉｌｉｃａｔｅ　ｇｌａｓｓ）からなる絶縁膜２１３、Ｐ－ＳｉＮからなる絶縁膜（パシベーション膜）２１４、透明樹脂等からなる平坦化膜２１５からなる透明な中間層が設けられている。カラーフィルタ２０２は、中間層上に形成されている。
On the vertical transfer electrode 211, a light shielding film 212 is formed so as to cover the surface thereof. The light-shielding film 212 has an opening at a position immediately above the light-receiving element 201, and shields other areas from light. The light shielding film of the present invention may be used as the light shielding film 212.

On the light-shielding film 212, an insulating film 213 made of borophosphosilicate glass (BPSG), an insulating film (passivation film) 214 made of P-SiN, and a transparent intermediate layer made of a flattening film 215 made of a transparent resin or the like are provided. ing. The color filter 202 is formed on the intermediate layer.

［画像表示装置］

　本発明の画像表示装置は、本発明の遮光膜を具備する。

　画像表示装置が遮光膜を有する形態としては、例えば、ブラックマトリクスとして遮光膜を含有するカラーフィルタが、画像表示装置に使用される形態が挙げられる。

　次に、ブラックマトリクス及びブラックマトリクスを含有するカラーフィルタについて説明し、更に、画像表示装置の具体例として、このようなカラーフィルタを含有する液晶表示装置について説明する。
[Image display device]

The image display device of the present invention includes the light-shielding film of the present invention.

Examples of the mode in which the image display device has a light-shielding film include a mode in which a color filter containing a light-shielding film as a black matrix is used in the image display device.

Next, a black matrix and a color filter containing a black matrix will be described, and a liquid crystal display device containing such a color filter will be described as a specific example of an image display device.

〔ブラックマトリクス〕

　本発明の遮光膜は、ブラックマトリクスとして使用されることも好ましい。ブラックマトリクスは、カラーフィルタ、固体撮像素子、及び、液晶表示装置等の画像表示装置に含有される場合がある。

　ブラックマトリクスとしては、上記で既に説明したもの；液晶表示装置等の画像表示装置の周縁部に設けられた黒色の縁；赤、青、及び、緑の画素間の格子状、及び／又は、ストライプ状の黒色の部分；ＴＦＴ（ｔｈｉｎ　ｆｉｌｍ　ｔｒａｎｓｉｓｔｏｒ）遮光のためのドット状、及び／又は、線状の黒色パターン；等が挙げられる。このブラックマトリクスの定義については、例えば、菅野泰平著、「液晶ディスプレイ製造装置用語辞典」、第２版、日刊工業新聞社、１９９６年、ｐ．６４に記載がある。

　ブラックマトリクスは表示コントラストを向上させるため、また薄膜トランジスタ（ＴＦＴ）を用いたアクティブマトリックス駆動方式の液晶表示装置の場合には光の電流リークによる画質低下を防止するため、高い遮光性（光学濃度ＯＤで３以上）を有することが好ましい。
[Black matrix]

The light-shielding film of the present invention is also preferably used as a black matrix. The black matrix may be included in an image display device such as a color filter, a solid-state imaging device, and a liquid crystal display device.

As the black matrix, those already described above; black edges provided on the periphery of an image display device such as a liquid crystal display device; grids between red, blue, and green pixels, and / or stripes A black portion; and a dot and / or linear black pattern for light blocking of a thin film transistor (TFT). For the definition of the black matrix, see, for example, Taihei Kanno, “Dictionary of Liquid Crystal Display Manufacturing Equipment”, 2nd edition, Nikkan Kogyo Shimbun, 1996, p. 64.

The black matrix has a high light-shielding property (at an optical density OD) in order to improve display contrast and, in the case of an active matrix drive type liquid crystal display device using a thin film transistor (TFT), to prevent deterioration in image quality due to light current leakage. 3 or more).

　ブラックマトリクスの製造方法としては特に制限されないが、上記の遮光膜の製造方法と同様の方法により製造できる。具体的には、基板に組成物を塗布して、塗膜を形成し、露光、及び、現像してパターン状の黒色層を形成した後、黒色層上に酸素遮断層を形成することにより、ブラックマトリクスを製造できる。なお、ブラックマトリクスとして用いられる遮光膜の膜厚としては、０．１～４．０μｍが好ましい。
Although the method for producing the black matrix is not particularly limited, it can be produced by the same method as the above-mentioned method for producing the light shielding film. Specifically, by applying the composition to the substrate, forming a coating film, exposure, and, after forming a patterned black layer by developing, by forming an oxygen barrier layer on the black layer, A black matrix can be manufactured. The thickness of the light shielding film used as the black matrix is preferably from 0.1 to 4.0 μm.

　上記基板の材料としては、特に制限されないが、可視光（波長４００～８００ｎｍ）に対して８０％以上の透過率を有することが好ましい。このような材料としては、具体的には、例えば、ソーダライムガラス、無アルカリガラス、石英ガラス、及び、ホウケイ酸ガラス等のガラス；ポリエステル系樹脂、及び、ポリオレフィン系樹脂等のプラスチック；等が挙げられ、耐薬品性、及び、耐熱性の点から、無アルカリガラス、又は、石英ガラス等が好ましい。
The material of the substrate is not particularly limited, but preferably has a transmittance of 80% or more with respect to visible light (wavelength: 400 to 800 nm). Specific examples of such a material include glasses such as soda lime glass, non-alkali glass, quartz glass, and borosilicate glass; and plastics such as polyester resin and polyolefin resin. In view of chemical resistance and heat resistance, alkali-free glass or quartz glass is preferred.

＜カラーフィルタ＞

　本発明の遮光膜は、カラーフィルタに含有されることも好ましい。

　カラーフィルタが遮光膜を含有する形態としては、特に制限されないが、基板と、上記ブラックマトリクスと、を備えるカラーフィルタが挙げられる。すなわち、基板上に形成された上記ブラックマトリクスの開口部に形成された赤色、緑色、及び、青色の着色画素と、を備えるカラーフィルタが例示できる。
<Color filter>

The light-shielding film of the present invention is preferably contained in a color filter.

The form in which the color filter contains a light-shielding film is not particularly limited, and examples thereof include a color filter including a substrate and the above-described black matrix. That is, a color filter including red, green, and blue colored pixels formed in the openings of the black matrix formed on the substrate can be exemplified.

　ブラックマトリクスを含有するカラーフィルタは、例えば、以下の方法により製造できる。

　まず、基板上に形成されたパターン状のブラックマトリクスの開口部に、カラーフィルタの各着色画素に対応する顔料を含有した組成物の塗膜を形成する。なお、各色用組成物としては特に制限されず、公知の組成物を使用できるが、本明細書で説明した組成物において、黒色色材を、各画素に対応した着色剤に置き換えた組成物を使用することが好ましい。

　次に、塗膜に対して、ブラックマトリクスの開口部に対応したパターンを有するフォトマスクを介して露光する。次いで、現像処理により未露光部を除去した後、ベークしてブラックマトリクスの開口部に着色画素を形成できる。一連の操作を、例えば、赤色、緑色、及び、青色顔料を含有した各色用組成物を用いて行えば、赤色、緑色、及び、青色画素を有するカラーフィルタを製造できる。
A color filter containing a black matrix can be manufactured, for example, by the following method.

First, a coating film of a composition containing a pigment corresponding to each colored pixel of a color filter is formed in an opening of a patterned black matrix formed on a substrate. The composition for each color is not particularly limited, and a known composition can be used.However, in the composition described in this specification, a composition in which a black coloring material is replaced with a coloring agent corresponding to each pixel is used. It is preferred to use.

Next, the coating film is exposed through a photomask having a pattern corresponding to the opening of the black matrix. Next, after removing the unexposed portions by a development process, baking is performed to form colored pixels in the openings of the black matrix. By performing a series of operations using, for example, a composition for each color containing red, green, and blue pigments, a color filter having red, green, and blue pixels can be manufactured.

＜液晶表示装置＞

　本発明の遮光膜は、液晶表示装置に含有されることも好ましい。液晶表示装置が遮光膜を含有する形態としては特に制限されないが、すでに説明したブラックマトリクスを含有するカラーフィルタを含有する形態が挙げられる。
<Liquid crystal display device>

The light-shielding film of the present invention is preferably contained in a liquid crystal display device. The mode in which the liquid crystal display device includes the light-shielding film is not particularly limited, and examples include a mode in which the color filter including the black matrix described above is included.

　本実施形態に係る液晶表示装置としては、例えば、対向して配置された一対の基板と、それらの基板の間に封入されている液晶化合物とを備える形態が挙げられる。上記基板としては、ブラックマトリクス用の基板として既に説明したとおりである。
The liquid crystal display device according to the present embodiment includes, for example, a mode including a pair of substrates arranged to face each other and a liquid crystal compound sealed between the substrates. The substrate is as described above for the substrate for the black matrix.

　上記液晶表示装置の具体的な形態としては、例えば、使用者側から、偏光板／基板／カラーフィルタ／透明電極層／配向膜／液晶層／配向膜／透明電極層／ＴＦＴ（Ｔｈｉｎ　Ｆｉｌｍ　Ｔｒａｎｓｉｓｔｏｒ）素子／基板／偏光板／バックライトユニットをこの順に含有する積層体が挙げられる。
As a specific form of the liquid crystal display device, for example, from a user side, a polarizing plate / substrate / color filter / transparent electrode layer / alignment film / liquid crystal layer / alignment film / transparent electrode layer / TFT (Thin Film Transistor) A laminated body containing an element / substrate / polarizing plate / backlight unit in this order is exemplified.

　なお、液晶表示装置としては、上記に制限されず、例えば「電子ディスプレイデバイス（佐々木　昭夫著、株式会社工業調査会　１９９０年発行）」、「ディスプレイデバイス（伊吹　順章著、産業図書株式会社　平成元年発行）」等に記載されている液晶表示装置が挙げられる。また、例えば「次世代液晶ディスプレイ技術（内田　龍男編集、株式会社工業調査会　１９９４年発行）」に記載されている液晶表示装置が挙げられる。
The liquid crystal display device is not limited to the above. For example, “Electronic display device (by Akio Sasaki, published by the Industrial Research Institute, Inc., 1990)”, “display device (by Junsho Ibuki, Sangyo Tosho Co., Ltd., Heisei Gen) Liquid crystal display device described in “A. Further, for example, a liquid crystal display device described in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by the Industrial Research Institute, Inc., 1994)” may be mentioned.

［赤外線センサ］

　本発明の遮光膜は、赤外線センサに含有されることも好ましい。

　上記実施態様に係る赤外線センサについて、図３を用いて説明する。図３は、本発明の遮光膜を備える赤外線センサの構成例を示す概略断面図である。図３に示す赤外線センサ３００は、固体撮像素子３１０を備える。

　固体撮像素子３１０上に設けられている撮像領域は、赤外線吸収フィルタ３１１と本発明の実施形態に係るカラーフィルタ３１２とを組み合せて構成されている。

　赤外線吸収フィルタ３１１は、可視光領域の光（例えば、波長４００～７００ｎｍの光）を透過し、赤外領域の光（例えば、波長８００～１３００ｎｍの光、好ましくは波長９００～１２００ｎｍの光、より好ましくは波長９００～１０００ｎｍの光）を遮蔽する膜であり、着色剤として赤外線吸収剤（赤外線吸収剤の形態としては既に説明したとおりである。）を含有する硬化膜を使用できる。

　カラーフィルタ３１２は、可視光領域における特定波長の光を透過及び吸収する画素が形成されたカラーフィルタであって、例えば、赤色（Ｒ）、緑色（Ｇ）、青色（Ｂ）の画素が形成されたカラーフィルタ等が用いられ、その形態は既に説明したとおりである。

　赤外線透過フィルタ３１３と固体撮像素子３１０との間には、赤外線透過フィルタ３１３を透過した波長の光を透過可能な樹脂膜３１４（例えば、透明樹脂膜等）が配置されている。

　赤外線透過フィルタ３１３は、可視光遮蔽性を有し、かつ、特定波長の赤外線を透過させるフィルタであって、可視光領域の光を吸収する着色剤（例えば、ペリレン化合物、及び／又は、ベンゾフラノン化合物等）と、赤外線吸収剤（例えば、ピロロピロール化合物、フタロシアニン化合物、ナフタロシアニン化合物、及び、ポリメチン化合物等）と、を含有する、本発明の遮光膜を使用できる。赤外線透過フィルタ３１３は、例えば、波長４００～８３０ｎｍの光を遮光し、波長９００～１３００ｎｍの光を透過させることが好ましい。

　カラーフィルタ３１２及び赤外線透過フィルタ３１３の入射光ｈν側には、マイクロレンズ３１５が配置されている。マイクロレンズ３１５を覆うように平坦化膜３１６が形成されている。

　図３に示す形態では、樹脂膜３１４が配置されているが、樹脂膜３１４に代えて赤外線透過フィルタ３１３を形成してもよい。すなわち、固体撮像素子３１０上に、赤外線透過フィルタ３１３を形成してもよい。

　また、図３に示す形態では、カラーフィルタ３１２の膜厚と、赤外線透過フィルタ３１３の膜厚が同一であるが、両者の膜厚は異なっていてもよい。

　また、図３に示す形態では、カラーフィルタ３１２が、赤外線吸収フィルタ３１１よりも入射光ｈν側に設けられているが、赤外線吸収フィルタ３１１と、カラーフィルタ３１２との順序を入れ替えて、赤外線吸収フィルタ３１１を、カラーフィルタ３１２よりも入射光ｈν側に設けてもよい。

　また、図３に示す形態では、赤外線吸収フィルタ３１１とカラーフィルタ３１２は隣接して積層しているが、両フィルタは必ずしも隣接している必要はなく、間に他の層が設けられていてもよい。本発明の遮光膜は、赤外線吸収フィルタ３１１の表面の端部及び／又は側面等の遮光膜として使用できるほか、赤外線センサの装置内壁に用いれば、内部反射及び／又は受光部への意味しない光の入射を防ぎ、感度を向上させられる。

　この赤外線センサによれば、画像情報を同時に取り込めるため、動きを検知する対象を認識したモーションセンシング等が可能である。また、この赤外線センサによれば、距離情報を取得できるため、３Ｄ情報を含んだ画像の撮影等も可能である。更に、この赤外線センサは、生体認証センサとしても使用できる。
[Infrared sensor]

The light-shielding film of the present invention is preferably contained in an infrared sensor.

The infrared sensor according to the above embodiment will be described with reference to FIG. FIG. 3 is a schematic sectional view showing a configuration example of an infrared sensor having the light-shielding film of the present invention. The infrared sensor 300 shown in FIG.

The imaging region provided on the solid-state imaging device 310 is configured by combining an infrared absorption filter 311 and a color filter 312 according to the embodiment of the present invention.

The infrared absorption filter 311 transmits light in the visible light range (for example, light having a wavelength of 400 to 700 nm), and transmits light in the infrared range (for example, light having a wavelength of 800 to 1300 nm, preferably light having a wavelength of 900 to 1200 nm). Preferably, it is a film that blocks light having a wavelength of 900 to 1000 nm), and a cured film containing an infrared absorbing agent as a coloring agent (the form of the infrared absorbing agent is as described above) can be used.

The color filter 312 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible light region are formed. For example, red (R), green (G), and blue (B) pixels are formed. A color filter or the like is used, and the form is as described above.

Between the infrared transmission filter 313 and the solid-state imaging device 310, a resin film 314 (for example, a transparent resin film or the like) capable of transmitting light having a wavelength transmitted through the infrared transmission filter 313 is arranged.

The infrared transmission filter 313 is a filter that has a visible light shielding property and transmits infrared light of a specific wavelength, and is a colorant that absorbs light in a visible light region (for example, a perylene compound and / or a benzofuranone compound). And the like, and an infrared absorber (for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, and a polymethine compound) can be used as the light-shielding film of the present invention. For example, the infrared transmission filter 313 preferably blocks light having a wavelength of 400 to 830 nm and transmits light having a wavelength of 900 to 1300 nm.

A micro lens 315 is arranged on the side of the incident light hν of the color filter 312 and the infrared transmission filter 313. A flattening film 316 is formed so as to cover the microlens 315.

In the embodiment shown in FIG. 3, the resin film 314 is provided, but an infrared transmission filter 313 may be formed instead of the resin film 314. That is, the infrared transmission filter 313 may be formed on the solid-state imaging device 310.

Further, in the embodiment shown in FIG. 3, the thickness of the color filter 312 and the thickness of the infrared transmission filter 313 are the same, but the thicknesses of the two may be different.

Further, in the embodiment shown in FIG. 3, the color filter 312 is provided on the incident light hν side of the infrared absorption filter 311, but the order of the infrared absorption filter 311 and the color filter 312 is changed, and 311 may be provided closer to the incident light hν than the color filter 312.

Further, in the embodiment shown in FIG. 3, the infrared absorption filter 311 and the color filter 312 are stacked adjacent to each other, but the two filters do not necessarily have to be adjacent to each other, and another layer may be provided between them. Good. The light-shielding film of the present invention can be used as a light-shielding film at the end and / or the side surface of the surface of the infrared absorption filter 311, and when it is used on the inner wall of the device of the infrared sensor, light that does not imply internal reflection and / or light to the light-receiving unit. Can be prevented and sensitivity can be improved.

According to this infrared sensor, since image information can be taken in at the same time, motion sensing or the like that recognizes a target whose motion is to be detected is possible. Further, according to this infrared sensor, since distance information can be obtained, it is possible to capture an image including 3D information. Further, this infrared sensor can be used as a biometric authentication sensor.

　次に、上記赤外線センサを適用した固体撮像装置について説明する。

　上記固体撮像装置は、レンズ光学系と、固体撮像素子と、赤外発光ダイオード等を含有する。なお、固体撮像装置の各構成については、特開２０１１－２３３９８３号公報の段落００３２～００３６を参酌でき、この内容は本願明細書に組み込まれる。
Next, a solid-state imaging device to which the infrared sensor is applied will be described.

The solid-state imaging device includes a lens optical system, a solid-state imaging device, an infrared light emitting diode, and the like. Note that, regarding each configuration of the solid-state imaging device, paragraphs 0032 to 0036 of JP-A-2011-233983 can be referred to, and the contents thereof are incorporated in the specification of the present application.

［ヘッドライトユニット］

　本発明の遮光膜は、自動車等の車両用灯具のヘッドライトユニットに含有されることも好ましい。ヘッドライトユニットに含有される本発明の遮光膜は、光源から出射される光の少なくとも一部を遮光するように、パターン状に形成されることが好ましい。

　上記実施態様に係るヘッドライトユニットについて、図４及び図５を用いて説明する。

図４は、ヘッドライトユニットの構成例を示す模式図であり、図５はヘッドライトユニットの遮光部の構成例を示す模式的斜視図である。

　図４に示すように、ヘッドライトユニット１０は、光源１２と、遮光部１４と、レンズ１６とを有し、光源１２、遮光部１４、及びレンズ１６の順で配置されている。

　遮光部１４は、図５に示すように基体２０と、遮光膜２２とを有する。

　遮光膜２２は、光源１２から出射される光を特定の形状に照射するためのパターン状の開口部２３が形成されている。遮光膜２２の開口部２３の形状により、レンズ１６から照射される配光パターンが決定される。レンズ１６は、遮光部１４を通過した光源１２からの光Ｌを投影するものである。光源１２から、特定の配光パターンを照射することができれば、レンズ１６は、必ずしも必要ではない。レンズ１６は、光Ｌの照射距離、及び照射範囲に応じて適宜決定されるものである。

　また、基体２０は、遮光膜２２を保持することができれば、その構成は、特に限定されるものではないが、光源１２の熱等により変形しないものであることが好ましく、例えば、ガラスで構成される。

　図５では、配光パターンの一例を示したが、これに限定されるものではない。

　また、光源１２も１つに限定されるものではなく、例えば、列状に配置してもよく、マトリクス状に配置してもよい。光源を複数設ける場合、例えば、１つの光源１２に対して、１つの遮光部１４を設ける構成でもよい。この場合、複数の遮光部１４の各遮光膜２２は、全て同じパターンでもよく、それぞれ異なるパターンでもよい。
[Headlight unit]

The light-shielding film of the present invention is also preferably contained in a headlight unit of a vehicle lamp such as an automobile. The light-shielding film of the present invention contained in the headlight unit is preferably formed in a pattern so as to shield at least a part of light emitted from the light source.

The headlight unit according to the above embodiment will be described with reference to FIGS.

FIG. 4 is a schematic diagram illustrating a configuration example of a headlight unit, and FIG. 5 is a schematic perspective view illustrating a configuration example of a light blocking unit of the headlight unit.

As shown in FIG. 4, the headlight unit 10 includes a light source 12, a light shielding unit 14, and a lens 16, and the light source 12, the light shielding unit 14, and the lens 16 are arranged in this order.

The light shielding part 14 has a base 20 and a light shielding film 22 as shown in FIG.

The light-shielding film 22 has a pattern-shaped opening 23 for irradiating light emitted from the light source 12 in a specific shape. The light distribution pattern emitted from the lens 16 is determined by the shape of the opening 23 of the light shielding film 22. The lens 16 projects the light L from the light source 12 that has passed through the light shielding unit 14. If a specific light distribution pattern can be emitted from the light source 12, the lens 16 is not always necessary. The lens 16 is appropriately determined according to the irradiation distance of the light L and the irradiation range.

The configuration of the base 20 is not particularly limited as long as the base 20 can hold the light-shielding film 22, but it is preferable that the base 20 is not deformed by heat of the light source 12, and is made of, for example, glass. You.

FIG. 5 shows an example of the light distribution pattern, but the present invention is not limited to this.

Further, the number of the light sources 12 is not limited to one. For example, the light sources 12 may be arranged in a row or in a matrix. When a plurality of light sources are provided, for example, a configuration in which one light shielding unit 14 is provided for one light source 12 may be employed. In this case, all the light shielding films 22 of the plurality of light shielding portions 14 may have the same pattern or different patterns.

　遮光膜２２のパターンによる配光パターンについて説明する。

　図６はヘッドライトユニットによる配光パターンの一例を示す模式図であり、図７はヘッドライトユニットによる配光パターンの他の例を示す模式図である。なお、図６に示す配光パターン３０と図７に示す配光パターン３２はいずれも光が照射される領域を示している。また、図６に示す領域３１及び図７に示す領域３１は、いずれも遮光膜２２を設けていない場合に光源１２（図４参照）で照射される照射領域を示す。

　遮光膜２２のパターンにより、例えば、図６に示す配光パターン３０のように、エッジ３０ａで光の強度が急激に低下している。図６に示す配光パターン３０は、例えば、左側通行において、対向車に光を照らさないパターンとなる。

　また、図７に示す配光パターン３２のように、図６に示す配光パターン３０の一部を切り欠いたパターンとすることもできる。この場合も、図６に示す配光パターン３０と同じく、エッジ３２ａで光の強度が急激に低下しており、例えば、左側通行において、対向車に光を照らさないパターンとなる。更に、切欠部３３でも光の強度が急激に低下している。このため、切欠部３３に対応する領域に、例えば、道路がカーブしている、上り傾斜、下り傾斜等の状態を示すマークを表示することができる。これにより、夜間走行時の安全性を向上させることができる。
A light distribution pattern based on the pattern of the light shielding film 22 will be described.

FIG. 6 is a schematic diagram illustrating an example of a light distribution pattern by a headlight unit, and FIG. 7 is a schematic diagram illustrating another example of a light distribution pattern by a headlight unit. Each of the light distribution pattern 30 shown in FIG. 6 and the light distribution pattern 32 shown in FIG. 7 shows an area to be irradiated with light. In addition, the region 31 shown in FIG. 6 and the region 31 shown in FIG. 7 indicate irradiation regions irradiated with the light source 12 (see FIG. 4) when the light shielding film 22 is not provided.

Due to the pattern of the light-shielding film 22, the light intensity sharply decreases at the edge 30a, for example, as in the light distribution pattern 30 shown in FIG. The light distribution pattern 30 shown in FIG. 6 is, for example, a pattern that does not illuminate oncoming vehicles when traveling on the left.

Further, like the light distribution pattern 32 shown in FIG. 7, a part of the light distribution pattern 30 shown in FIG. 6 may be cut out. Also in this case, similarly to the light distribution pattern 30 shown in FIG. 6, the intensity of the light is sharply reduced at the edge 32a. For example, the pattern does not illuminate the oncoming vehicle when traveling on the left. Further, the intensity of the light is also sharply reduced in the notch 33. For this reason, in the area corresponding to the notch 33, for example, a mark indicating a state such as a curved road, an upward slope, a downward slope, or the like can be displayed. As a result, safety during night driving can be improved.

　なお、遮光部１４は、光源１２とレンズ１６との間に固定されて配置されることに限定されるものではなく、図示しない駆動機構により、光源１２とレンズ１６との間に、必要に応じて進入させて、特定の配光パターンを得る構成とすることもできる。

　また、遮光部１４で、光源１２からの光を遮光可能なシェード部材を構成してもよい。

この場合、図示しない駆動機構により、光源１２とレンズ１６との間に、必要に応じて進入させて、特定の配光パターンを得る構成とすることもできる。
In addition, the light shielding unit 14 is not limited to being fixedly arranged between the light source 12 and the lens 16, and may be disposed between the light source 12 and the lens 16 by a driving mechanism (not shown) as necessary. , And a specific light distribution pattern can be obtained.

Further, a shade member capable of blocking the light from the light source 12 may be configured by the light shielding unit 14.

In this case, it is also possible to adopt a configuration in which a specific light distribution pattern is obtained by entering the light source 12 and the lens 16 as needed by a driving mechanism (not shown).

　以下に実施例に基づいて本発明を更に詳細に説明する。以下の実施例に示す材料、使用量、割合、処理内容、及び、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更できる。したがって、本発明の範囲は以下に示す実施例により限定的に解釈されるべきではない。
Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

［色材組成物の調製］

　以下の黒色色材を含有する色材組成物を調製して、遮光性組成物の調製に用いた。
[Preparation of coloring material composition]

A coloring material composition containing the following black coloring material was prepared and used for preparing a light-shielding composition.

＜チタンブラック分散液（色材組成物Ａ－１）の調製＞

　平均粒径１５ｎｍの酸化チタンＭＴ－１５０Ａ（商品名、テイカ株式会社製）を１００ｇ、ＢＥＴ表面積３００ｍ２／ｇの酸化ケイ素粒子ＡＥＲＯＧＩＬ（登録商標）３００／３０（エボニック社製）を２５ｇ、及び、分散剤Ｄｉｓｐｅｒｂｙｋ１９０（商品名、ビックケミー社製）を１００ｇ秤量し、これらを混合した。得られた混合物に、イオン電気交換水７１ｇを加えた。得られた混合物を、ＫＵＲＡＢＯ製ＭＡＺＥＲＳＴＡＲ　ＫＫ－４００Ｗを使用して、公転回転数１３６０ｒｐｍ、自転回転数１０４７ｒｐｍにて２０分間処理することにより均一な分散液を得た。この分散液を、石英容器に充填し、小型ロータリーキルン（株式会社モトヤマ製）を用いて酸素雰囲気中で９２０℃に加熱した。その後、窒素で雰囲気を置換し、同温度でアンモニアガスを１００ｍＬ／ｍｉｎで５時間流すことにより、窒化還元処理を実施した。窒化還元処理の終了後、回収した粉末を乳鉢で粉砕し、粉末状の比表面積７３ｍ２／ｇのチタンブラック（色材ａ－１）を得た。
<Preparation of titanium black dispersion (colorant composition A-1)>

100 g of titanium oxide MT-150A (trade name, manufactured by Teika Co., Ltd.) having an average particle diameter of 15 nm, 25 g of silicon oxide particles AEROGIL (registered trademark) 300/30 (manufactured by Evonik) having a BET surface area of 300 m 2 / g, and 100 g of a dispersant Disperbyk 190 (trade name, manufactured by Big Chemie) was weighed and mixed. 71 g of ion-exchanged water was added to the obtained mixture. The obtained mixture was treated at a revolution speed of 1360 rpm and a revolution speed of 1047 rpm for 20 minutes using MAZERSTAR KK-400W manufactured by KURABO to obtain a uniform dispersion. This dispersion was filled in a quartz container and heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Corporation). Thereafter, the atmosphere was replaced with nitrogen, and a nitriding reduction treatment was performed by flowing ammonia gas at the same temperature at 100 mL / min for 5 hours. After completion of the nitridation reduction treatment, the recovered powder was pulverized in a mortar to obtain a powdery titanium black (coloring material a-1) having a specific surface area of 73 m 2 / g.

　上記で得られた色材ａ－１（２０質量部）に対し、下記式（Ｘ－１）で表される構造を有する分散樹脂Ｘ－１（５．５質量部）を加えた後、固形分濃度が３５質量％となるようにプロピレングリコールモノメチルエーテルアセテート（以下「ＰＧＭＥＡ」と記載する）を更に加えた。
The dispersion resin X-1 (5.5 parts by mass) having a structure represented by the following formula (X-1) was added to the coloring material a-1 (20 parts by mass) obtained above, Propylene glycol monomethyl ether acetate (hereinafter, referred to as “PGMEA”) was further added so that the concentration of the components became 35% by mass.

Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026

　上記式（Ｘ－１）において、各繰り返し単位に付した数字は、各繰り返し単位のモル比を意味する。また、上記分散樹脂Ｘ－１の重量平均分子量は３２０００であった。

　得られた分散物を攪拌機により十分に攪拌し、プレミキシングを行った。得られた分散物に対し、分散機ＮＰＭ　Ｐｉｌｏｔ（商品名、株式会社シンマルエンタープライゼス製）を使用して下記条件にて分散処理を行い、色材ａ－１を含有する分散液である色材組成物Ａ－１を得た。
In the formula (X-1), the number given to each repeating unit means the molar ratio of each repeating unit. The weight average molecular weight of the above-mentioned dispersed resin X-1 was 32,000.

The obtained dispersion was sufficiently stirred by a stirrer to perform premixing. The obtained dispersion is subjected to a dispersion treatment using a dispersing machine NPM Pilot (trade name, manufactured by Shinmaru Enterprises Co., Ltd.) under the following conditions to obtain a color which is a dispersion containing the coloring material a-1. A material composition A-1 was obtained.

（分散条件）

・ビーズ径：φ０．０５ｍｍ

・ビーズ充填率：６５体積％

・ミル周速：１０ｍ／ｓｅｃ

・セパレーター周速：１１ｍ／ｓ

・分散処理する混合液量：１５．０ｇ

・循環流量（ポンプ供給量）：６０ｋｇ／ｈｏｕｒ

・処理液温度：２０～２５℃

・冷却水：水道水（５℃）

・ビーズミル環状通路内容積：２．２Ｌ

・パス回数：８４パス
(Dispersion conditions)

・ Bead diameter: φ0.05mm

・ Bead filling rate: 65% by volume

・ Mill peripheral speed: 10m / sec

・ Separator peripheral speed: 11m / s

-The amount of the mixed solution to be dispersed: 15.0 g

・ Circulation flow (pump supply): 60 kg / hour

・ Treating liquid temperature: 20-25 ° C

・ Cooling water: tap water (5 ° C)

・ Bead mill annular passage inner volume: 2.2L

-Number of passes: 84 passes

＜有機顔料分散液（色材組成物Ａ－２）の調製＞

　色材ａ－２としてベンゾフラノン化合物を含有する有機顔料（商品名「Ｉｒｇａｐｈｏｒ　Ｂｌａｃｋ　Ｓ０１００ＣＦ」、ＢＡＳＦ社製）（１５０質量部）、分散樹脂Ｘ－１（７５質量部）、ソルスパース２００００（顔料誘導体、ルーブリゾール社製）（２５質量部）、及び、３－メトキシブチルアセテート（ＭＢＡ）を（７５０質量部）を混合した。分散樹脂Ｘ－１は、上記の色材組成物Ａ－２の分散液の調製に使用したものと同じである。

　得られた混合物を、ホモミキサー（プライミクス社製）で２０分間撹拌して、予備分散液を得た。更に、得られた予備分散液に対し、遠心分離セパレーターを具備したウルトラアペックスミル（寿工業株式会社製）を使用して、下記分散条件にて３時間分散処理を行い、分散組成物を得た。分散終了後、フィルターによりビーズと分散液を分離して、色材ａ－２を含有する分散液である色材組成物Ａ－２を得た。得られた分散液の固形分濃度は２５質量％であり、色材ａ－２／樹脂成分（分散樹脂Ｘ－１と顔料誘導体との合計）の割合は６０／４０（質量比）であった。

　なお、ソルスパース２００００は、アミン価が２９ｍｇＫＯＨ／ｇであり、酸価はなく、顔料吸着基として３級アミンを有する化合物である。
<Preparation of Organic Pigment Dispersion (Coloring Material Composition A-2)>

Organic pigment containing a benzofuranone compound (trade name “Irgaphor Black S0100CF”, manufactured by BASF) (150 parts by mass), dispersing resin X-1 (75 parts by mass), Solsperse 20000 (pigment derivative, Lubri (Zol Co.) (25 parts by mass) and 3-methoxybutyl acetate (MBA) (750 parts by mass). The dispersion resin X-1 is the same as that used for preparing the dispersion of the coloring material composition A-2.

The obtained mixture was stirred with a homomixer (manufactured by Primix) for 20 minutes to obtain a preliminary dispersion. Further, the obtained preliminary dispersion liquid was subjected to a dispersion treatment under the following dispersion conditions for 3 hours using an Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.) equipped with a centrifugal separator to obtain a dispersion composition. . After the dispersion was completed, the beads and the dispersion were separated by a filter to obtain a colorant composition A-2 as a dispersion containing the colorant a-2. The solid content concentration of the obtained dispersion was 25% by mass, and the ratio of the coloring material a-2 / the resin component (the total of the dispersion resin X-1 and the pigment derivative) was 60/40 (mass ratio). .

Solsperse 20000 is a compound having an amine value of 29 mgKOH / g, no acid value, and having a tertiary amine as a pigment adsorbing group.

（分散条件）

・使用ビーズ：φ０．３０ｍｍのジルコニアビーズ（ＹＴＺボール、ネツレン社製）

・ビーズ充填率：７５体積％

・ミル周速：８ｍ／ｓｅｃ

・分散処理する混合液量：１０００ｇ

・循環流量（ポンプ供給量）：１３ｋｇ／ｈｏｕｒ

・処理液温度：２５～３０℃

・冷却水：水道水（５℃）

・ビーズミル環状通路内容積：０．１５Ｌ

・パス回数：９０パス
(Dispersion conditions)

・ Beads used: φ0.30 mm zirconia beads (YTZ balls, manufactured by Netren Corporation)

・ Bead filling rate: 75% by volume

・ Mill peripheral speed: 8m / sec

・ Amount of mixed solution to be dispersed: 1000 g

・ Circulation flow (pump supply): 13 kg / hour

・ Treating liquid temperature: 25-30 ° C

・ Cooling water: tap water (5 ° C)

・ Bead mill inner passage volume: 0.15L

-Number of passes: 90 passes

＜有機顔料分散液（色材組成物Ａ－３）の調製＞

　色材ａ－２に代えて、ペリレン化合物を含有する有機顔料（商品名「ＰＡＬＩＯＧＥＮ　Ｂｌａｃｋ　Ｓ００８４」、ＢＡＳＦ社製）を色材ａ－３として使用したこと以外は、上記の色材組成物Ａ－２の製造方法に従って、色材ａ－３を含有する分散液である色材組成物Ａ－３を得た。
<Preparation of Organic Pigment Dispersion (Coloring Material Composition A-3)>

The above-described coloring material composition A- was used except that an organic pigment containing a perylene compound (trade name “PALIOGEN Black S0084”, manufactured by BASF) was used as the coloring material a-3 instead of the coloring material a-2. According to the production method 2, a coloring material composition A-3 which is a dispersion containing the coloring material a-3 was obtained.

＜カーボンブラック分散液（色材組成物Ａ－４）の調製＞

　通常のオイルファーネス法で、カーボンブラックを製造した。但し、原料油としては、Ｎａ分量、Ｃａ分量、及び、Ｓ分量の少ないエチレンボトム油を用い、ガス燃料を用いて燃焼を行った。更に、反応停止水としては、イオン交換樹脂で処理した純水を用いた。

　ホモミキサーを用いて、得られたカーボンブラック（５４０ｇ）を純水（１４５００ｇ）と共に５，０００～６，０００ｒｐｍで３０分間撹拌し、スラリーを得た。このスラリーをスクリュー型撹拌機付容器に移して、約１，０００ｒｐｍで混合しながら、その容器内に、エポキシ樹脂「エピコート８２８」（ジャパンエポキシレジン社製）（６０ｇ）を溶解したトルエン（６００ｇ）を少量ずつ添加した。約１５分間で、水に分散していたカーボンブラックは全量トルエン側に移行し、粒径約１ｍｍの粒となった。

　次に、６０メッシュ金網で水切りを行った後、分離された粒を真空乾燥機に入れ、７０℃で７時間乾燥し、トルエン及び水を除去して、樹脂被覆カーボンブラック（色材ａ－４）を得た。得られた樹脂被覆カーボンブラックの樹脂被覆量は、カーボンブラックと樹脂の合計量に対して１０質量％であった。
<Preparation of carbon black dispersion (colorant composition A-4)>

Carbon black was produced by the usual oil furnace method. However, as a raw material oil, ethylene bottom oil having a small Na content, a small Ca content, and a small S content was used, and combustion was performed using gas fuel. Further, pure water treated with an ion exchange resin was used as reaction stop water.

Using a homomixer, the obtained carbon black (540 g) was stirred with pure water (14500 g) at 5,000 to 6,000 rpm for 30 minutes to obtain a slurry. This slurry was transferred to a container equipped with a screw-type stirrer, and while mixing at about 1,000 rpm, toluene (600 g) in which epoxy resin “Epicoat 828” (manufactured by Japan Epoxy Resin) (60 g) was dissolved in the container. Was added in small portions. In about 15 minutes, all of the carbon black dispersed in the water migrated to the toluene side, and became particles having a particle size of about 1 mm.

Next, after draining with a 60-mesh wire net, the separated granules are put into a vacuum drier and dried at 70 ° C. for 7 hours to remove toluene and water, and the resin-coated carbon black (coloring material a-4) ) Got. The resin coating amount of the obtained resin-coated carbon black was 10% by mass based on the total amount of the carbon black and the resin.

　上記で得られた色材ａ－４（２０質量部）、分散樹脂Ｘ－１（４．５質量部）、及び、ソルスパース１２０００（日本ルーブリゾール社製）（１質量部）を混合し、得られた混合物に、固形分濃度が３５質量％となるようにＰＧＭＥＡを加えた。分散樹脂Ｘ－１は、上記の色材組成物Ａ－１の調製に使用したものと同じである。

　得られた分散物を攪拌機により十分に攪拌し、プレミキシングを行った。得られた分散物に対し、寿工業株式会社製のウルトラアペックスミルＵＡＭ０１５を使用して下記条件にて分散処理を行い、分散組成物を得た。分散終了後、フィルターによりビーズと分散液を分離して、色材ａ－４を含有する分散液である色材組成物Ａ－４を得た。
The coloring material a-4 (20 parts by mass) obtained above, the dispersing resin X-1 (4.5 parts by mass), and Solsperse 12000 (manufactured by Nippon Lubrizol) (1 part by mass) were mixed to obtain a mixture. PGMEA was added to the obtained mixture so that the solid content concentration became 35% by mass. The dispersion resin X-1 is the same as that used in the preparation of the coloring material composition A-1.

The obtained dispersion was sufficiently stirred by a stirrer to perform premixing. The obtained dispersion was subjected to a dispersion treatment using Ultra Apex Mill UAM015 manufactured by Kotobuki Industries Co., Ltd. under the following conditions to obtain a dispersion composition. After the dispersion was completed, the beads and the dispersion were separated by a filter to obtain a colorant composition A-4, which is a dispersion containing the colorant a-4.

（分散条件）

・ビーズ径：φ０．０５ｍｍ

・ビーズ充填率：７５体積％

・ミル周速：８ｍ／ｓｅｃ

・分散処理する混合液量：５００ｇ

・循環流量（ポンプ供給量）：１３ｋｇ／ｈｏｕｒ

・処理液温度：２５～３０℃

・冷却水：水道水（５℃）

・ビーズミル環状通路内容積：０．１５Ｌ

・パス回数：９０パス
(Dispersion conditions)

・ Bead diameter: φ0.05mm

・ Bead filling rate: 75% by volume

・ Mill peripheral speed: 8m / sec

・ Amount of mixed solution to be dispersed: 500 g

・ Circulation flow (pump supply): 13 kg / hour

・ Treating liquid temperature: 25-30 ° C

・ Cooling water: tap water (5 ° C)

・ Bead mill inner passage volume: 0.15L

-Number of passes: 90 passes

＜チタンブラック分散液（色材組成物Ａ－５）の調製＞

　分散樹脂Ｘ－１に代えて、下記式（Ｘ－２）で表される構造を有する分散樹脂Ｘ－２を使用したこと以外は、上記の色材組成物Ａ－１の製造方法に従って、色材ａ－１を含有する分散液である色材組成物Ａ－５を得た。
<Preparation of titanium black dispersion (colorant composition A-5)>

Except for using the dispersion resin X-2 having the structure represented by the following formula (X-2) in place of the dispersion resin X-1, the coloration was carried out according to the above-described method for producing the coloring material composition A-1. A coloring material composition A-5 as a dispersion containing the material a-1 was obtained.

Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027

　上記式（Ｘ－２）において、各繰り返し単位に付した数字は、各繰り返し単位のモル比を意味する。また、上記分散樹脂Ｘ－２の重量平均分子量は３３０００であった。
In the above formula (X-2), the number given to each repeating unit means the molar ratio of each repeating unit. The weight average molecular weight of the above-mentioned dispersed resin X-2 was 33,000.

［アルカリ可溶性樹脂］

＜アルカリ可溶性樹脂Ｂ－１の合成＞

　乾燥窒素気流下、３０．０３ｇの２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン（０．０８２モル）、１．２４ｇの１，３－ビス（３－アミノプロピル）テトラメチルジシロキサン（０．００５モル）、及び、末端封止剤である２．７３ｇの３－アミノフェノール（０．０２５モル）を、１００ｇのＮ－メチル－２－ピロリドン（以下、「ＮＭＰ」とも記載する）に溶解した。得られた溶液に、３１．０２ｇのビス（３，４－ジカルボキシフェニル）エーテル二無水物（０．１０モル）及び３０ｇのＮＭＰを加えた。得られた溶液を、２０℃で１時間撹拌し、更に、水を除去しながら１８０℃で４時間撹拌した。反応終了後、反応液を２Ｌの水に投入し、生成した沈殿物をろ過により集めた。得られた沈殿物を、水で３回洗浄し、８０℃の真空乾燥機で２０時間乾燥して、アルカリ可溶性樹脂Ｂ－１（ポリイミド樹脂）を合成した。
[Alkali-soluble resin]

<Synthesis of alkali-soluble resin B-1>

Under a stream of dry nitrogen, 30.03 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (0.082 mol), 1.24 g of 1,3-bis (3-aminopropyl) tetra Methyldisiloxane (0.005 mol) and 2.73 g of 3-aminophenol (0.025 mol) as a terminal blocking agent were combined with 100 g of N-methyl-2-pyrrolidone (hereinafter also referred to as “NMP”). Described). To the resulting solution was added 31.02 g of bis (3,4-dicarboxyphenyl) ether dianhydride (0.10 mol) and 30 g of NMP. The obtained solution was stirred at 20 ° C. for 1 hour, and further stirred at 180 ° C. for 4 hours while removing water. After the completion of the reaction, the reaction solution was poured into 2 L of water, and the generated precipitate was collected by filtration. The resulting precipitate was washed three times with water and dried in a vacuum dryer at 80 ° C. for 20 hours to synthesize an alkali-soluble resin B-1 (polyimide resin).

＜アルカリ可溶性樹脂Ｂ－２＞

　また、アルカリ可溶性樹脂Ｂ－２として、下記式（Ｂ－２）で表される構造を有する樹脂を用いた。
<Alkali-soluble resin B-2>

Further, as the alkali-soluble resin B-2, a resin having a structure represented by the following formula (B-2) was used.

Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028

＜アルカリ可溶性樹脂Ｂ－３の合成＞

　窒素気流下、ジフェニルエーテル－４，４’－ジカルボン酸４１．３ｇと１－ヒドロキシ－１，２，３－ベンゾトリアゾール４３．２ｇを反応させて得られたジカルボン酸誘導体の混合物０．１６モルと２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン７３．３ｇをＮＭＰ５６０ｇに溶解させ、その後７５℃で１２時間反応させた。次に、ＮＭＰ７０ｇに溶解させた５－ノルボルネン－２，３－ジカルボン酸無水物１３．１ｇを加え、更に１２時間撹拌した。反応混合物をろ過した後、水／メタノール＝３／１（体積比）の溶液に滴下し、白色沈殿を得た。沈殿を水で３回洗浄した後、真空乾燥機で８０℃、２４時間乾燥し、アルカリ可溶性樹脂Ｂ－３（ポリベンゾオキサゾール前駆体からなる樹脂）を得た。
<Synthesis of alkali-soluble resin B-3>

0.16 mol of a mixture of dicarboxylic acid derivatives obtained by reacting 41.3 g of diphenyl ether-4,4'-dicarboxylic acid with 43.2 g of 1-hydroxy-1,2,3-benzotriazole under a nitrogen stream and 2 73.3 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 560 g of NMP, and then reacted at 75 ° C. for 12 hours. Next, 13.1 g of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 70 g of NMP was added, and the mixture was further stirred for 12 hours. After filtering the reaction mixture, the reaction mixture was added dropwise to a solution of water / methanol = 3/1 (volume ratio) to obtain a white precipitate. After the precipitate was washed three times with water, it was dried in a vacuum dryer at 80 ° C. for 24 hours to obtain an alkali-soluble resin B-3 (a resin composed of a polybenzoxazole precursor).

［重合開始剤］

　以下の重合開始剤を、遮光性組成物の調製に用いた。

・重合開始剤Ｃ－１：下記式（Ｃ－１）で表される化合物

・重合開始剤Ｃ－２：ＩＲＧＡＣＵＲＥ　ＯＸＥ－０２（商品名、ＢＡＳＦ社製）

・重合開始剤Ｃ－３：ＩＲＧＡＣＵＲＥ　３６９（商品名、ＢＡＳＦ社製）

　上記重合開始剤はいずれも光重合開始剤であり、上記重合開始剤のうち、重合開始剤Ｃ－１及びＣ－２は、オキシムエステル系重合開始剤である。
[Polymerization initiator]

The following polymerization initiator was used for preparing the light-shielding composition.

A polymerization initiator C-1: a compound represented by the following formula (C-1)

-Polymerization initiator C-2: IRGACURE OXE-02 (trade name, manufactured by BASF)

-Polymerization initiator C-3: IRGACURE 369 (trade name, manufactured by BASF)

Each of the above polymerization initiators is a photopolymerization initiator, and among the above polymerization initiators, the polymerization initiators C-1 and C-2 are oxime ester-based polymerization initiators.

Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029

［重合性化合物］

　下記式（Ｄ－１）で表される重合性化合物Ｄ－１、及び、下記式（Ｄ－２）で表される重合性化合物Ｄ－２を、組成物の調製に用いた。

　重合性化合物Ｄ－１は、５官能の重合性化合物と６官能の重合性化合物との混合物であり、その混合比は、５官能の重合性化合物／６官能の重合性化合物＝３０／７０（質量比）である。

　なお、上記「官能」の値は、重合性化合物１分子が有するエチレン性不飽和基の数を示す。
[Polymerizable compound]

A polymerizable compound D-1 represented by the following formula (D-1) and a polymerizable compound D-2 represented by the following formula (D-2) were used for preparing a composition.

The polymerizable compound D-1 is a mixture of a pentafunctional polymerizable compound and a hexafunctional polymerizable compound, and the mixing ratio thereof is pentafunctional polymerizable compound / hexafunctional polymerizable compound = 30/70 ( Mass ratio).

The value of the above “functionality” indicates the number of ethylenically unsaturated groups in one molecule of the polymerizable compound.

Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030

Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031

［界面活性剤］

　下記式（Ｓ－１）で表される界面活性剤を、組成物の調製に用いた。

　なお、式（Ｓ－１）中の各繰り返し単位に付された符号は、各繰り返し単位のモル比を示し、ｌ＋ｎ＝１４、ｍ＝１７である。また、式（Ｓ－１）で表される界面活性剤の重量平均分子量は１５０００である。
[Surfactant]

The surfactant represented by the following formula (S-1) was used for preparing a composition.

The symbol given to each repeating unit in the formula (S-1) indicates the molar ratio of each repeating unit, and 1 + n = 14 and m = 17. The weight average molecular weight of the surfactant represented by the formula (S-1) is 15,000.

Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032

［重合禁止剤］

　重合禁止剤として、ｐ－メトキシフェノールを、遮光性組成物の調製に用いた。
[Polymerization inhibitor]

As a polymerization inhibitor, p-methoxyphenol was used for preparing a light-shielding composition.

［溶剤］

　溶剤として、シクロヘキサノンを、遮光性組成物の調製に用いた。
[solvent]

Cyclohexanone was used as a solvent for preparing the light-shielding composition.

［実施例１］

＜遮光性組成物１の調製＞

　下記の成分を攪拌機で混合することで、実施例１の遮光性組成物１を調製した。

・上記で調製された色材組成物Ａ－１　　６３質量部

・アルカリ可溶性樹脂Ｂ－１　　３．５質量部

・重合開始剤Ｃ－１　　１．８質量部

・重合性化合物Ｄ－１　　６．１質量部

・界面活性剤　　０．０２質量部

・重合禁止剤　　０．００３質量部

・溶剤　　２５．５質量部
[Example 1]

<Preparation of light-shielding composition 1>

The light-shielding composition 1 of Example 1 was prepared by mixing the following components with a stirrer.

-63 parts by mass of the coloring material composition A-1 prepared above

・ 3.5 parts by mass of alkali-soluble resin B-1

・ 1.8 parts by mass of polymerization initiator C-1

-Polymerizable compound D-1 6.1 parts by mass

・ Surfactant 0.02 parts by mass

・ Polymerization inhibitor 0.003 parts by mass

・ Solvent 25.5 parts by mass

＜黒色層の作製＞

　上記で得られた遮光性組成物１を、ガラス基板上に、スピンコート法により塗布し、厚さ１．７μｍの塗膜を形成した。塗膜付き基板に対して１００℃で１２０秒間のプリベークを行った。次いで、開口線幅５０μｍのＬ／Ｓ（ラインアンドスペース）パターンのマスクを介して、ＵＸ－１０００ＳＭ－ＥＨ０４（商品名、ウシオ電機株式会社製）を用いて、高圧水銀ランプ（ランプパワー５０ｍＷ／ｃｍ２）にて、プロキシミティ方式による露光を、塗膜付き基板に対して行った。次にＡＤ－１２００（ミカサ株式会社製）を使用して現像液「ＣＤ－２０６０」（商品名、富士フイルムエレクトロニクスマテリアルズ社製）をパドルで１５秒間現像した。次いで、シャワーノズルを用いて純水で３０秒間洗浄して、未硬化部を除去することにより、基板上に黒色層を形成した。
<Preparation of black layer>

The light-shielding composition 1 obtained above was applied on a glass substrate by a spin coating method to form a coating film having a thickness of 1.7 μm. The coated substrate was prebaked at 100 ° C. for 120 seconds. Then, using a UX-1000SM-EH04 (trade name, manufactured by Ushio Inc.) through a L / S (line and space) pattern mask having an opening line width of 50 μm, a high-pressure mercury lamp (lamp power 50 mW / cm). In 2 ), exposure by the proximity method was performed on the substrate with the coating film. Next, a developing solution “CD-2060” (trade name, manufactured by Fuji Film Electronics Materials Co., Ltd.) was developed with a paddle using AD-1200 (manufactured by Mikasa Corporation) for 15 seconds. Next, the substrate was washed with pure water for 30 seconds using a shower nozzle to remove uncured portions, thereby forming a black layer on the substrate.

＜酸素遮断層Ｅ－１の形成＞

　スパッタリング装置（神港精機社製、商品名「ＳＲＶ－４３００」）の真空チャンバ内に、アルゴンと酸素との混合ガス（酸素：４０体積％）を導入し、シリコンターゲットを用いてスパッタリングを行うことにより、上記で作製された黒色層の表面に、酸化ケイ素（ＳｉＯ２）からなる酸素遮断層Ｅ－１（厚さ：１００ｎｍ）を形成した。

　これにより、基板上に黒色層及び酸素遮断層Ｅ－１がこの順序で形成されてなる、実施例１の遮光膜が得られた。
<Formation of oxygen barrier layer E-1>

A mixed gas of argon and oxygen (oxygen: 40% by volume) is introduced into a vacuum chamber of a sputtering apparatus (trade name “SRV-4300” manufactured by Shinko Seiki Co., Ltd.) and sputtering is performed using a silicon target. As a result, an oxygen barrier layer E-1 (thickness: 100 nm) made of silicon oxide (SiO 2 ) was formed on the surface of the black layer prepared above.

Thus, the light-shielding film of Example 1 in which the black layer and the oxygen blocking layer E-1 were formed on the substrate in this order, was obtained.

［実施例２～６、８、９、１４～１７］

　遮光性組成物の組成が表１及び表２に記載された組成になるように、使用する各成分を代えたこと、又は、色材組成物Ａ－１の添加量を調整したこと以外は、実施例１に記載の方法に従って、各実施例の遮光性組成物をそれぞれ調製した。

　上記で得られた各遮光性組成物を用いること以外は実施例１に記載の方法に従って、基板上に、黒色層及び酸素遮断層がこの順序で形成されてなる、実施例２～６、８、９及び１４～１７の遮光膜を、それぞれ作製した。
[Examples 2 to 6, 8, 9, 14 to 17]

Except that the components used were changed or the addition amount of the coloring material composition A-1 was adjusted so that the composition of the light-shielding composition became the composition described in Tables 1 and 2, According to the method described in Example 1, the light-shielding compositions of each Example were prepared.

Examples 2 to 6, 8 in which a black layer and an oxygen blocking layer are formed in this order on a substrate according to the method described in Example 1 except that each light-shielding composition obtained above is used. , 9 and 14 to 17 were produced, respectively.

［実施例７］

　スパッタリング工程において、真空チャンバ内にアルゴンと窒素との混合ガス（窒素：５０体積％）を導入してスパッタリングを行うことにより、黒色層の表面に、窒化ケイ素（Ｓｉ３Ｎ４）からなる酸素遮断層Ｅ－２（厚さ：１００ｎｍ）を形成すること以外は、実施例１に記載の方法に従って、基板上に、黒色層及び酸素遮断層Ｅ－２がこの順序で形成されてなる、実施例７の遮光膜を作製した。
[Example 7]

In the sputtering process, by introducing a mixed gas of argon and nitrogen (nitrogen: 50% by volume) into the vacuum chamber and performing sputtering, the surface of the black layer is blocked from oxygen made of silicon nitride (Si 3 N 4 ). An example in which a black layer and an oxygen barrier layer E-2 are formed in this order on a substrate according to the method described in Example 1 except that a layer E-2 (thickness: 100 nm) is formed. 7 light-shielding films were produced.

［実施例１０～１３］

　スパッタリング工程において、放電電力及び成膜時間を調整し、表２に記載の厚さを有する酸化ケイ素（ＳｉＯ２）からなる酸素遮断層Ｅ－３～Ｅ－６をそれぞれ形成すること以外は、実施例１に記載の方法に従って、基板上に、黒色層及び酸素遮断層がこの順序で形成されてなる、実施例１０～１３の遮光膜を、それぞれ作製した。
[Examples 10 to 13]

In the sputtering step, the procedure was performed except that the discharge power and the film formation time were adjusted, and the oxygen barrier layers E-3 to E-6 made of silicon oxide (SiO 2 ) having the thicknesses shown in Table 2 were formed. According to the method described in Example 1, the light-shielding films of Examples 10 to 13 each having a black layer and an oxygen blocking layer formed in this order on a substrate were produced.

［比較例１］

＜酸素遮断層形成用組成物の調製＞

　下記の成分を混合して、比較用組成物１を調製した。

・ポリビニルアルコール（ＰＶＡ）：３２．２質量部（商品名：ＰＶＡ２０５、株式会社クラレ製、鹸化度＝８８％、重合度５５０）

・ポリビニルピロリドン（ＰＶＰ）：１４．９質量部（商品名：Ｋ－３０、アイエスピー・ジャパン株式会社製）

・蒸留水：５２４質量部

・メタノール：４２９質量部
[Comparative Example 1]

<Preparation of composition for forming oxygen barrier layer>

The following components were mixed to prepare Comparative Composition 1.

-Polyvinyl alcohol (PVA): 32.2 parts by mass (trade name: PVA205, manufactured by Kuraray Co., Ltd., saponification degree = 88%, polymerization degree 550)

・ Polyvinyl pyrrolidone (PVP): 14.9 parts by mass (trade name: K-30, manufactured by ASP Japan Co., Ltd.)

・ Distilled water: 524 parts by mass

・ Methanol: 429 parts by mass

＜比較用酸素遮断層ＣＥ－１の形成＞

　実施例１に記載の黒色層の作製方法に従って、基板上に黒色層を形成した。

　作製された黒色層の表面に、スピンコーターを用いて組成物１を塗布した。組成物１の塗布量は、乾燥後の層の厚さが１０００ｎｍとなるように調整した。その後、ホットプレートを用いて、樹脂組成物１の塗膜を１００℃で１２０秒間乾燥し、比較用酸素遮断層ＣＥ－１（厚さ：１０００ｎｍ）を形成した。

　これにより、基板上に黒色層及び酸素遮断層ＣＥ－１がこの順序で形成されてなる、比較例１の遮光膜が得られた。
<Formation of Comparative Oxygen Blocking Layer CE-1>

According to the method for manufacturing a black layer described in Example 1, a black layer was formed on a substrate.

Composition 1 was applied to the surface of the produced black layer using a spin coater. The coating amount of the composition 1 was adjusted so that the thickness of the layer after drying was 1000 nm. Thereafter, the coating film of the resin composition 1 was dried at 100 ° C. for 120 seconds using a hot plate to form a comparative oxygen barrier layer CE-1 (thickness: 1000 nm).

Thus, the light-shielding film of Comparative Example 1 in which the black layer and the oxygen blocking layer CE-1 were formed on the substrate in this order, was obtained.

［比較例２］

　酸素遮断層の形成工程において、乾燥後の層の厚さが５００ｎｍとなるように組成物１の塗布量を調整したこと以外は、比較例１に記載の方法に従って、基板上に、黒色層及び酸素遮断層ＣＥ－２がこの順序で形成されてなる、比較例２の遮光膜を作製した。
[Comparative Example 2]

In the step of forming the oxygen blocking layer, a black layer and a black layer were formed on the substrate according to the method described in Comparative Example 1 except that the amount of the composition 1 was adjusted so that the thickness of the layer after drying was 500 nm. A light-shielding film of Comparative Example 2 in which the oxygen blocking layer CE-2 was formed in this order was produced.

［比較例３］

　遮光性組成物の調製工程において、アルカリ可溶性樹脂Ｂ－１に代えてアルカリ可溶性樹脂Ｂ－２を使用すること以外は、比較例１に記載の方法に従って、基板上に、黒色層及び酸素遮断層ＣＥ－１がこの順序で形成されてなる、比較例３の遮光膜を作製した。
[Comparative Example 3]

In the step of preparing the light-shielding composition, a black layer and an oxygen-blocking layer were formed on a substrate according to the method described in Comparative Example 1, except that the alkali-soluble resin B-2 was used instead of the alkali-soluble resin B-1. A light-shielding film of Comparative Example 3 in which CE-1 was formed in this order was produced.

［比較例４～６］

　スパッタリング工程において、放電電力及び成膜時間を調整し、表３に記載の厚さを有する層をそれぞれ形成したこと以外は、実施例１に記載の方法に従って、基板上に、黒色層及び酸素遮断層ＣＥ－３～ＣＥ－５がこの順序で形成されてなる、比較例４～６の遮光膜を、それぞれ作製した。
[Comparative Examples 4 to 6]

In the sputtering process, a black layer and an oxygen barrier were formed on a substrate according to the method described in Example 1, except that the discharge power and the film formation time were adjusted and layers having the thicknesses described in Table 3 were formed. Light-shielding films of Comparative Examples 4 to 6, in which the layers CE-3 to CE-5 were formed in this order, were produced.

［比較例７］

＜酸素遮断層形成用組成物の調製＞

　特開２０１３－２５３１４５号公報の段落００３２～００３４及び００４２（実施例１－１）に記載の方法に従って、テトラメトキシシラン（ＴＭＯＳ）とトリフルオロプロピルトリメトキシシラン（ＴＦＰＴＭＳ）との加水分解物、及び、数珠状コロイダルシリカ粒子が分散したシリカゾルを混合して、比較用組成物２を調製した。
[Comparative Example 7]

<Preparation of composition for forming oxygen barrier layer>

A hydrolyzate of tetramethoxysilane (TMOS) and trifluoropropyltrimethoxysilane (TFPTMS) according to the method described in paragraphs 0032 to 0034 and 0042 (Example 1-1) of JP-A-2013-253145, and A silica sol in which beaded colloidal silica particles were dispersed was mixed to prepare Comparative Composition 2.

＜比較用酸素遮断層ＣＥ－６の形成＞

　酸素遮断層の形成工程において、組成物１に代えて上記で調製された比較用組成物２を使用したこと、及び、乾燥後の層の厚さが１９０ｎｍとなるように比較用組成物２の塗布量を調整したこと以外は、比較例１に記載の方法に従って、基板上に、黒色層及び酸素遮断層ＣＥ－６がこの順序で形成されてなる、比較例７の遮光膜を作製した。

　なお、酸素遮断層ＣＥ－６の表面を研磨して平滑な面を形成し、次いで、形成した平滑面を電子線マイクロアナライザー（日本電子株式会社社製「ＪＸＡ－８５３０Ｆ」（商品名））を用いて分析した。その結果、酸素遮断層ＣＥ－６を構成する材料中の炭素原子の含有量は、酸素遮断層の総質量に対して２７質量％であった。
<Formation of Comparative Oxygen Blocking Layer CE-6>

In the step of forming the oxygen barrier layer, the comparative composition 2 prepared above was used in place of the composition 1, and the comparative composition 2 was dried so that the thickness of the layer after drying was 190 nm. A light-shielding film of Comparative Example 7 was formed by forming a black layer and an oxygen-blocking layer CE-6 on a substrate in this order according to the method described in Comparative Example 1 except that the amount of coating was adjusted.

The surface of the oxygen blocking layer CE-6 was polished to form a smooth surface, and then the formed smooth surface was analyzed with an electron beam microanalyzer (“JXA-8530F” (trade name) manufactured by JEOL Ltd.). And analyzed. As a result, the content of carbon atoms in the material constituting the oxygen barrier layer CE-6 was 27% by mass relative to the total mass of the oxygen barrier layer.

［比較例８～１０］

　酸素遮断層Ｅ－１を形成しないこと以外は、実施例１、６及び５に記載の方法に従って、基板上に、黒色層のみが形成されてなる比較例８～１０の遮光膜を、それぞれ作製した。
[Comparative Examples 8 to 10]

Except that the oxygen barrier layer E-1 was not formed, the light-shielding films of Comparative Examples 8 to 10 in which only the black layer was formed on the substrate were produced in accordance with the methods described in Examples 1, 6 and 5, respectively. did.

〔評価〕

　上記で得られた各酸素遮断層又は各遮光膜を、以下の試験及び評価に供した。
[Evaluation]

Each oxygen barrier layer or each light shielding film obtained above was subjected to the following tests and evaluations.

［酸素透過率の測定］

　黒色層付き基板に代えて、剥離層付き基板を使用して、剥離層上に各酸素遮断層を形成すること以外は、実施例１、７及び１０～１３、並びに、比較例１、２及び４～７に記載の方法に従って、基板上に、剥離層及び酸素遮断層がこの順序で形成されてなる積層体を、それぞれ作製した。次いで、得られた酸素遮断層から酸素遮断層を剥離し、酸素透過率評価用の酸素遮断層を作製した。

　上記で作製された評価用酸素遮断層の酸素透過率（ｍｌ／（ｍ２・ｄａｙ・ａｔｍ））を、酸素透過測定装置（Ｍｏｄｅｌ８００１、イリノイ株式会社製）を用いて測定した。
[Measurement of oxygen permeability]

Examples 1, 7, and 10 to 13, and Comparative Examples 1, 2, and 7, except that a substrate with a release layer was used instead of the substrate with a black layer, and each oxygen barrier layer was formed on the release layer. According to the methods described in 4 to 7, laminates each having a release layer and an oxygen blocking layer formed on the substrate in this order were produced. Next, the oxygen barrier layer was peeled off from the obtained oxygen barrier layer to prepare an oxygen barrier layer for evaluating oxygen permeability.

The oxygen permeability (ml / (m 2 · day · atm)) of the oxygen barrier layer for evaluation produced as described above was measured using an oxygen permeation measuring device (Model 8001, Illinois).

［耐光性の評価］

＜照射試験＞

　上記で得られた遮光膜に対して、耐光試験機（スガ試験機株式会社製、Ｓｕｐｅｒ　Ｘｅｎｏｎ　Ｗｅａｔｈｅｒ　Ｍｅｔｅｒ（商品名））を用いて、ランプ照度７５Ｗ／ｍ２（３００－４００ｎｍ）及び湿度５０％ＲＨの条件下、５００時間の照射試験を行った。
[Evaluation of light resistance]

<Irradiation test>

Using a light fastness tester (Super Xenon Weather Meter (trade name), manufactured by Suga Test Instruments Co., Ltd.), the lamp illuminance is 75 W / m 2 (300-400 nm) and the humidity is 50% for the light-shielding film obtained above. An irradiation test was performed for 500 hours under the condition of RH.

＜照射試験前後での膜厚変化＞

　照射試験の前後での遮光膜の膜厚を、接触式膜厚計を用いて測定した。照射試験前後での遮光膜の膜厚の変化率を、下記式を用いて算出し、下記の観点により評価した。

　なお、「遮光膜の膜厚」とは、黒色層の厚さと酸素遮断層の厚さとの合計を意味し、基板の厚さを含有しない。

　膜厚の変化率（％）＝（（照射試験前の遮光膜の膜厚－照射試験後の遮光膜の膜厚）／（照射試験前の遮光膜の膜厚）×１００）

　Ａ：膜厚の変化率が、２％未満

　Ｂ：膜厚の変化率が、２％以上５％未満

　Ｃ：膜厚の変化率が、５％以上１０％未満

　Ｄ：膜厚の変化率が、１０％以上
<Change in film thickness before and after irradiation test>

The thickness of the light-shielding film before and after the irradiation test was measured using a contact-type film thickness meter. The rate of change in the thickness of the light-shielding film before and after the irradiation test was calculated using the following equation, and evaluated from the following viewpoints.

The “film thickness of the light-shielding film” means the sum of the thickness of the black layer and the thickness of the oxygen blocking layer, and does not include the thickness of the substrate.

Change rate of film thickness (%) = ((film thickness of light-shielding film before irradiation test−film thickness of light-shielding film after irradiation test) / (film thickness of light-shielding film before irradiation test) × 100)

A: Change rate of film thickness is less than 2%

B: Change rate of film thickness is 2% or more and less than 5%

C: Change rate of film thickness is 5% or more and less than 10%

D: Change rate of film thickness is 10% or more

＜照射試験前後での透過率及び反射率の変化＞

　分光器Ｖ７２００（商品名、日本分光株式会社製）を用いて、照射試験の前後の遮光膜に対して角度５°の入射角で光を入射し、得られた透過スペクトル及び反射スペクトルのうち、波長３５０～１２００ｎｍでの最大透過率（以下、透過率と記載する。）及び波長５５０ｎｍの反射率を測定した。

　下記式より算出される、照射試験前後での遮光膜の透過率及び反射率の変化率を、以下の観点により評価した。

　透過率の変化率（％）＝（（照射試験前の透過率－照射試験後の透過率）／照射試験前の透過率×１００）

　反射率の変化率（％）＝（（照射試験前の反射率－照射試験後の反射率）／照射試験前の反射率×１００）

　Ａ：透過率の変化率及び反射率の変化率が、いずれも２％未満

　Ｂ：透過率の変化率及び反射率の変化率の一方が２％以上であり、他方が２％未満

　Ｃ：透過率の変化率及び反射率の変化率が、いずれも、２％以上
<Changes in transmittance and reflectance before and after irradiation test>

Using a spectroscope V7200 (trade name, manufactured by JASCO Corporation), light was incident on the light-shielding film before and after the irradiation test at an incident angle of 5 °, and the transmission spectrum and the reflection spectrum were obtained. The maximum transmittance at a wavelength of 350 to 1200 nm (hereinafter referred to as transmittance) and the reflectance at a wavelength of 550 nm were measured.

The rates of change in transmittance and reflectance of the light-shielding film before and after the irradiation test, which were calculated from the following formula, were evaluated from the following viewpoints.

Change rate (%) of transmittance = ((transmittance before irradiation test-transmittance after irradiation test) / transmittance before irradiation test x 100)

Change rate of reflectance (%) = ((reflectance before irradiation test−reflectance after irradiation test) / reflectance before irradiation test × 100)

A: The rate of change of transmittance and the rate of change of reflectance are both less than 2%

B: One of the rate of change of transmittance and the rate of change of reflectance is 2% or more, and the other is less than 2%

C: Both the rate of change of transmittance and the rate of change of reflectance are 2% or more.

［耐熱性の評価］

　上記で得られた遮光膜をオーブンに入れ、１５０℃の条件下で５００時間の耐熱試験を行った。

　耐熱試験の前後での遮光膜の膜厚を、接触式膜厚計を用いて測定した。耐熱試験前後での遮光膜の膜厚の変化率を、下記式を用いて算出し、下記の観点により評価した。

　膜厚の変化率（％）＝（（耐熱試験前の膜厚－耐熱試験後の膜厚）／（耐熱試験前の遮光膜の膜厚－基板の厚さ）×１００）

　Ａ：膜厚の変化率が、２％未満

　Ｂ：膜厚の変化率が、２％以上４％未満

　Ｃ：膜厚の変化率が、４％以上６％未満

　Ｄ：膜厚の変化率が、６％以上
[Evaluation of heat resistance]

The light-shielding film obtained above was placed in an oven and subjected to a heat resistance test at 150 ° C. for 500 hours.

The thickness of the light-shielding film before and after the heat test was measured using a contact-type film thickness meter. The rate of change in the thickness of the light-shielding film before and after the heat resistance test was calculated using the following equation, and evaluated from the following viewpoints.

Rate of change of film thickness (%) = ((film thickness before heat resistance test−film thickness after heat resistance test) / (film thickness of light-shielding film before heat resistance test−substrate thickness) × 100)

A: Change rate of film thickness is less than 2%

B: Change rate of film thickness is 2% or more and less than 4%

C: Change rate of film thickness is 4% or more and less than 6%

D: Change rate of film thickness is 6% or more

［耐湿性の評価］

　上記で得られた遮光膜を恒温恒湿槽内に入れ、８５℃及び８５％ＲＨの条件下で５００時間の耐湿性試験を行った。耐湿性試験後の基板に対して、走査型電子顕微鏡（ＳＥＭ）Ｓ－４８００（商品名、日本電子株式会社製）を用いて、開口線幅５０μｍのラインパターンの断面を観察した。得られた断面のＳＥＭ画像から、パターン剥がれの有無に関して、以下の観点により評価した。

　Ａ：パターン全体で剥がれが見られない。

　Ｂ：パターン全体の２０％未満に、剥がれが見られる。

　Ｃ：パターン全体の２０％以上５０％未満に、剥がれが見られる。

　Ｄ：パターン全体の５０％以上に、剥がれが見られる。
[Evaluation of moisture resistance]

The light-shielding film obtained above was placed in a thermo-hygrostat, and a moisture resistance test was performed at 85 ° C. and 85% RH for 500 hours. Using a scanning electron microscope (SEM) S-4800 (trade name, manufactured by JEOL Ltd.), a cross section of a line pattern having an opening line width of 50 μm was observed on the substrate after the moisture resistance test. From the SEM image of the obtained cross section, the presence or absence of pattern peeling was evaluated from the following viewpoints.

A: No peeling is observed in the entire pattern.

B: Peeling is observed in less than 20% of the entire pattern.

C: Peeling is observed in 20% or more and less than 50% of the entire pattern.

D: Peeling is observed in 50% or more of the entire pattern.

［結果］

　表１～３に、実施例１～１７及び比較例１～１０で調製された遮光性組成物の組成、並びに、それらの遮光性組成物を用いて作製された遮光膜についての各試験の結果を示す。

　表１～３中、「色材含有量」の欄は、各遮光性組成物の全固形分に対する、黒色色材の含有量の比率（質量％）を意味する。
[result]

Tables 1 to 3 show the compositions of the light-shielding compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 10, and the results of each test for the light-shielding films produced using those light-shielding compositions. Is shown.

In Tables 1 to 3, the column of "colorant content" means the ratio (% by mass) of the content of the black colorant to the total solid content of each light-shielding composition.

　表１～３中、「酸素遮断層」の「組成」の欄は、酸素遮断層が下記の材料により構成された層であることを意味する。

　Ａ：酸化ケイ素（ＳｉＯ２）のスパッタ層

　Ｂ：窒化ケイ素（Ｓｉ３Ｎ４）のスパッタ層

　Ｃ：ＰＶＡ及びＰＶＰからなる有機層

　Ｄ：酸化ケイ素粒子を含有するポリオルガノシロキサンからなる有機層
In Tables 1 to 3, the column of “Composition” of “Oxygen barrier layer” means that the oxygen barrier layer is a layer composed of the following materials.

A: Sputtered layer of silicon oxide (SiO 2 )

B: Sputtered layer of silicon nitride (Si 3 N 4 )

C: Organic layer composed of PVA and PVP

D: Organic layer composed of polyorganosiloxane containing silicon oxide particles

　表１～３中、「酸素遮断層」の「厚さ」の欄は、接触式膜厚計を用いて測定された、各酸素遮断層の厚さ（ｎｍ）を意味する。

　また、表１～３中、「黒色層の厚さ／酸素遮断層の厚さ」の欄は、接触式膜厚計を用いて測定された、酸素遮断層の厚さに対する黒色層の厚さの比率を意味する。
In Tables 1 to 3, the column of “thickness” of “oxygen blocking layer” means the thickness (nm) of each oxygen blocking layer measured using a contact type film thickness meter.

In Tables 1 to 3, the column of “thickness of black layer / thickness of oxygen blocking layer” indicates the thickness of the black layer with respect to the thickness of the oxygen blocking layer measured using a contact-type film thickness meter. Means the ratio of

Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033

Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034

Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035

　表１～表３に示した結果より、本発明の遮光性組成物によれば、本発明の課題を解決できることが確認された。
From the results shown in Tables 1 to 3, it was confirmed that the problem of the present invention can be solved by the light-shielding composition of the present invention.

　黒色色材の含有量は、遮光膜の耐湿性がより優れる点から、７０質量％以下が好ましく、６５質量％以下がより好ましいことが確認された（実施例１、実施例１５及び１７の比較）。

　黒色色材の含有量は、遮光膜の耐熱性がより優れる点から、３０質量％以上が好ましく、５０質量％以上がより好ましいことが確認された（実施例１、実施例１４及び１６の比較）。
It was confirmed that the content of the black coloring material is preferably 70% by mass or less, and more preferably 65% by mass or less, from the viewpoint that the moisture resistance of the light-shielding film is more excellent (comparison of Example 1, Examples 15 and 17). ).

It was confirmed that the content of the black coloring material is preferably 30% by mass or more, and more preferably 50% by mass or more from the viewpoint that the heat resistance of the light-shielding film is more excellent (comparison of Example 1, Examples 14 and 16). ).

　黒色色材は、遮光膜の耐湿性がより優れる点から、チタン酸窒化物、ベンゾフラノン化合物、又は、ペリレン化合物を含有することが好ましいことが確認された（実施例１、３、４及び５の比較）。

　また、黒色色材は、遮光膜の耐光性がより優れる点から、チタン酸窒化物、又は、カーボンブラックを含有することが好ましいことが確認された（実施例１、３、４及び５の比較）。

　さらに、後述する実施例１８～２０より、窒化バナジウム、窒化ニオブ又は窒化ジルコニウムを含有する黒色色材は、遮光膜の耐湿性及び耐光性がより優れる点から、チタン酸窒化物を含有する黒色色材と同様に好ましいことが確認された。
It was confirmed that the black coloring material preferably contains a titanium oxynitride, a benzofuranone compound, or a perylene compound from the viewpoint that the moisture resistance of the light-shielding film is more excellent (Examples 1, 3, 4, and 5). Comparison).

In addition, it was confirmed that the black coloring material preferably contains titanium oxynitride or carbon black from the viewpoint that the light resistance of the light-shielding film is more excellent (comparison of Examples 1, 3, 4 and 5). ).

Further, from Examples 18 to 20 described later, the black color material containing vanadium nitride, niobium nitride or zirconium nitride is more suitable for black color containing titanium oxynitride because the light-shielding film is more excellent in moisture resistance and light resistance. It was confirmed that it was preferable as well as the material.

　分散樹脂は、遮光膜の耐光性、耐熱性及び耐湿性がより優れる点から、エチレン性不飽和基を含有することが好ましいことが確認された（実施例１と実施例９との比較）。

　アルカリ可溶性樹脂は、遮光膜の耐光性及び耐熱性がより優れる点から、ポリイミド樹脂が好ましいことが確認された（実施例１と実施例６との比較）。また、後述する実施例２１より、遮光膜の耐光性及び耐湿性がより優れる点から、アルカリ可溶性樹脂としては、ポリベンゾオキサゾール前駆体からなる樹脂が、ポリイミド樹脂と同様に好ましいことが確認された。

　重合開始剤は、遮光膜の耐光性及び耐熱性がより優れる点から、重合開始剤Ｃ－１が好ましいことが確認された（実施例１と実施例８との比較）。

　重合性化合物は、遮光膜の耐熱性及び耐湿性がより優れる点から、重合性化合物Ｄ－１が好ましいことが確認された（実施例１と実施例２との比較）。
It was confirmed that the dispersing resin preferably contains an ethylenically unsaturated group from the viewpoint of more excellent light resistance, heat resistance, and moisture resistance of the light-shielding film (comparison between Example 1 and Example 9).

It was confirmed that the alkali-soluble resin is preferably a polyimide resin because the light resistance and the heat resistance of the light-shielding film are more excellent (comparison between Example 1 and Example 6). In addition, from Example 21 described later, it was confirmed that, as the alkali-soluble resin, a resin composed of a polybenzoxazole precursor was preferable, similarly to the polyimide resin, from the viewpoint that the light resistance and the moisture resistance of the light-shielding film were more excellent. .

As the polymerization initiator, it was confirmed that the polymerization initiator C-1 was preferable because the light resistance and the heat resistance of the light-shielding film were more excellent (comparison between Example 1 and Example 8).

As the polymerizable compound, it was confirmed that the polymerizable compound D-1 was preferable because the heat resistance and the moisture resistance of the light-shielding film were more excellent (comparison between Example 1 and Example 2).

　酸素遮断層は、遮光膜の耐光性及び耐湿性がより優れる点から、酸化ケイ素を含有することが好ましいことが確認された（実施例１と実施例７との比較）。

　酸素遮断層の厚さは、遮光膜の耐湿性及び耐熱性がより優れる点から、５０ｎｍ超２５０ｎｍ未満が好ましいことが確認された（実施例１、２４及び２５と実施例１０及び１１との比較）。

　酸素遮断層の厚さに対する黒色層の厚さの比率は、遮光膜の耐湿性及び耐熱性がより優れる点から、７～３０が好ましいことが確認された（実施例１と実施例１０及び１１との比較）。
It was confirmed that the oxygen blocking layer preferably contains silicon oxide in terms of the light resistance and the moisture resistance of the light-shielding film being more excellent (comparison between Example 1 and Example 7).

It was confirmed that the thickness of the oxygen blocking layer is preferably more than 50 nm and less than 250 nm from the viewpoint that the moisture resistance and the heat resistance of the light-shielding film are more excellent (comparison between Examples 1, 24 and 25 and Examples 10 and 11). ).

It has been confirmed that the ratio of the thickness of the black layer to the thickness of the oxygen blocking layer is preferably 7 to 30 from the viewpoint that the light-shielding film has more excellent moisture resistance and heat resistance (Example 1 and Examples 10 and 11). And comparison).

［実施例１８～２０］

　チタンブラック（色材ａ－１）に代えて下記の色材ａ－５～ａ－７をそれぞれ使用すること以外は、上記の色材組成物Ａ－１の調製方法に従って、色材組成物Ａ－６～Ａ－８をそれぞれ調製した。

・色材ａ－５：窒化バナジウム（商品名「ＶＮ－Ｏ」、日本新金属株式会社製）

・色材ａ－６：窒化ニオブ（商品名「ＮｂＮ－Ｏ」、日本新金属株式会社製）

・色材ａ－７：窒化ジルコニウム（特開２０１７－２２２５５９号公報の実施例１の方法で調製した。）

　上記で調製された色材組成物Ａ－６～Ａ－８のそれぞれを色材組成物Ａ－１に代えて使用すること以外は、実施例１の遮光性組成物１の調製方法に従って、実施例１８～２０の遮光性組成物をそれぞれ調製した。得られた各遮光性組成物を遮光性組成物１に代えて使用すること以外は、実施例１に記載の方法に従って、基板上に、黒色層及び酸素遮断層がこの順序で形成されてなる、実施例１８～２０の遮光膜を、それぞれ作製した。実施例１８～２０の遮光膜の評価結果はいずれも、実施例１と同等であった。

　チタンブラック（色材ａ－１）に代えて、色材ａ－８を使用した以外は、上記の色材組成物Ａ－１の調製方法に従って、色材組成物を調製し、実施例１と同様の評価を行った。

・色材ａ－８：シリカ被覆窒化ジルコニウム（特開２０１５－１１７３０２号公報）

　評価結果は、実施例１と同様であった。

　チタンブラック（色材ａ－１）に代えて、色材ａ－１および色材ａ－７の重量比が、それぞれ、ａ－１：ａ－７＝１：９、３：７、５：５、７：３、９：１である混合物を用いた以外は、上記の色材組成物Ａ－１の調製方法に従って、色材組成物を調製し、実施例１と同様の評価を行った。

　評価結果は、実施例１と同様であった。

　また、チタンブラック（色材ａ－１）に代えて、色材ａ－１および色材ａ－８の重量比が、それぞれ、ａ－１：ａ－８＝１：９、３：７、５：５、７：３、９：１である、混合物を用いた以外は、上記の色材組成物Ａ－１の調製方法に従って、色材組成物を調製し、実施例１と同様の評価を行った。

　評価結果は、実施例１と同様であった。
[Examples 18 to 20]

Except for using the following coloring materials a-5 to a-7 instead of titanium black (coloring material a-1), the coloring material composition A was prepared in accordance with the above-described method for preparing the coloring material composition A-1. -6 to A-8 were prepared respectively.

・ Coloring material a-5: Vanadium nitride (trade name “VN-O”, manufactured by Nippon Shinkin Co., Ltd.)

-Coloring material a-6: niobium nitride (trade name "NbN-O", manufactured by Nippon Shinmetal Co., Ltd.)

Coloring material a-7: zirconium nitride (prepared by the method of Example 1 in JP-A-2017-222559)

Except that each of the coloring material compositions A-6 to A-8 prepared above was used in place of the coloring material composition A-1, the procedure was performed in accordance with the method for preparing the light-shielding composition 1 of Example 1. Light-shielding compositions of Examples 18 to 20 were respectively prepared. A black layer and an oxygen blocking layer are formed in this order on a substrate according to the method described in Example 1, except that each of the obtained light-shielding compositions is used in place of the light-shielding composition 1. The light-shielding films of Examples 18 to 20 were produced. The evaluation results of the light-shielding films of Examples 18 to 20 were all the same as Example 1.

A coloring material composition was prepared according to the above-described method for preparing the coloring material composition A-1, except that the coloring material a-8 was used instead of titanium black (coloring material a-1). The same evaluation was performed.

Coloring material a-8: silica-coated zirconium nitride (Japanese Patent Laid-Open No. 2015-117302)

The evaluation results were the same as in Example 1.

Instead of titanium black (coloring material a-1), the weight ratios of coloring material a-1 and coloring material a-7 are respectively a-1: a-7 = 1: 9, 3: 7, 5: 5. , 7: 3, and 9: 1, a colorant composition was prepared according to the method for preparing the colorant composition A-1 described above, and the same evaluation as in Example 1 was performed.

The evaluation results were the same as in Example 1.

In place of titanium black (coloring material a-1), the weight ratios of coloring material a-1 and coloring material a-8 are a-1: a-8 = 1: 9, 3: 7, 5 respectively. : 5, 7: 3, 9: 1, except that a mixture was used. went.

The evaluation results were the same as in Example 1.

［実施例２１］

　アルカリ可溶性樹脂Ｂ－１に代えてアルカリ可溶性樹脂Ｂ－３を使用すること以外は、実施例１の遮光性組成物１の調製方法に従って、実施例２１の遮光性組成物を調製した。

得られた遮光性組成物を遮光性組成物１に代えて使用すること以外は、実施例１に記載の方法に従って、基板上に、黒色層及び酸素遮断層がこの順序で形成されてなる、実施例２１の遮光膜を作製した。実施例２１の遮光膜の評価結果はいずれも、実施例１と同等であった。
[Example 21]

A light-shielding composition of Example 21 was prepared in accordance with the preparation method of light-shielding composition 1 of Example 1, except that alkali-soluble resin B-3 was used instead of alkali-soluble resin B-1.

Except that the obtained light-shielding composition is used instead of light-shielding composition 1, a black layer and an oxygen-shielding layer are formed in this order on a substrate according to the method described in Example 1. A light-shielding film of Example 21 was produced. The evaluation results of the light-shielding film of Example 21 were all the same as those of Example 1.

［実施例２２］

　重合開始剤Ｃ－２に代えて重合開始剤Ｃ－３を使用すること以外は、実施例１の遮光性組成物１の調製方法に従って、実施例２２の遮光性組成物を調製した。得られた遮光性組成物を遮光性組成物１に代えて使用すること以外は、実施例１に記載の方法に従って、基板上に、黒色層及び酸素遮断層がこの順序で形成されてなる、実施例２２の遮光膜を作製した。実施例２２の遮光膜の評価結果は、耐熱性がＣであったこと以外は、実施例８と同等であった。
[Example 22]

A light-shielding composition of Example 22 was prepared in accordance with the preparation method of light-shielding composition 1 of Example 1, except that polymerization initiator C-3 was used instead of polymerization initiator C-2. Except that the obtained light-shielding composition is used instead of light-shielding composition 1, a black layer and an oxygen-shielding layer are formed in this order on a substrate according to the method described in Example 1. A light-shielding film of Example 22 was produced. The evaluation result of the light-shielding film of Example 22 was the same as that of Example 8 except that the heat resistance was C.

［実施例２３］

　遮光性組成物１の調製において、６．１質量部の重合性化合物Ｄ－１に代えて、質量比が１：１である重合性化合物Ｄ－１及び重合性化合物Ｄ－２の混合物を６．１質量部使用すること以外は、実施例１の方法に従って、実施例２３の遮光性組成物を調製した。得られた遮光性組成物を遮光性組成物１に代えて使用すること以外は、実施例１に記載の方法に従って、基板上に、黒色層及び酸素遮断層がこの順序で形成されてなる、実施例２３の遮光膜を作製した。実施例２３の遮光膜の評価結果は、耐湿性がＢであったこと以外は、実施例１と同等であった。
[Example 23]

In the preparation of the light-shielding composition 1, a mixture of the polymerizable compound D-1 and the polymerizable compound D-2 having a mass ratio of 1: 1 was replaced with 6.1 parts by mass of the polymerizable compound D-1. Except for using 0.1 part by mass, the light-shielding composition of Example 23 was prepared according to the method of Example 1. Except that the obtained light-shielding composition is used instead of light-shielding composition 1, a black layer and an oxygen-shielding layer are formed in this order on a substrate according to the method described in Example 1. A light-shielding film of Example 23 was produced. The evaluation result of the light-shielding film of Example 23 was the same as that of Example 1 except that the moisture resistance was B.

［実施例２４～２５］

　スパッタリング工程において、放電電力及び成膜時間を調整し、７０ｎｍ及び２００ｎｍの厚さを有する酸化ケイ素（ＳｉＯ２）からなる酸素遮断層Ｅ－７及びＥ－８をそれぞれ形成すること以外は、実施例１に記載の方法に従って、基板上に、黒色層及び酸素遮断層がこの順序で形成されてなる、実施例２４及び２５の遮光膜を、それぞれ作製した。実施例２４及び２５の遮光膜の評価結果はいずれも、実施例１と同等であった。
[Examples 24 and 25]

Except that in the sputtering process, the discharge power and the film formation time were adjusted, and oxygen barrier layers E-7 and E-8 made of silicon oxide (SiO 2 ) having a thickness of 70 nm and 200 nm were formed, respectively. According to the method described in No. 1, the light-shielding films of Examples 24 and 25 each having a black layer and an oxygen blocking layer formed in this order on a substrate were produced. The evaluation results of the light-shielding films of Examples 24 and 25 were the same as those of Example 1.

［実施例２６～２７］

　重合禁止剤を使用しないこと以外は、実施例１の遮光性組成物１の調製方法に従って、実施例２６の遮光性組成物を調製した。また、界面活性剤を使用しないこと以外は、実施例１の遮光性組成物１の調製方法に従って、実施例２７の遮光性組成物を調製した。得られた各遮光性組成物を遮光性組成物１に代えて使用すること以外は実施例１に記載の方法に従って、基板上に、黒色層及び酸素遮断層がこの順序で形成されてなる、実施例２６及び２７の遮光膜をそれぞれ作製した。実施例２６及び２７の遮光膜の評価結果はいずれも、実施例１と同等であった。
[Examples 26 and 27]

A light-shielding composition of Example 26 was prepared in accordance with the preparation method of light-shielding composition 1 of Example 1, except that the polymerization inhibitor was not used. Further, a light-shielding composition of Example 27 was prepared in accordance with the preparation method of light-shielding composition 1 of Example 1, except that no surfactant was used. According to the method described in Example 1, except that each obtained light-shielding composition is used in place of light-shielding composition 1, a black layer and an oxygen-shielding layer are formed in this order on a substrate. The light-shielding films of Examples 26 and 27 were produced, respectively. The evaluation results of the light-shielding films of Examples 26 and 27 were the same as those of Example 1.

［実施例２８］

＜ブラックマトリクスを備えるカラーフィルタの作製＞

　実施例１の遮光性組成物１をガラスウェハにスピンコート法で塗布し、組成物層を形成した。次に、ガラスウェハをホットプレート上に載置して、１２０℃で２分間のプリベークを行った。次いで、ｉ線ステッパーを用い、０．１ｍｍのＩｓｌａｎｄパターンを有するフォトマスクを通して５００ｍＪ／ｃｍ２の露光量で、組成物層を露光した。

　次に、露光後の組成物層を、テトラメチルアンモニウムヒドロキシド０．３％水溶液を用い、２３℃で６０秒間パドル現像し、硬化膜を得た。得られた硬化膜を、スピンシャワーを用いてリンスし、更に、純水にて洗浄して、パターン状の黒色層を形成した。

　次に、実施例１の酸素遮断層Ｅ－１の形成方法に準じて、上記で作製された黒色層の表面に、酸化ケイ素からなる酸素遮断層を形成することにより、ガラスウェハ上に黒色層及び酸素遮断層がこの順序で形成されてなる遮光膜（ブラックマトリクス）を作製した。上記ブラックマトリクスを用いてカラーフィルタを作製したところ、良好な性能を有していた。
[Example 28]

<Production of color filter with black matrix>

The light-shielding composition 1 of Example 1 was applied to a glass wafer by spin coating to form a composition layer. Next, the glass wafer was placed on a hot plate and prebaked at 120 ° C. for 2 minutes. Next, the composition layer was exposed at an exposure amount of 500 mJ / cm 2 through a photomask having a 0.1 mm Island pattern using an i-line stepper.

Next, the exposed composition layer was paddle-developed with a 0.3% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds to obtain a cured film. The obtained cured film was rinsed using a spin shower, and further washed with pure water to form a patterned black layer.

Next, an oxygen barrier layer made of silicon oxide was formed on the surface of the black layer produced above in accordance with the method for forming the oxygen barrier layer E-1 of Example 1, whereby a black layer was formed on the glass wafer. And a light-shielding film (black matrix) in which an oxygen barrier layer was formed in this order. When a color filter was produced using the above black matrix, it had good performance.

［実施例２９］

＜遮光膜を備える固体撮像素子の作製＞

　レンズ用硬化性組成物（脂環式エポキシ樹脂（ダイセル化学社製、商品名「ＥＨＰＥ－３１５０」）にアリールスルホニウム塩誘導体（ＡＤＥＫＡ社製、商品名「ＳＰ－１７２」）を１質量％添加した組成物）（２ｍＬ）を５×５ｃｍのガラス基板（厚さ１ｍｍ、Ｓｃｈｏｔｔ社製、商品名「ＢＫ７」）上に塗布し、塗膜を２００℃で１分間加熱して硬化させ、レンズ上の残渣が評価できるレンズ膜を形成した。

　上記レンズ膜を形成したガラスウェハ上に、実施例１の遮光性組成物１を塗布し、組成物層を形成した。次に、上記ガラスウェハをホットプレート上に載置し、１２０℃で、１２０秒間のプリベークを行った。加熱後の組成物層の厚さは２．０μｍであった。

　次に、組成物層を、高圧水銀灯を用いて、１０ｍｍのホールパターンを有するフォトマスクを介して５００ｍＪ／ｃｍ２の露光量で露光した。次に、露光した組成物層に対し、テトラメチルアンモニウムヒドロキシド０．３％水溶液を用い、２３℃の温度で６０秒間パドル現像して、硬化膜を得た。得られた硬化膜を、スピンシャワーを用いてリンスし、更に、純水にて洗浄して、パターン状の黒色層を形成した。

　次に、実施例１の酸素遮断層Ｅ－１の形成方法に準じて、上記で作製された黒色層の表面に、酸化ケイ素からなる酸素遮断層を形成することにより、ガラスウェハ上に黒色層及び酸素遮断層がこの順序で形成されてなる遮光膜を作製した。
[Example 29]

<Preparation of solid-state imaging device including light-shielding film>

1% by mass of an arylsulfonium salt derivative (trade name “SP-172” manufactured by ADEKA Corporation) was added to a curable composition for lenses (alicyclic epoxy resin (trade name “EHPE-3150” manufactured by Daicel Chemical Industries, Ltd.)). Composition) (2 mL) was applied on a 5 × 5 cm glass substrate (1 mm thick, manufactured by Schott, trade name “BK7”), and the coating was cured by heating at 200 ° C. for 1 minute. A lens film was formed from which the residue could be evaluated.

The light-shielding composition 1 of Example 1 was applied on a glass wafer on which the lens film was formed to form a composition layer. Next, the glass wafer was placed on a hot plate and prebaked at 120 ° C. for 120 seconds. The thickness of the composition layer after heating was 2.0 μm.

Next, the composition layer was exposed using a high-pressure mercury lamp at an exposure amount of 500 mJ / cm 2 through a photomask having a hole pattern of 10 mm. Next, the exposed composition layer was paddle-developed with a 0.3% aqueous solution of tetramethylammonium hydroxide at a temperature of 23 ° C. for 60 seconds to obtain a cured film. The obtained cured film was rinsed using a spin shower, and further washed with pure water to form a patterned black layer.

Next, an oxygen barrier layer made of silicon oxide was formed on the surface of the black layer produced above in accordance with the method for forming the oxygen barrier layer E-1 of Example 1, whereby a black layer was formed on the glass wafer. And a light-shielding film in which an oxygen blocking layer was formed in this order.

　上記で作製した遮光膜を形成したガラスウェハの上に、レンズ用硬化性組成物（脂環式エポキシ樹脂（ダイセル化学社製、商品名「ＥＨＰＥ－３１５０」）にアリールスルホニウム塩誘導体（ＡＤＥＫＡ社製、商品名「ＳＰ－１７２」）を１質量％添加した組成物）を用いて、硬化性樹脂層を形成した。次に、レンズ形状を持つ石英モールドで形状を転写して、高圧水銀ランプにより４００ｍＪ／ｃｍ２の露光量で露光し、硬化性樹脂層を硬化させることにより、ウェハレベルレンズを複数有するウェハレベルレンズアレイを作製した。

　作製されたウェハレベルレンズアレイを切断し、得られたウェハレベルレンズを用いてレンズモジュールを作製した後に、撮像素子及びセンサ基板を取り付け、本発明の遮光膜を備える固体撮像素子を作製した。

　得られた固体撮像素子では、ウェハレベルレンズのレンズ開口部に残渣物が無く良好な透過性を有し、かつ、遮光膜についても塗布面の均一性が高く、遮光性が高いものであった。
A curable composition for lenses (alicyclic epoxy resin (manufactured by Daicel Chemical Industries, trade name "EHPE-3150") and an arylsulfonium salt derivative (manufactured by ADEKA Co.) And a composition (trade name “SP-172”) added at 1% by mass) to form a curable resin layer. Next, a wafer-level lens having a plurality of wafer-level lenses is obtained by transferring the shape with a quartz mold having a lens shape, exposing it with a high-pressure mercury lamp at an exposure amount of 400 mJ / cm 2 , and curing the curable resin layer. An array was made.

After cutting the manufactured wafer-level lens array and manufacturing a lens module using the obtained wafer-level lens, an image sensor and a sensor substrate were attached, and a solid-state image sensor including the light-shielding film of the present invention was manufactured.

In the obtained solid-state imaging device, there was no residue in the lens opening of the wafer-level lens, the film had good transparency, and the light-shielding film had high uniformity of the coated surface and high light-shielding properties. .

［実施例３０］

＜遮光膜を備えるヘッドライトユニットの作製＞

　１０ｃｍ角のガラス基板上に、上記で得られた実施例１の遮光性組成物１をスピンコート法により塗布して、組成物層を形成した。上記ガラス基板をホットプレート上で載置し、１２０℃で２分間のプリベークを行った。

　得られた組成物層に対し、ｉ線ステッパーを用い、図６に示す配光パターンを有する硬化膜が得られるように、マスクを介して露光（露光量１０００ｍＪ／ｃｍ２）した。

次いで、現像装置（東京エレクトロン製Ａｃｔ－８）を使用し現像処理を行った。現像液としてはテトラメチルアンモニウムヒドロキシド０．３％水溶液を用い、２３℃で６０秒間パドル現像した。その後、得られた硬化膜を、純水を用いたスピンシャワーにてリンスして、所定の配光パターンを有する黒色層を得た。

　次に、実施例１の酸素遮断層Ｅ－１の形成方法に準じて、上記で作製された黒色層の表面に、酸化ケイ素からなる酸素遮断層を形成することにより、ガラス基板上に黒色層及び酸素遮断層がこの順序で形成されてなる遮光膜を作製した。

　得られた遮光膜と、光源と、レンズとを用いてヘッドライトユニットを作製したところ、良好な性能を有していた。
[Example 30]

<Production of headlight unit with light-shielding film>

The light-shielding composition 1 of Example 1 obtained above was applied on a 10 cm square glass substrate by a spin coating method to form a composition layer. The glass substrate was placed on a hot plate and prebaked at 120 ° C. for 2 minutes.

The obtained composition layer was exposed through a mask (exposure amount: 1000 mJ / cm 2 ) using an i-line stepper so that a cured film having a light distribution pattern shown in FIG. 6 was obtained.

Next, development processing was performed using a developing device (Act-8 manufactured by Tokyo Electron). Using a 0.3% aqueous solution of tetramethylammonium hydroxide as a developing solution, paddle development was performed at 23 ° C. for 60 seconds. Thereafter, the obtained cured film was rinsed with a spin shower using pure water to obtain a black layer having a predetermined light distribution pattern.

Next, an oxygen barrier layer made of silicon oxide was formed on the surface of the black layer prepared above in accordance with the method for forming the oxygen barrier layer E-1 of Example 1, whereby a black layer was formed on the glass substrate. And a light-shielding film in which an oxygen blocking layer was formed in this order.

A headlight unit was produced using the obtained light-shielding film, light source, and lens, and had good performance.

１０・・・ヘッドライトユニット

１２・・・光源

１４・・・遮光部

１６・・・レンズ

２０・・・基体

２２・・・遮光膜

２３・・・開口部

３０・・・配光パターン

３０ａ・・・エッジ

３１・・・領域

３２・・・配光パターン

３２ａ・・・エッジ

３３・・・切欠部

１００・・・固体撮像装置

１０１・・・固体撮像素子

１０２・・・撮像部

１０３・・・カバーガラス

１０４・・・スペーサー

１０５・・・積層基板

１０６・・・チップ基板

１０７・・・回路基板

１０８・・・電極パッド

１０９・・・外部接続端子

１１０・・・貫通電極

１１１・・・レンズ層

１１２・・・レンズ材

１１３・・・支持体

１１４、１１５・・・遮光膜

２０１・・・受光素子

２０２・・・カラーフィルタ

２０３・・・マイクロレンズ

２０４・・・基板

２０５ｂ・・・青色画素

２０５ｒ・・・赤色画素

２０５ｇ・・・緑色画素

２０５ｂｍ・・・ブラックマトリクス

２０６・・・ｐウェル層

２０７・・・読み出しゲート部

２０８・・・垂直転送路

２０９・・・素子分離領域

２１０・・・ゲート絶縁膜

２１１・・・垂直転送電極

２１２・・・遮光膜

２１３、２１４・・・絶縁膜

２１５・・・平坦化膜

３００・・・赤外線センサ

３１０・・・固体撮像素子

３１１・・・赤外線吸収フィルタ

３１２・・・カラーフィルタ

３１３・・・赤外線透過フィルタ

３１４・・・樹脂膜

３１５・・・マイクロレンズ

３１６・・・平坦化膜
10 ・ ・ ・ Headlight unit

12 Light source

14 ... Shading part

16 ... Lens

20 ... substrate

22 ... light shielding film

23 ・ ・ ・ Opening

30 ... Light distribution pattern

30a ・ ・ ・ Edge

31 ... area

32 ... Light distribution pattern

32a ... edge

33 ・ ・ ・ Notch

100 ・ ・ ・ Solid-state imaging device

101 solid-state imaging device

102 ・ ・ ・ Imaging unit

103 ・ ・ ・ Cover glass

104 ・ ・ ・ Spacer

105 ・ ・ ・ Laminated substrate

106 ··· Chip substrate

107 ... circuit board

108 ... electrode pad

109 ・ ・ ・ External connection terminal

110 ... through electrode

111 ... Lens layer

112 ・ ・ ・ Lens material

113 ・ ・ ・ Support

114, 115: light shielding film

201 ・ ・ ・ light receiving element

202 ・ ・ ・ Color filter

203 ・ ・ ・ Micro lens

204 ... substrate

205b: blue pixel

205r: red pixel

205g: green pixel

205bm ··· Black matrix

206 ... p-well layer

207 ・ ・ ・ Readout gate unit

208: vertical transfer path

209: element isolation region

210 ・ ・ ・ Gate insulating film

211 ・ ・ ・ vertical transfer electrode

212 ・ ・ ・ Light shielding film

213, 214 ... insulating film

215 ··· Flattening film

300 ・ ・ ・ Infrared sensor

310 ・ ・ ・ Solid-state image sensor

311 ... Infrared absorption filter

312 ・ ・ ・ Color filter

313 ... Infrared transmission filter

314 ... resin film

315 ... micro lens

316 ・ ・ ・ Planarization film

Claims (17)


  1. 　黒色色材を含有する黒色層と、

    　前記黒色層上に形成された酸素遮断層と、を備える遮光膜であって、

    　前記酸素遮断層が、無機材料からなる単層であり、

    　前記酸素遮断層の厚さが、１０～５００ｎｍである、遮光膜。
    A black layer containing a black coloring material,

    An oxygen blocking layer formed on the black layer, and a light-shielding film comprising:

    The oxygen barrier layer is a single layer made of an inorganic material,

    A light shielding film, wherein the thickness of the oxygen blocking layer is 10 to 500 nm.

  2. 　前記黒色色材が、チタン、バナジウム、ジルコニウム及びニオブからなる群より選択される少なくとも１種の金属の酸窒化物を含有する、請求項１に記載の遮光膜。
    The light-shielding film according to claim 1, wherein the black color material contains at least one metal oxynitride selected from the group consisting of titanium, vanadium, zirconium, and niobium.

  3. 　前記黒色色材が、カーボンブラック、ベンゾフラノン化合物又はペリレン化合物を含有する、請求項１に記載の遮光膜。
    The light-shielding film according to claim 1, wherein the black color material contains carbon black, a benzofuranone compound, or a perylene compound.

  4. 　前記黒色色材の含有量が、前記黒色層の総質量に対して２０～８０質量％である、請求項１～３のいずれか一項に記載の遮光膜。
    4. The light-shielding film according to claim 1, wherein the content of the black colorant is 20 to 80% by mass based on the total mass of the black layer.

  5. 　前記酸素遮断層が、酸化ケイ素を含有する、請求項１～４のいずれか一項に記載の遮光膜。
    The light-shielding film according to claim 1, wherein the oxygen barrier layer contains silicon oxide.

  6. 　前記酸素遮断層の厚さに対する、前記黒色層の厚さの比率が、２～１００である、請求項１～５のいずれか一項に記載の遮光膜。
    The light-shielding film according to claim 1, wherein a ratio of a thickness of the black layer to a thickness of the oxygen barrier layer is 2 to 100.

  7. 　前記酸素遮断層の酸素透過率が、１０ｍｌ／（ｍ２・ｄａｙ・ａｔｍ）以下である、請求項１～６のいずれか一項に記載の遮光膜。
    The light-shielding film according to any one of claims 1 to 6, wherein the oxygen barrier layer has an oxygen permeability of 10 ml / (m 2 · day · atm) or less.

  8. 　前記酸素遮断層が、実質的に粒子を含まない、請求項１～７のいずれか一項に記載の遮光膜。
    The light-shielding film according to any one of claims 1 to 7, wherein the oxygen barrier layer is substantially free of particles.

  9. 　支持体上に、黒色色材、樹脂、重合性化合物、及び、重合開始剤を含有する遮光性組成物を塗布し、得られた塗膜を硬化して、黒色層を形成する工程と、

    　前記黒色層上に、酸素遮断層を形成する工程と、を備え、

    　前記酸素遮断層が、無機材料からなる単層であり、

    　前記酸素遮断層の厚さが、１０～５００ｎｍである、遮光膜の製造方法。
    On a support, a black colorant, a resin, a polymerizable compound, and a light-shielding composition containing a polymerization initiator is applied, and the obtained coating film is cured to form a black layer,

    Forming an oxygen barrier layer on the black layer,

    The oxygen barrier layer is a single layer made of an inorganic material,

    A method for producing a light-shielding film, wherein the thickness of the oxygen barrier layer is 10 to 500 nm.

  10. 　前記酸素遮断層を形成する工程が、無機材料を蒸着する工程を含む、請求項９に記載の遮光膜の製造方法。
    The method for manufacturing a light-shielding film according to claim 9, wherein the step of forming the oxygen barrier layer includes a step of depositing an inorganic material.

  11. 　前記樹脂が、ポリイミド前駆体、ポリベンゾオキサゾール前駆体、及び、それらの共重合体からなる群より選択される少なくとも１種を含有するアルカリ可溶性樹脂を含有する、請求項９又は１０に記載の遮光膜の製造方法。
    The light shielding according to claim 9 or 10, wherein the resin contains an alkali-soluble resin containing at least one selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a copolymer thereof. Manufacturing method of membrane.

  12. 　前記遮光性組成物が、少なくとも２種の重合性化合物を含有する、請求項９～１１のいずれか一項に記載の遮光膜の製造方法。
    The method for producing a light-shielding film according to any one of claims 9 to 11, wherein the light-shielding composition contains at least two kinds of polymerizable compounds.

  13. 　前記重合開始剤が、下記式（Ｃ－１３）で表わされる化合物である、請求項９～１２のいずれか一項に記載の遮光膜の製造方法。

    Figure JPOXMLDOC01-appb-C000001
    The method for producing a light-shielding film according to any one of claims 9 to 12, wherein the polymerization initiator is a compound represented by the following formula (C-13).

    Figure JPOXMLDOC01-appb-C000001

  14. 　前記樹脂が、エチレン性不飽和基を有する樹脂を含有する、請求項９～１３のいずれか一項に記載の遮光膜の製造方法。
    14. The method for producing a light-shielding film according to claim 9, wherein the resin contains a resin having an ethylenically unsaturated group.

  15. 　請求項１～８のいずれか一項に記載の遮光膜を含有する光学素子。
    An optical element containing the light-shielding film according to any one of claims 1 to 8.

  16. 　請求項１～８のいずれか一項に記載の遮光膜を含有する固体撮像素子。
    A solid-state imaging device containing the light-shielding film according to any one of claims 1 to 8.

  17. 　車両用灯具のヘッドライトユニットであって、

    　光源と、

    　前記光源から出射された光の少なくとも一部を遮光する遮光部とを有し、

    　前記遮光部が、請求項１～８のいずれか一項に記載の遮光膜を含有する、ヘッドライトユニット。
    A headlight unit for a vehicle lamp,

    Light source,

    Having a light-shielding portion that shields at least a part of light emitted from the light source,

    A headlight unit, wherein the light-shielding portion contains the light-shielding film according to any one of claims 1 to 8.
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