WO2019069609A1 - Method for producing cured film, method for producing solid-state imaging element, and method for producing image display device - Google Patents

Method for producing cured film, method for producing solid-state imaging element, and method for producing image display device Download PDF

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WO2019069609A1
WO2019069609A1 PCT/JP2018/032662 JP2018032662W WO2019069609A1 WO 2019069609 A1 WO2019069609 A1 WO 2019069609A1 JP 2018032662 W JP2018032662 W JP 2018032662W WO 2019069609 A1 WO2019069609 A1 WO 2019069609A1
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group
cured film
curable composition
nitride
producing
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PCT/JP2018/032662
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French (fr)
Japanese (ja)
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達郎 石川
貴規 田口
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富士フイルム株式会社
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Priority to JP2019546581A priority Critical patent/JP6994044B2/en
Priority to KR1020207007436A priority patent/KR102379844B1/en
Publication of WO2019069609A1 publication Critical patent/WO2019069609A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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

Definitions

  • the present invention relates to a method of manufacturing a cured film, a method of manufacturing a solid-state imaging device, and a method of manufacturing an image display device.
  • the method for producing a cured film used for a solid-state imaging device and an image display device is carried out after forming a curable composition layer on a substrate
  • the method of hardening this is common.
  • the curable composition layer is irradiated with light through a predetermined mask pattern and then developed.
  • the optical density (OD: Optical Density) of the curable composition layer with respect to a specific wavelength may be adjusted within a predetermined range.
  • Patent Document 1 discloses that when a film having a thickness of 2.0 ⁇ m after drying is formed using a colored photosensitive composition, the film has an optical density of 1.5 or more at a wavelength of 365 nm.
  • a photosensitive composition is disclosed (Claim 1).
  • the present inventors examined the colored photosensitive composition described in Patent Document 1, and there is room for improvement in rectangularity of the cross-sectional shape of a cured film formed using this colored photosensitive composition. Found out. In addition, it is required that a cured film of stable quality can be produced under various production conditions, and after a curable composition layer is formed, a period (for example, one week) until exposure is left. However, it is also required that the rectangularity of the cross-sectional shape of the obtained cured film be good.
  • retention the fact that the object to be treated which has undergone a specific process can be made to stand by until the next process is also referred to as "retention.”
  • the present invention can provide a method for producing a cured film capable of producing a cured film excellent in rectangularity of the cross-sectional shape and maintaining excellent rectangularity even when using a drawn curable composition layer. It will be an issue.
  • Another object of the present invention is to provide a method of manufacturing a solid-state imaging device and a method of manufacturing an image display device.
  • the optical density A at a wavelength of 365 nm per 1.5 ⁇ m of film thickness is 2.60 to 10.00, and the film thickness of 1.5 ⁇ m
  • Forming a curable composition layer having an optical density B of 2.00 to 10.00 at a wavelength of 550 nm, and exposing the curable composition layer under conditions of an oxygen concentration of 30 to 50% by volume A method for producing a cured film, comprising the steps of: developing the curable composition layer after the exposure to form a cured film.
  • the black pigment is a nitride or oxynitride of titanium, a nitride or oxynitride of zirconium, a nitride or oxynitride of vanadium, a nitride or oxynitride of niobium, or carbon black
  • the manufacturing method of the cured film as described in [1] or [2].
  • the black pigment is a nitride or oxynitride of titanium, a nitride or oxynitride of zirconium, a nitride or oxynitride of vanadium, or a nitride or oxynitride of niobium [1] ] The manufacturing method of the cured film in any one of-[3]. [5] The method for producing a cured film according to any one of [1] to [4], wherein the black pigment is a nitride or oxynitride of titanium, or a nitride or oxynitride of zirconium.
  • [6] The method for producing a cured film according to any one of [1] to [5], wherein the irradiance is from 20000 to 50000 W / m 2 in the exposure.
  • [7] The method for producing a cured film according to any one of [1] to [6], wherein the irradiance is 25000 to 40000 W / m 2 in the exposure.
  • [8] The cured film according to any one of [1] to [7], wherein the optical density A is 2.80 to 4.00, and the optical density B is 2.50 to 7.00. Production method.
  • [9] The method for producing a cured film according to any one of [1] to [8], wherein the ratio of the optical density B to the optical density A is 0.5 to 2.0.
  • the curable composition further contains a resin, and the resin contains a resin containing an ethylenically unsaturated group, and the content of the ethylenically unsaturated group with respect to the total mass of the resin Of from 0.10 to 3.00 mmol / g.
  • the method for producing a cured film according to any one of [1] to [10] wherein the curable composition further contains a polymerization initiator.
  • the cured film which is excellent in the rectangularity of cross-sectional shape can be manufactured, and the manufacturing method of the cured film which can maintain excellent rectangularity even when using the curable composition layer drawn can be provided.
  • the present invention can also provide a method of manufacturing a solid-state imaging device and a method of manufacturing an image display device.
  • a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
  • the notation not describing substitution and non-substitution also includes a group containing a substituent together with a group not containing a substituent.
  • the "alkyl group” includes not only an alkyl group containing no substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).
  • active light or “radiation” in the present specification means, for example, far ultraviolet, extreme ultraviolet (EUV), X-ray, electron beam and the like.
  • light means actinic rays and radiation.
  • exposure in the present specification includes not only exposure by far ultraviolet rays, X-rays, EUV light and the like but also drawing by particle beams such as electron beams and ion beams.
  • (meth) acrylate represents acrylate and methacrylate.
  • (meth) acryl represents an acryl and a methacryl.
  • (meth) acryloyl represents acryloyl and methacryloyl.
  • (meth) acrylamide refers to acrylamide and methacrylamide.
  • “monomer” and “monomer” are synonymous.
  • the weight-average molecular weight (Mw) is a polystyrene conversion value by GPC (Gel Permeation Chromatography) method.
  • GPC method uses HLC-8020GPC (made by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ 2000 (made by Tosoh Corp., 4.6 mm ID ⁇ 15 cm) as columns, and THF (tetrahydrofuran as the eluent Based on the method using
  • the optical density A at a wavelength of 365 nm per film thickness of 1.5 ⁇ m is 2.60 to 10.00 using a curable composition containing a black pigment and a polymerizable compound, and a film A step of forming a curable composition layer having an optical density B at a wavelength of 550 nm per 1.5 ⁇ m of 2.00 to 10.00, and the curable composition layer having an oxygen concentration of 30 to 50% by volume And exposing the curable composition layer after the exposure to form a cured film.
  • the reason why the cured film (patterned cured film) excellent in the rectangularity of the cross-sectional shape can be obtained by using the production method of the present invention is not necessarily clear, but the present inventors are as follows. I am thinking about it. That is, by exposing the curable composition layer exhibiting a predetermined optical density to a specific wavelength under high oxygen concentration, oxygen appropriately inhibits the curing reaction in the surface layer portion, and the curable composition It is believed that this is because curing can proceed in a well-balanced manner in the surface layer portion and the lower layer portion of the object layer.
  • the optical density A and the optical density B being within the predetermined range contributes to the improvement of the rectangularity of the cross-sectional shape of the cured film. ing.
  • the curable composition layer containing a specific component and exhibiting a predetermined optical density is exposed under a constant oxygen concentration to produce a cured film.
  • a curable composition used in the production method of the present invention will be described.
  • a curable composition layer is formed using this curable composition, and the method of exposing the said curable composition layer and manufacturing a cured film is demonstrated.
  • the use of the cured film obtained using the manufacturing method of this invention is demonstrated.
  • the curable composition contains a black pigment.
  • the black pigment various known black pigments can be used.
  • the black pigment may be an inorganic pigment or an organic pigment.
  • Examples of black 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), chromium Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and one or two selected from the group consisting of silver (Ag) Examples thereof include metal oxides, metal nitrides, metal oxynitrides, and the like containing a metal element of a kind or more.
  • the inorganic pigment may be subjected to surface modification treatment.
  • examples include inorganic particles that have been surface-modified with a surface treatment agent having both a silicone group and an alkyl group, such as the “KTP-09” series (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • metal oxides, metal nitrides, and metal oxynitrides may be used as particles in which other atoms are mixed.
  • it may be used as a metal nitride-containing particle further containing an atom (preferably an oxygen atom and / or a sulfur atom) selected from periodic table elements 13-17.
  • the black pigment also includes carbon black. Specific examples of carbon black include C.I. I. Organic pigments such as C.I. pigment black 1; I. And inorganic pigments such as CI pigment black 7.
  • nitrides or oxides of Group 4 metal elements, nitrides or oxynitrides of Group 5 metal elements, or carbon black are preferable, and titanium nitride or oxynitride , Zirconium nitride or oxynitride, vanadium nitride or oxynitride, niobium nitride or oxynitride, or carbon black is more preferable, titanium nitride or oxynitride, zirconium nitride or Oxynitrides, nitrides or oxynitrides of vanadium, or nitrides or oxynitrides of niobium are more preferable, and nitrides or oxynitrides of titanium, or nitrides or oxynitrides of zirconium are particularly preferable.
  • the nitride of titanium is titanium nitride
  • the nitride of zirconium is zirconium nitride
  • the nitride of vanadium is vanadium nitride
  • the nitride of niobium is niobium nitride.
  • the titanium oxynitride is titanium oxynitride
  • the zirconium oxynitride is zirconium oxynitride
  • the vanadium oxynitride is vanadium oxynitride
  • the niobium oxynitride is oxynitride. It is niobium.
  • black pigment a commercially available product "NITRBLACK (night black) UB-1" (manufactured by Mitsubishi Materials Co., Ltd., zirconium nitride powder described in JP-A-2017-222559, and JP-A-4931011)
  • black pigments such as particulate low-order zirconium oxide-zirconium nitride composites.
  • nitrides or oxynitrides of titanium, nitrides or oxynitrides of zirconium, nitrides or oxynitrides of vanadium, or nitrides or oxynitrides of niobium In the case of using the composition, it is surprising that, after the curable composition is used to form the curable composition layer, the resulting cured film is obtained even if there is a period (eg 1 week) until exposure. Deterioration of the rectangularity of the cross-sectional shape of can be further suppressed.
  • the black pigment is preferably as fine as possible.
  • the average primary particle size of the black pigment is preferably 0.01 to 0.1 ⁇ m, and more preferably 0.01 to 0.05 ⁇ m.
  • the average primary particle size of the black pigment can be measured using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • a transmission electron microscope for example, a transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
  • Maximum length of particle image obtained using transmission electron microscope (Dmax: maximum length at two points on the contour of particle image), and maximum vertical length (DV-max: two straight lines parallel to the maximum length When the image is sandwiched, the shortest length connecting two straight lines vertically is measured, and the geometric mean value (Dmax ⁇ DV-max) 1/2 is defined as the particle diameter.
  • the particle diameter of 100 particles is measured by this method, and the arithmetic mean value is taken as an average particle diameter to obtain an average primary particle diameter of the black pigment.
  • titanium nitride is intended to be TiN, and may contain unavoidable oxygen atoms in production (for example, unintentional oxidation of the surface of TiN particles, etc.).
  • titanium nitride means a compound having a diffraction angle 2 ⁇ of 42.5 ° to 42.8 ° of a peak derived from the (200) plane when a CuK ⁇ ray is used as an X-ray source.
  • titanium oxynitride means a compound having a diffraction angle 2 ⁇ of a peak derived from the (200) plane in the case of using CuK ⁇ radiation as an X-ray source over 42.8 °.
  • the upper limit value of the above-mentioned diffraction angle 2 ⁇ of titanium oxynitride is not particularly limited, but 43.5 ° or less is preferable.
  • the titanium nitride for example, include titanium black or the like, more specifically, for example, low-order titanium oxide represented by TiO 2, Ti n O 2n- 1 (1 ⁇ n ⁇ 20), and / or, forms containing TiN x O y titanium oxynitride represented by (0 ⁇ x ⁇ 2.0,0.1 ⁇ y ⁇ 2.0) can be mentioned.
  • titanium nitride (the diffraction angle 2 ⁇ is 42.5 ° to 42.8 °) and titanium oxynitride (the diffraction angle 2 ⁇ is more than 42.8 °) are collectively referred to as titanium nitride, The form will be described.
  • titanium nitride may be used as particles in which other atoms are further mixed.
  • titanium nitride may be used as titanium nitride-containing particles further containing atoms (preferably, sulfur atoms) selected from Periodic Table Group 13-17 elements.
  • the metal nitride which is a combination of metal nitride and metal oxynitride may be used as particles in which other atoms are mixed.
  • the metal nitride may be used as a metal nitride-containing particle further containing an atom (preferably, a sulfur atom) selected from elements of periodic table 13-17.
  • titanium nitride contains titanium oxide TiO 2
  • TiO 2 is white and is a factor to reduce the light shielding property of the light shielding film obtained by curing the curable composition, and therefore, it is preferable to be reduced to such an extent that it is not observed as a peak.
  • the crystallite size of titanium nitride can be determined from the half width of the peak obtained by the measurement of the X-ray diffraction spectrum described above.
  • the crystallite size can be calculated using Scheller's equation.
  • a crystallite size which constitutes titanium nitride 50 nm or less is preferable and 20 nm or more is preferable.
  • the cured film formed using the curable composition is likely to have a higher transmittance of ultraviolet light (especially i-line (wavelength 365 nm)), and the photosensitivity is higher. A composition is obtained.
  • the specific surface area of titanium nitride is not particularly limited, but can be determined by the BET (Brunauer, Emmett, Teller) method.
  • the specific surface area of the titanium nitride is preferably 5 ⁇ 100m 2 / g, more preferably 10 ⁇ 60m 2 / g.
  • a well-known manufacturing method can be used, for example, a gas phase reaction method is mentioned.
  • the gas phase reaction method include an electric furnace method and a thermal plasma method, but the thermal plasma method is preferable from the viewpoint that the mixing of impurities is small, the particle diameter is easy to be uniform, and the productivity is high.
  • the thermal plasma method the method of generating thermal plasma is not particularly limited, and direct current arc discharge, multilayer arc discharge, radio frequency (RF) plasma, hybrid plasma, etc. may be mentioned, and contamination with impurities from the electrode is small. High frequency plasma is more preferred.
  • a specific method for producing a black pigment by a thermal plasma method is not particularly limited.
  • a method for producing a titanium nitride a method of reacting titanium tetrachloride and ammonia gas in a plasma flame (Japanese Patent Laid-Open No. 2-22110) Gazette), a method of evaporating titanium powder by high-frequency thermal plasma, introducing nitrogen as a carrier gas, nitriding it in the cooling process (JP-A-61-11140), and ammonia gas at the periphery of plasma And the like (Japanese Patent Application Laid-Open No. 63-85007) and the like.
  • the method for producing a black pigment is not limited to the above, and the production method is not limited as long as a black pigment having desired physical properties is obtained.
  • the black pigment may contain a layer of a silicon-containing compound (hereinafter referred to as "silicon-containing compound”) on its surface. That is, the (acid) nitride of the metal atom may be coated with a silicon-containing compound to form a black pigment.
  • the method for coating the (acid) nitride of the metal atom is not particularly limited, and any known method can be used.
  • 40 to 70 mass% is preferable with respect to the total solid of a curable composition, as for content of the black pigment in a curable composition, 45 to 70 mass% is more preferable, and 50 to 65 mass% is still more preferable. .
  • the black pigment may be used alone or in combination of two or more. When two or more types of black pigments are used in combination, the total content is preferably in the above range.
  • the curable composition may contain a colorant other than the black pigment.
  • the colorant is not particularly limited, and known colorants can be used.
  • various known pigments (colored pigments), dyes (colored dyes) and the like can be used.
  • the content of the colorant in the curable composition is not particularly limited, but is preferably 20 to 99% by mass, and more preferably 20 to 80% by mass, with respect to the total solid content of the curable composition.
  • the colorant may be used alone or in combination of two or more. When two or more colorants are used in combination, the total content is preferably within the above range.
  • colored dyes include, in addition to colored dyes such as R (red), G (green) and B (blue) (chromatic dyes), those described in paragraphs 0027 to 0200 of JP-A 2014-42375. Colorants can also be used. Also, black dyes can be used. As the color pigment, for example, chromatic color pigments (chromatic color pigments) such as R (red), G (green), and B (blue) can also be used.
  • the pigment used as a colorant may be an inorganic pigment or an organic pigment.
  • the inorganic pigment is not particularly limited, and known inorganic pigments can be used.
  • inorganic pigments include zinc flower, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead, zinc yellow (zinc yellow 1 type, Zinc yellow 2), ultramarine blue, Prussian blue (ferrous iron potassium) zircon gray, praseodymium yellow, chromium titanium yellow, chromium green, peacock, Victoria green, bitumen blue (independent of Prussian blue), vanadium zirconium blue Chrome tin pink, pottery test pink, and salmon pink etc. are mentioned.
  • the inorganic pigment may be surface-modified.
  • examples thereof include inorganic pigments that have been surface-modified with a surface treatment agent having both a silicone group and an alkyl group, such as the “KTP-09” series (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Pigments having infrared absorptivity can also be used.
  • the pigment having infrared absorptivity tungsten compounds, metal borides and the like are preferable.
  • tungsten compounds are preferable from the viewpoint of being excellent in the light shielding property at the wavelength in the infrared region.
  • a tungsten compound is preferable from the viewpoint of the excellent light absorption wavelength region of the oxime polymerization initiator related to the curing efficiency by exposure and the light transmittance of the visible light region.
  • pigments may be used in combination of two or more, and may be used in combination with the dyes described later.
  • pigments having black color or infrared ray shielding property such as red, green, yellow, orange, purple, and blue
  • the form which mixes a pigment or the dye mentioned later is mentioned. It is preferable to mix a red pigment or dye, or a violet pigment or dye, with the pigment having infrared light shielding properties, and more preferable to mix a red pigment with the pigment having infrared light shielding properties.
  • an infrared absorber described later may be added.
  • color index (CI) pigment yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,18, for example.
  • CI color index
  • 20 24, 31, 32, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37, 1, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 16 7, 168, 169, 170, 171, 172, 173, 174, 176, 177, 179, 180, 181,
  • pigments may be used alone or in combination of two or more.
  • dyes examples include, for example, JP-A 64-90403, JP-A 64-91102, JP-A 1-94301, JP-A 6-11614, JP-B 2592 207, and US Pat. No. 4,808,501.
  • the disclosed dyes can be used.
  • pyrazole azo compounds When classified as a chemical structure, pyrazole azo compounds, pyrromethene compounds, anilino azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, or pyrrolopyrazole azomethines Compounds etc. can be used.
  • the dye a dye multimer may be used as the dye. Examples of the dye multimer include the compounds described in JP-A-2011-213925 and JP-A-2013-041097. Moreover, you may use the polymeric dye which has a polymerizability in a molecule
  • the colorant may further contain an infrared absorber.
  • the infrared absorber means a compound having absorption in a wavelength range of infrared range (preferably, wavelength of 650 to 1300 nm).
  • the infrared absorber is preferably a compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm.
  • Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squalilium compounds, naphthalocyanine compounds, quaterrylene A compound, a dithiol metal complex type compound, and a croconium compound etc.
  • phthalocyanine compound naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and croconium compound
  • the compounds disclosed in paragraphs [0010] to [0081] of JP-A-2010-111750 may be used, and the contents of this specification are as described herein. Incorporated into the book.
  • the cyanine compound can be referred to, for example, "Functional pigment, Shin Ookawara / Ken Matsuoka / Keijiro Kitao / Tsunehiro Hiraiso, Kodansha Scientific", the contents of which are incorporated herein.
  • the compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is preferably at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, and naphthalocyanine compounds.
  • the infrared absorber is preferably a compound soluble in water at 25 ° C. in 1% by mass or more, and more preferably a compound soluble in water at 25 ° C. in 10% by mass or more. The solvent resistance is improved by using such a compound.
  • the pyrrolopyrrole compounds can be referred to paragraphs 0049 to 0062 of JP-A-2010-222557, the contents of which are incorporated herein.
  • Cyanine compounds and squarylium compounds are disclosed in paragraphs 0022 to 0063 in WO 2014/088063, 0053 to 0118 in WO 2014/030628, 0028 to 0074 in JP 2014-59550, WO 2012 / JP-A-2015-147, JP-A-2015-176046, JP-A-2014-63144, JP-A-2014-63144, JP-A-2014-52431, JP-A-2014-523, paragraph Paragraphs 0076 to 0124 of 2014-44301, paragraphs 0045 to 0078 of JP 2012-8532, 0027 to 0067 of JP 2015-172102, 0029 ...
  • JP 2015-172004 Paragraph 067 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, JP-A-2015-157893 Paragraphs 0010 to 0025, paragraphs 0013 to 0026 of JP 2014-095007, paragraphs 0013 to 0047 of JP 2014-80487, and paragraphs 0007 to 0028 of JP 2013-227403 can be referred to. This content is incorporated herein.
  • the curable composition contains a polymerizable compound.
  • the term "polymerizable compound” is intended to mean a compound which is polymerized under the action of a polymerization initiator described later, and intends a component different from the dispersant and the alkali-soluble resin described later.
  • the content of the polymerizable compound in the curable composition is not particularly limited, but it is preferably 5 to 30% by mass with respect to the total solid content of the curable composition.
  • the polymerizable compounds may be used alone or in combination of two or more. When two or more types of polymerizable compounds are used in combination, the total content is preferably in the above range.
  • the molecular weight of the polymerizable compound is preferably 2000 or less.
  • the polymerizable compound is preferably a compound containing one or more groups containing an ethylenic unsaturated bond (hereinafter, also simply referred to as "ethylenically unsaturated group"), more preferably a compound containing two or more, and three or more.
  • the compound to contain is further more preferable, and the compound which contains 5 or more is especially preferable.
  • the upper limit is, for example, 15 or less.
  • ethylenically unsaturated group a vinyl group, a (meth) allyl group, and a (meth) acryloyl group etc. are mentioned, for example.
  • polymerizable compound for example, compounds described in paragraph 0050 of JP-A 2008-260927 and paragraph 0040 of JP-A 2015-68893 can be used, and the above contents are incorporated in the present specification.
  • the polymerizable compound may be, for example, any of chemical forms such as monomers, prepolymers, oligomers, and mixtures thereof, and multimers thereof.
  • the polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 6 functional (meth) acrylate compound.
  • the polymerizable compound is also preferably a compound having one or more ethylenically unsaturated groups and having a boiling point of 100 ° C. or more under normal pressure.
  • the compounds described in paragraph 0227 of JP-A-2013-29760 and paragraphs 0254 to 0257 of JP-A-2008-292970 can be referred to, the contents of which are incorporated herein.
  • the polymerizable compound is dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), Pentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH- 12E; Shin-Nakamura Chemical Co., Ltd.) and structures in which these (meth) acryloyl groups are mediated by ethylene glycol residue or propylene glycol residue (for example, SR454, SR499 commercially available from Sartmar) are preferable.
  • NK ester A-TMMT penentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd.
  • the aspect of a preferable polymeric compound is shown below.
  • 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 a nonaromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to produce an acid.
  • a polymerizable compound having a group is more preferable, and in this ester, one in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol is more preferable.
  • Examples of commercially available products include ALONIX TO-2349, M-305, M-510, and M-520 manufactured by Toa Gosei Co., Ltd.
  • the acid value of the polymerizable compound containing an acid group is preferably 0.1 to 40 mg KOH / g, and more preferably 5 to 30 mg KOH / g.
  • the acid value of the polymerizable compound is 0.1 mg KOH / g or more, the developing dissolution property is good, and when it is 40 mg KOH / g or less, it is advantageous in terms of production and / or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.
  • a compound having a caprolactone structure is also a preferred embodiment.
  • the compound having a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentacene.
  • ⁇ -caprolactone modified polyfunctional (meth) obtained by esterifying a polyhydric alcohol such as erythritol, tripentaerythritol, glycerin, diglycerol or trimethylolmelamine with (meth) acrylic acid and ⁇ -caprolactone ) Acrylates.
  • a polyhydric alcohol such as erythritol, tripentaerythritol, glycerin, diglycerol or trimethylolmelamine
  • (meth) acrylic acid and ⁇ -caprolactone ) Acrylates Among them, compounds having a caprolactone structure represented by the following formula (Z-1) are preferable.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents a number of 1 or 2
  • “*” represents a bond.
  • R 1 represents a hydrogen atom or a methyl group, and “*” represents a bond.
  • a compound represented by the following formula (Z-4) or (Z-5) can also be used.
  • E are each independently, - ((CH 2) y CH 2 O) -, or ((CH 2) y CH ( CH 3) O) - a
  • y each independently represents an integer of 0 to 10
  • each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
  • the total of (meth) acryloyl groups is three or four
  • m each independently represents an integer of 0 to 10
  • the total of each m is an integer of 0 to 40.
  • the total of (meth) acryloyl groups is five or six
  • n independently represents an integer of 0 to 10
  • the sum of each n is an integer of 0 to 60.
  • n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.
  • the compounds represented by Formula (Z-4) or Formula (Z-5) may be used alone or in combination of two or more.
  • a compound in which all six X's are an acryloyl group in the formula (Z-5) and A preferred embodiment is a mixture with a compound in which at least one hydrogen atom is present. With such a configuration, developability can be further improved.
  • the total content of the compound represented by Formula (Z-4) or Formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
  • pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
  • the polymerizable compound may contain a cardo skeleton.
  • the polymerizable compound containing a cardo skeleton is preferably a polymerizable compound containing a 9,9-bisarylfluorene skeleton.
  • Examples of the polymerizable compound containing a cardo skeleton include, but are not limited to, On Coat EX series (manufactured by Nagase Sangyo Co., Ltd.) and ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).
  • the polymerizable compound is also preferably a compound containing an isocyanuric acid skeleton as a central core.
  • NK ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd.
  • the content of the ethylenically unsaturated group in the polymerizable compound is 5.0 mmol / It is preferably g or more.
  • the upper limit is not particularly limited, it is generally 20.0 mmol / g or less.
  • the mass ratio of each polymerizable compound in all the polymerizable compounds and the respective polymerizability It is preferable that the sum of the products of the compounds and the double bond equivalents be in the above range.
  • the curable composition preferably contains a resin.
  • the resin include dispersants and alkali-soluble resins.
  • the content of the resin in the curable composition is not particularly limited, but is preferably 3 to 60% by mass, and more preferably 5 to 40% by mass, with respect to the total solid content of the curable composition.
  • the resins may be used alone or in combination of two or more. When two or more resins are used in combination, the total content is preferably in the above range.
  • the molecular weight of the resin is greater than 2000. When the molecular weight of the resin is polydispersed, the weight average molecular weight is more than 2000.
  • the curable composition preferably contains a dispersant.
  • the dispersant is intended to be a compound different from the alkali-soluble resin described later.
  • the content of the dispersant in the curable composition is not particularly limited, but is preferably 2 to 40% by mass, and more preferably 5 to 30% by mass, relative to the total solid content of the curable composition.
  • the dispersant may be used alone or in combination of two or more. When two or more dispersants are used in combination, the total content is preferably in the above range.
  • a well-known dispersing agent can be used selecting it suitably, for example. Among these, high molecular compounds are preferable.
  • the dispersant polymer dispersants [for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type Copolymers, naphthalenesulfonic acid formalin condensates], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, and pigment derivatives.
  • the polymer compounds can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers according to their structures.
  • Polymer compound The polymer compound is adsorbed on the surface of a material to be dispersed, such as a black pigment and other pigments optionally used in combination (hereinafter, the black pigment and other pigments are collectively referred to simply as “pigments”) , Acts to prevent reaggregation of the material to be dispersed. Therefore, terminal modified polymers, grafted polymers (containing polymer chains), or block polymers containing anchor sites on the pigment surface are preferred.
  • the polymer compound may contain a curable group.
  • the curable group include ethylenically unsaturated groups (eg, (meth) acryloyl group, vinyl group, and styryl group), and cyclic ether groups (eg, epoxy group, oxetanyl group etc.), etc. But not limited to. Among them, an ethylenically unsaturated group is preferable as the curable group in that polymerization can be controlled by a radical reaction.
  • the ethylenically unsaturated group is more preferably a (meth) acryloyl group.
  • 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, and as described later, when the resin contains a structural unit containing a graft chain, the above polymer
  • the chain may contain a polyester structure and / or a polyether structure.
  • the said polymeric chain contains a polyester structure.
  • the polymer compound preferably contains a structural unit containing a graft chain.
  • structural unit is synonymous with “repeating unit”.
  • the polymer compound containing a structural unit containing such a graft chain has an affinity to a solvent by the graft chain, and thus the dispersibility of the pigment etc. and the dispersion stability after aging (stability over time) Excellent. Further, due to the presence of the graft chain, the polymer compound containing a structural unit containing a graft chain has an affinity to a polymerizable compound or other usable resin and the like. As a result, alkaline development is less likely to produce a residue.
  • the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and more than 40 atoms excluding hydrogen atoms. More preferably, it is 60 to 500.
  • the graft chain means 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 end of the group branched from the main chain.
  • the graft chain preferably contains a polymer structure, and as such a polymer structure, for example, poly (meth) acrylate structure (eg, poly (meth) acrylic structure), polyester structure, polyurethane structure, polyurea structure, polyamide And polyether structures and the like.
  • 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, thereby enhancing the dispersibility of the pigment etc. It is preferable that it is a graft chain containing at least one, more preferably a graft chain containing 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 being bonded to the main chain of the copolymer to constitute the graft chain) is not particularly limited, but a reactive double bondable group may be used.
  • the macromonomer contained can be used suitably.
  • AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (Trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, produced by Toa Gosei Co., Ltd.), AS-6 (trade name, produced by Toa Gosei Co., Ltd.), AN-6 (trade name, produced by Toa Gosei Co., Ltd.), AW -6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, produced by Toa Gosei Co., Ltd.), AY-707 (trade name, produced by Toa Gosei Co., Ltd.), AY-714 (trade name, produced by Toa Gosei Co., Ltd.
  • AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-30 (trade name, Toa Gosei Co., Ltd.), AK-32 (trade name, Toa Gosei Co., Ltd.), Blenmer PP-100 (trade name, NOF Corporation) Brenmer PP-500 (trade name, manufactured by NOF Corporation), Brenmer PP-800 Product name, manufactured by NOF Corporation, BLEMMER PP-1000 (trade name, manufactured by NOF Corporation), BLEMMER 55-PET-800 (trade name, manufactured by NOF Corporation), BLEMMER PME-4000 (trade name, manufactured by NOF Corporation) Blemmer PSE-400 (trade name, manufactured by NOF Corporation), Blemmer PSE-1300 (trade name, manufactured by NOF Corporation), or Blemmer 43PAPE-600B (trade name, manufactured by NOF Corporation), etc.
  • AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, Toa Gosei Co., Ltd.), AB-6 (trade name, produced by Toa Gosei Co., Ltd.), AS-6 (trade name, Preferably, Toa Gosei Co., Ltd., AN-6 (trade name, Toa Gosei Co., Ltd.), or Blenmer PME-4000 (trade name, NOF Corporation).
  • the dispersant preferably contains at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate and cyclic or chain polyester, and is preferably polymethyl acrylate or polymethacrylic acid. It is more preferable to contain at least one structure selected from the group consisting of methyl and linear polyesters, and a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure More preferably, it contains at least one structure selected from the group consisting of
  • the dispersing agent may be a dispersing agent containing the above structure alone in one dispersing agent, or may be a dispersing agent containing a plurality of these structures in one dispersing agent.
  • 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.
  • the dispersing agent containing a polycaprolactone structure the dispersing agent whose j and k in a following formula (1) and a following formula (2) are 5 is mentioned.
  • the dispersing agent containing a polyvalerolactone structure the dispersing agent whose j and k in following formula (1) and following formula (2) are 4 is mentioned.
  • dispersants containing polymethyl acrylate structure, X 5 in formula (4) is a hydrogen atom
  • R 4 can be cited dispersants are methyl groups.
  • the polymer compound preferably contains, as a structural unit containing a graft chain, a structural unit represented by any one of the following formulas (1) to (4), and the following formula It is more preferable to contain the structural unit represented by either of (1A), following formula (2A), following formula (3A), following formula (3B), and 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.
  • Each of X 1 , X 2 , X 3 , X 4 and X 5 independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (number of carbon atoms), from the viewpoint of the restriction on synthesis
  • Y 1 , Y 2 , Y 3 and Y 4 each independently represent a divalent linking group, and the linking group is not particularly restricted 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) and the like.
  • a and B respectively indicate bonding sites to the left end group and the right end group in the formulas (1) to (4).
  • (Y-2) or (Y-13) is more preferable in terms of easiness 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 Etc.
  • a group having a steric repulsion effect is particularly preferable from the viewpoint of improving the dispersibility, and each of them independently has carbon number
  • An alkyl group or alkoxy group of 5 to 24 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 having 5 to 24 carbon atoms is particularly independently of each other. Groups are 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 in the formulas (1) and (2) are preferably integers of 4 to 6, and more preferably 5 from the viewpoint of the temporal stability and developability of the composition.
  • n and m are preferably integers of 10 or more, and more preferably 20 or more.
  • the sum of the repeating number of the polycaprolactone structure and the repeating number of the polyvalerolactone is preferably an integer of 10 or more, 20 or more An integer is more preferred.
  • R 3 represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, plural R 3 s may be the same as or different from each other.
  • R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. 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.
  • the alkyl group may be a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms.
  • the linear alkyl group having 1 to 20 carbon atoms is more preferable, and the linear alkyl group having 1 to 6 carbon atoms is further preferable.
  • a plurality of X 5 and R 4 in the graft copolymer may be the same or different.
  • the polymer compound can contain a graft chain-containing structural unit in which two or more kinds of structures are different. That is, structural units represented by formulas (1) to (4) having mutually different structures may be contained in the molecule of the polymer compound, and n, m, p in formulas (1) to (4) And q each represents an integer of 2 or more, in the formulas (1) and (2), j and k may contain structures different from each other in the side chain, and formulas (3) and (4) In the above, R 3 , R 4 and X 5 which are present in plural in the molecule may be the same as or different from each other.
  • the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of the temporal stability of the composition and the developability.
  • a structural unit represented by Formula (2) it is more preferable that it is a structural unit represented by following formula (2A) from a time-lapse stability of a composition, and a developability.
  • a structural unit represented by Formula (3) it is more preferable that it is a structural unit represented by a following formula (3A) or Formula (3B) from a time-lapse stability of a composition, and a developability viewpoint. .
  • the polymer compound more preferably contains a structural unit represented by the formula (1A) as a structural unit containing a graft chain.
  • structural units containing a graft chain are 2 to 90% by mass in terms of mass relative to the total mass of the polymer compound Is preferably contained in the range of 5 to 30% by mass, and more preferably in the range of 5 to 30% by mass.
  • the structural unit containing a graft chain is contained in this range, the dispersibility of the pigment is high, and the developability at the time of forming a cured film is good.
  • the polymer compound preferably contains a hydrophobic structural unit which is different from the structural unit containing a graft chain (that is, not corresponding to a structural unit containing a 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, etc.).
  • the hydrophobic structural unit is preferably a (corresponding) structural unit derived from a compound (monomer) having a C log P value of 1.2 or more, and is a structural unit derived from a compound having a C log P value of 1.2 to 8. Is more preferable. Thereby, the effects of the present invention can be more reliably exhibited.
  • ClogP values are from Daylight Chemical Information System, Inc. Is a value calculated by the program "CLOGP” available from This program provides the value of "computed logP” calculated by the fragment approach of Hansch, Leo (see the following document). The fragment approach is based on the chemical structure of the compound, dividing the chemical structure into substructures (fragments) and estimating the logP value of the compound by summing the logP contributions assigned to the fragment. The details are described in the following documents.
  • the ClogP value calculated by the program CLOGP v4.82 is used herein. A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P .; G. Sammnens, J.J. B. Taylor and C. A.
  • log P means the common logarithm of partition coefficient P (Partition Coefficient), and it quantitatively determines how an organic compound is distributed in the equilibrium of oil (generally 1-octanol) and water. Is a physical property value represented as a 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, one or more structural units 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 (eg, a fluorine atom, a chlorine atom, a bromine atom etc.), or a carbon number Represents an alkyl group of 1 to 6 (eg, a methyl group, an ethyl group, a propyl group, etc.).
  • 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 hydrogen atoms.
  • X represents an oxygen atom (-O-) or an imino group (-NH-), preferably an oxygen atom.
  • L is a single bond or a divalent linking group.
  • a divalent aliphatic group for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group
  • a divalent aromatic group for example, an arylene group) , substituted arylene group
  • a divalent heterocyclic group an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR 31 -, wherein R 31 And examples thereof include aliphatic groups, aromatic groups or heterocyclic groups), carbonyl groups (—CO—), and combinations thereof.
  • 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 6 to 20, more preferably 6 to 15, and still more preferably 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.
  • the divalent heterocyclic group preferably contains a 5- or 6-membered ring as a heterocyclic ring.
  • the heterocycle may be fused to another heterocycle, an aliphatic ring or an aromatic ring.
  • 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 contain a polyoxyalkylene structure containing an oxyalkylene structure repeated two or more times.
  • a polyoxyalkylene structure a polyoxyethylene structure or a polyoxypropylene structure is preferable.
  • the polyoxyethylene structure is represented by-(OCH 2 CH 2 ) n-, and n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.
  • an aliphatic group for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group
  • an aromatic group for example, an aryl group, a substituted aryl group, an arylene group, a substituted arylene group
  • heterocyclic groups or combinations thereof an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR 31 -, wherein R 31 is an aliphatic group, an aromatic A group or a heterocyclic group) or a carbonyl group (-CO-) may be included.
  • 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-aggregated hydrocarbon group and a crosslinked cyclic hydrocarbon group, and examples of the ring-aggregated hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and And-include cyclohexylphenyl and the like.
  • bridged cyclic hydrocarbon ring for example, pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) 2 Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredane, adamantane, tricyclo [5.2.1.0 2,6 ] decane, and tricyclo [4.3.1.1 2,5 ] undecane rings And tetracyclo [4.4.0.1 2,5 .
  • [1 7,10 ] dodecane and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring and the like can be mentioned.
  • a fused cyclic hydrocarbon ring for example, perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and Also included are fused rings in which a plurality of 5- to 8-membered cycloalkane rings such as perhydrophenalene rings are fused.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of substituents include halogen atoms, aromatic groups and heterocyclic groups. However, the aliphatic group does not have an acid group as a substituent.
  • the carbon number of the aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups and heterocyclic groups. However, the aromatic group does not have an acid group as a substituent.
  • the heterocyclic group preferably contains a 5- or 6-membered ring as a heterocyclic ring.
  • the heterocycle may be fused to another heterocycle, an aliphatic ring or an aromatic ring.
  • the heterocyclic 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 an alkyl group having 1 to 6 carbon atoms (Eg, methyl group, ethyl group, propyl group etc.), Z or LZ.
  • L and Z are as defined above.
  • 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
  • L contains a single bond or an alkylene group or an oxyalkylene structure.
  • X is an oxygen atom or an imino group
  • Z is an aliphatic group, a heterocyclic group or an aromatic group
  • an R 1 is hydrogen atom or a methyl group
  • L is an alkylene group
  • Z is an aliphatic group, a heterocyclic group, or an aromatic Compounds which are groups are preferred.
  • R 4, R 5, and, R 6 is a hydrogen atom or a methyl group
  • Z is an aliphatic group, a heterocyclic group, or an aromatic Compounds which are groups are preferred.
  • Examples of representative compounds represented by the formulas (i) to (iii) include radically polymerizable compounds selected from acrylic esters, methacrylic esters, styrenes and the like.
  • radically polymerizable compounds selected from acrylic esters, methacrylic esters, styrenes and the like.
  • the compound as described in stage 0089-0093 of Unexamined-Japanese-Patent No. 2013-249417 can be referred, and these contents are described in this specification. Incorporated into
  • the hydrophobic structural unit is preferably contained in a range of 10 to 90%, and more preferably in a range of 20 to 80%, based on the total mass of the polymer compound, in terms of mass. Sufficient pattern formation is obtained in the above range of content.
  • the polymer compound can introduce a functional group capable of forming an interaction with the pigment etc.
  • the polymer compound preferably further contains a structural unit containing 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 and the like include an acid group, a basic group, a coordinating group, and a functional group having reactivity.
  • the polymer compound contains an acid group, a basic group, a coordinating group, or a functional group having reactivity, a structural unit containing an acid group, a structural unit containing a basic group, It is preferable to contain a structural unit containing a reactive group or a structural unit having reactivity.
  • the polymer compound when the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, the polymer compound can be provided with developability for pattern formation by alkali development. That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound as the dispersant contributing to the dispersion of the pigment etc. contains alkali solubility by the composition described above. A composition containing such a polymer compound is excellent in the light shielding property of the exposed area, and the alkali developability of the unexposed area is improved.
  • the polymer compound when the polymer compound contains a structural unit containing an acid group, the polymer compound tends to be compatible with the solvent, and the coatability tends to be improved.
  • the acid group in the structural unit containing the 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 in which the pigment and the like are dispersed decreases. It is presumed that the polymer compound itself is also easily dispersed stably.
  • the structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the above-mentioned structural unit containing a graft chain, or may be a different structural unit, but an alkali as an acid group
  • the structural unit containing a soluble group is a structural unit different from the above-mentioned hydrophobic structural unit (that is, it does not correspond to the above-mentioned hydrophobic structural unit).
  • Examples of the acid group that is a functional group capable of forming an interaction with a pigment and the like include, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group. And at least one of phosphoric acid groups is preferable, and a carboxylic acid group is more preferable.
  • the carboxylic acid group has good adsorptivity to pigments and the like, and has 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 when it is contained, the content of the structural unit containing an acid group is the total mass of the polymer compound in terms of mass. On the other hand, the content is preferably 5 to 80% by mass, and more preferably 10 to 60% by mass from the viewpoint of suppressing damage to the image strength due to alkaline development.
  • a basic group which is a functional group capable of forming an interaction with a pigment etc. for example, a primary amino group, a secondary amino group, a tertiary amino group, a heterocycle containing N atom, and an amide
  • the preferred basic group is a tertiary amino group in that it has a group etc. and is preferable in that it has good adsorptivity to pigments etc and 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 the total of the polymer compound in terms of mass. The content is preferably 0.01 to 50% by mass, and more preferably 0.01 to 30% by mass from the viewpoint of development inhibition inhibition.
  • a coordinating group which is a functional group capable of forming an interaction with a pigment or the like, and as a functional group having reactivity, for example, acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, and acidification Things etc.
  • the preferred functional group is an acetylacetoxy group in that it has good adsorptivity to pigments and the like and high dispersibility of 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 functional group having reactivity, but when it is contained, the content of these structural units In terms of mass, 10 to 80% by mass is preferable based on the total mass of the polymer compound, and 20 to 60% by mass is more preferable from the viewpoint of development inhibition inhibition.
  • the polymer compound may contain a functional group capable of forming an interaction with the various pigments described above, There is no particular limitation on how these functional groups are introduced, but the polymer compound is selected from structural units derived from monomers represented by the following formulas (iv) to (vi). It is preferred to contain more than species of 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, etc.) or a carbon number of 1 to 6 represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.).
  • R 11 , R 12 and R 13 each independently represent preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently represents a hydrogen atom or methyl More preferred is a group.
  • each of R 12 and R 13 is more preferably a hydrogen atom.
  • X 1 in the formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), preferably an oxygen atom.
  • Y in Formula (v) represents a methine group or a nitrogen atom.
  • L 1 in 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 formula (i) described above.
  • 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 also include a polyoxyalkylene structure containing an oxyalkylene structure repeated two or more times.
  • a polyoxyalkylene structure a polyoxyethylene structure or a polyoxypropylene structure is preferable.
  • the polyoxyethylene structure is represented by-(OCH 2 CH 2 ) n-, and n is preferably an integer of 2 or more, 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 in addition to the graft chain, and is preferably a carboxylic acid group or a tertiary amino group, More preferred is an acid group.
  • R 14 , R 15 and R 16 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like), or an alkyl group having 1 to 6 carbon atoms for example, a methyl group, an ethyl group, a propyl group, etc.), - Z 1, or an L 1 -Z 1.
  • L 1 and Z 1 are the same meaning as L 1 and Z 1 in the above, it is the preferable examples.
  • R 1 As 4 , R 15 and R 16 each independently, 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 each independently represent a hydrogen atom or a methyl group, and L 1 is a divalent having an alkylene group or an oxyalkylene structure.
  • Compounds in which X 1 is an oxygen atom or an imino group and Z 1 is a carboxylic acid group are preferable.
  • R 11 is a hydrogen atom or a methyl group
  • L 1 is an alkylene group
  • Z 1 is a carboxylic acid group
  • Y is a methine group Compounds which are preferred.
  • R 14 , R 15 and R 16 each independently represent a hydrogen atom or a methyl group, and L 1 represents a single bond or an alkylene group, and Z Compounds in which 1 is a carboxylic acid group are preferred.
  • monomers represented by the formulas (iv) to (vi) are shown.
  • monomers include methacrylic acid, crotonic acid, isocrotonic acid, and the reaction of succinic anhydride with a compound having an addition-polymerizable double bond and hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate).
  • the content of the structural unit containing a functional group capable of forming an interaction with a pigment or the like is the total mass of the polymer compound from the viewpoint of the interaction with the pigment or the like, the temporal stability, and the permeability to the developer.
  • 0.05 to 90% by mass is preferable, 1.0 to 80% by mass is more preferable, and 10 to 70% by mass is more preferable.
  • the polymer compound is a structural unit containing a graft chain, a hydrophobic structural unit, and a pigment as long as the effects of the present invention are not impaired for the purpose of improving various performances such as image strength.
  • other structural units having various functions eg, structural units containing a functional group having an affinity for a solvent described later, etc.
  • Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles and methacrylonitriles and the like.
  • the polymer compound one or more of these other structural units can be used, and the content thereof is preferably 0 to 80% by mass with respect to the total mass of the polymer compound in terms of mass, 60 mass% or less is more preferable. Sufficient pattern formability is maintained in the above range of content.
  • the acid value of the polymer compound is preferably in the range of 0 mg to 250 mg KOH / g, more preferably in the range of 10 to 200 mg KOH / g, and still more preferably in the range of 20 to 120 mg KOH / g.
  • the acid value of the polymer compound is 160 mg KOH / g or less, pattern peeling during development when forming a cured film can be more effectively suppressed.
  • the acid value of the polymer compound is 10 mg KOH / g or more, the alkali developability becomes better.
  • the acid value of the polymer compound is 20 mg KOH / g or more, sedimentation of the pigment and the like can be further suppressed, the number of coarse particles can be further reduced, and the temporal stability of the composition can be further improved.
  • the acid value can be calculated, for example, from the average content of acid groups in a compound.
  • resin which has a desired acid value can be obtained by changing content of the structural unit containing the acidic radical which is a structural component of resin.
  • the weight average molecular weight of the polymer compound is preferably 4,000 to 300,000, more preferably 5,000 to 200,000, and still more preferably 6,000 to 100,000. Particular preference is given to 10,000 to 50,000.
  • the polymer compound can be synthesized based on a known method.
  • polymer compound examples include “DA-7301” manufactured by Kushimoto Chemical Co., Ltd., “Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (acid group-containing copolymer” manufactured by BYK Chemie ), 111 (phosphate based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer), “BYK-P104, P105 (high molecular weight non-polymer)” Saturated polycarboxylic acid) ", EFKA 4047, 4050 to 4010 to 4165 (polyurethane based), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (manufactured by EFKA) High molecular weight polycarboxylate), 6220 (fatty acid polyaceta) Ter), 6745
  • NIKKOL T106 polyoxyethylene sorbitan Monooleate
  • MYS-IEX polyoxyethylene monostearate
  • Hinoac T-8000 E etc., manufactured by Kawaken Fine Chemicals Co., Ltd., Shin-Etsu Chemical Co., Ltd., organosiloxane polymer, KP-341, Yusho "W 001: cationic surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene Nonionic surfactants such as glycol distearate, sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", "Morita Sangyo” "EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100"
  • amphoteric resin containing an acid group and a basic group.
  • the amphoteric resin is preferably a resin having an acid value of 5 mg KOH / g or more and an amine value of 5 mg KOH / g or more.
  • DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK-2001, DISPERBYK-2010, manufactured by BIC Chemie Examples include DISPERBYK-2012, DISPERBYK-2025, BYK-9076, and Ajisame Fine Techno Co., Ltd. Ajisper PB 821, Ajisper PB 822, and Ajisper PB 881 and the like.
  • One of these polymer compounds may be used alone, or two or more thereof may be used in combination.
  • graft copolymers of paragraphs 0037 to 0115 of JP 2010-106268 A (columns 0075 to 0133 of corresponding US 2011/0124824) can be used.
  • the contents of are incorporated herein by reference.
  • it contains the side chain structure which the acidic group of Unexamined-Japanese-Patent No.2011-153283, Paragraph 0028-0084 (Correspondence US2011 / 02729759 corresponding column 0075-0133 column) joins via a coupling group besides the above.
  • Polymer compounds containing the following components can be used, the contents of which can be incorporated and incorporated herein.
  • the curable composition preferably contains an alkali soluble resin.
  • an alkali-soluble resin is intended to be a resin containing a group that promotes alkali solubility (alkali-soluble group), and is intended to be a resin different from the dispersant described above.
  • the content of the alkali-soluble resin in the curable composition is not particularly limited, but is preferably 1 to 30% by mass, and more preferably 1 to 15% by mass with respect to the total solid content of the curable composition.
  • the alkali-soluble resin may be used alone or in combination of two or more. When using 2 or more types of alkali-soluble resin together, it is preferable that total content is in the said range.
  • alkali-soluble resin examples include resins containing at least one alkali-soluble group in the molecule, such as polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide resin, (meth) Acrylic / (meth) acrylamide copolymer resin, an epoxy resin, and a polyimide resin etc. are mentioned.
  • alkali-soluble resin examples include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds.
  • the unsaturated carboxylic acid is not particularly limited, but monocarboxylic acids such as (meth) acrylic acid, crotonic acid and vinyl acetic acid; itaconic acid, maleic acid and dicarboxylic acids such as fumaric acid or acid anhydride thereof And monohydric carboxylic acid monoesters such as phthalic acid mono (2- (meth) acryloyloxyethyl); and the like.
  • Examples of the copolymerizable ethylenically unsaturated compound include methyl (meth) acrylate and the like. Further, the compounds described in paragraph 0027 of JP-A-2010-97210 and in paragraphs 0036 to 0037 of JP-A-2015-68893 can also be used, and the above contents are incorporated in the present specification.
  • an ethylenically unsaturated compound which can be copolymerized Comprising: You may use combining the compound containing an ethylenically unsaturated group in a side chain.
  • 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. You can get it.
  • an alkali-soluble resin containing a curable group is also preferable.
  • the curable group which the above-mentioned high molecular compound may contain is mentioned similarly, A preferable range is also the same.
  • an alkali-soluble resin containing a curable group an alkali-soluble resin having a curable group in a side chain is preferable.
  • an alkali-soluble resin containing a curable group Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (containing COOH containing polyurethane acrylic oligomer.
  • Diamond Shamrock Co., Ltd. Biscoat R-264, KS resist 106 All of them are Osaka Organic Chemical Industry Co., Ltd., Cyclomer P series (for example, ACA 230 AA), Plaxcel CF 200 series (all of which are manufactured by Daicel), Ebecryl 3800 (manufactured by Daicel Ornex), And the like.
  • alkali-soluble resin for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-54-92723, JP-A-59- Radical polymers containing a carboxylic acid group in the side chain as described in JP-A-59-3836 and JP-A-59-71048; European Patent No. 993966, European Patent No. 1204000, and JP-A No. 2001-318463 Acetal-modified polyvinyl alcohol-based binder resin containing an alkali-soluble group described in each publication such as U.S.
  • 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 contents are incorporated herein.
  • a polyimide precursor can also be used as an alkali soluble resin.
  • the polyimide precursor intends a resin obtained by the addition polymerization reaction of a compound containing an acid anhydride group and a diamine compound at 40 to 100 ° C.
  • resin containing the repeating unit represented by Formula (1) is mentioned, for example.
  • the structure of the polyimide precursor include an amic acid structure represented by the following formula (2), a following formula (3) in which the amic acid structure is partially imide ring-closed, and a following formula (4) in which all imide ring closure
  • the polyimide precursor containing the imide structure shown by these) is mentioned.
  • 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 for example, compounds described in paragraphs 0011 to 0031 of JP 2008-106250 A, compounds described in paragraphs 0022 to 0039 of JP 2016-122101 A, and JP
  • the compounds described in paragraphs [0061] to [0092] of 2016-68401, and the like are included, and the above contents are incorporated in the present specification.
  • the alkali-soluble resin contains at least one selected from the group consisting of a polyimide resin and a polyimide precursor in that the pattern shape of the cured film in a pattern obtained by using the curable composition is more excellent. Is also preferred.
  • 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. The resins described in the paragraphs [0012] to [0013] and the like are mentioned, and the above contents are incorporated in the present specification.
  • the curable composition used for the manufacturing method of this invention contains resin containing an ethylenically unsaturated group from the point which the rectangularity of the cross-sectional shape of the cured film obtained is more excellent.
  • the resin containing an ethylenically unsaturated group may be a dispersant or an alkali soluble resin.
  • resin other than a dispersing agent or alkali-soluble resin may be sufficient.
  • the lower limit of the content of the resin having an ethylenically unsaturated group in the curable composition is preferably 40% by mass or more, more preferably 45% by mass or more based on the mass of the entire resin contained in the curable composition.
  • resin containing an ethylenically unsaturated group in the curable composition is preferably 100% by mass or less based on the total mass of the resin contained in the curable composition.
  • resin containing an ethylenically unsaturated group means resin which contains one or more ethylenically unsaturated groups in 1 molecule.
  • the content of the resin containing an ethylenically unsaturated group may be calculated from the amount of raw materials charged.
  • the content of the ethylenically unsaturated group is not particularly limited, but is preferably 0.001 to 5.00 mmol / g, more preferably 0.10 to 3.00 mmol / g, and the like. More preferred is 26 to 2.50 mmol / g.
  • the content of the ethylenically unsaturated group is in the range of 0.10 to 3.00 mmol / g, the rectangularity of the cross-sectional shape of a cured film obtained using the curable composition is more excellent.
  • the said resin total mass intends the total mass of resin contained in a curable composition, for example, curable composition of resin containing an ethylenically unsaturated group, and resin which does not contain an ethylenically unsaturated group
  • the content of the above-mentioned ethylenically unsaturated group represents the content of the ethylenically unsaturated group in the resin containing the ethylenically unsaturated group with respect to the total mass of the resin.
  • resin is a component which is melt
  • combining resin containing an ethylenically unsaturated group it can replace with measurement by calculating from the preparation amount of a raw material.
  • require C C number of.
  • the ethylenically unsaturated group content of the resin when the ethylenically unsaturated group is a (meth) acryloyl group, it is measured by the following method. First, solid components (black pigment and the like) in the curable composition are precipitated by centrifugation, and the remaining liquid component is separated. Further, from the obtained liquid component, a component having a weight average molecular weight of more than 2000 is separated by a GPC method, and this is used as a resin to be measured. Next, 0.25 mg of a resin to be measured is dissolved in 50 mL of THF (tetrahydrofuran), and 15 mL of methanol is further added to prepare a solution.
  • THF tetrahydrofuran
  • the ethylenically unsaturated group is a combination of a (meth) acryloyl group other than (meth) acryloyl group and a group other than a (meth) acryloyl group and a (meth) acryloyl group
  • a method of measuring the bromination of the resin to be measured that has been separated by the above-mentioned method may be mentioned.
  • the bromine number is measured in accordance with JIS K2605: 1996.
  • bromine was added to the resin 100g of measurements obtained in bromine number (Br 2) grams of (gBr 2 / 100g), the resin per 1g It is a value converted to the number of moles of added bromine (Br 2 ).
  • the curable composition preferably contains a polymerization initiator.
  • the polymerization initiator is not particularly limited, and known polymerization initiators can be used.
  • a polymerization initiator a photoinitiator, a thermal-polymerization initiator etc. are mentioned, for example, A photoinitiator is preferable.
  • a photoinitiator is preferable.
  • a polymerization initiator what is called a radical polymerization initiator is preferable.
  • the content of the polymerization initiator in the curable composition is not particularly limited, but it is preferably 0.5 to 20% by mass with respect to the total solid content of the curable composition.
  • the polymerization initiator may be used alone or in combination of two or more. When two or more polymerization initiators are used in combination, the total content is preferably in the above range.
  • thermal polymerization initiator As a thermal polymerization initiator, for example, 2,2′-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismaleonitrile, and dimethyl- (2,2 ′)-azobis (2) Azo compounds such as -methyl propionate) [V-601], and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
  • AIBN 2,2′-azobisisobutyronitrile
  • 3-carboxypropionitrile 3-carboxypropionitrile
  • azobismaleonitrile azobismaleonitrile
  • dimethyl- (2,2 ′)-azobis (2) Azo compounds such as -methyl propionate) [V-601]
  • organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
  • organic peroxides such as benzoyl peroxide, lauroyl per
  • the curable composition preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited as long as polymerization of the polymerizable compound can be initiated, and known photopolymerization initiators can be used.
  • a photopolymerization initiator having photosensitivity to an ultraviolet light region to a visible light region is preferable.
  • it may be an activator that produces an action with photoexcited sensitizers to generate active radicals, and may be an initiator that initiates cationic polymerization depending on the type of the polymerizable compound.
  • the photopolymerization initiator preferably contains at least one compound having a molar absorption 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 curable composition is not particularly limited, but it is preferably 0.5 to 20% by mass with respect to the total solid content of the curable composition.
  • the photopolymerization initiator may be used singly or in combination of two or more. When using 2 or more types of photoinitiators together, it is preferable that total content is in the said range.
  • the photopolymerization initiator for example, a halogenated hydrocarbon derivative (for example, one containing a triazine skeleton, one containing an oxadiazole skeleton, etc.), an acylphosphine compound such as an 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 in the present specification.
  • the photopolymerization initiator for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used.
  • the hydroxyacetophenone compound for example, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF Corporation) can be used.
  • the aminoacetophenone compound for example, commercially available products IRGACURE-907, IRGACURE-369, or IRGACURE-379EG (trade name: all manufactured by BASF Corp.) can be used.
  • aminoacetophenone compound a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long wave light source having a wavelength of 365 nm or a wavelength of 405 nm can also be used.
  • an acyl phosphine compound IRGACURE-819 which is a commercial item, or IRGACURE-TPO (trade name: all manufactured by BASF Corporation) can be used.
  • an oxime ester-type polymerization initiator (oxime compound) is more preferable.
  • oxime compounds are preferable because they have high sensitivity and high polymerization efficiency, and the black pigment content in the curable composition is easily designed to be high.
  • compounds described in JP-A-2001-233842 compounds described in JP-A-2000-80068, or compounds described in JP-A-2006-342166 can be used.
  • Examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 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 Examples include carbonyloxyimino-1-phenylpropan-1-one and the like. Also, J.J. C. S. Perkin II (1979) pp. 1653-1660), J.F. C. S.
  • IRGACURE-OXE01 manufactured by BASF
  • IRGACURE-OXE02 manufactured by BASF
  • IRGACURE-OXE03 manufactured by BASF
  • IRGACURE-OXE04 manufactured by BASF
  • TR-PBG-304 made by Changzhou Strong Electronic New Materials Co., Ltd.
  • Adeka Akuls NCI-831 Adeka Ark's NCI-930
  • N-1919 carboxylic acid
  • An initiator made by ADEKA
  • oxime compounds other than those described above compounds described in JP-A-2009-519904 in which an oxime is linked to the carbazole N-position; compounds described in US Pat. Compounds described in JP-A-2010-15025 and U.S. Patent Publication 2009-292039 in which a nitro group is introduced at a dye site; a ketoxime compound described in WO 2009-131189; and a triazine skeleton and an oxime skeleton
  • US Pat. No. 7,556,910 contained in the same molecule; the compound described in JP-A 2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source; etc. Good.
  • oxime compound a compound represented by the following formula (OX-1) is preferable. Whether the N-O bond of the oxime compound is an oxime compound of (E) form, an oxime compound of (Z) form, or a mixture of (E) form and (Z) form Good.
  • 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 nonmetal atomic group.
  • the monovalent nonmetal atom 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.
  • these groups may have one or more substituents.
  • the substituent mentioned above may be further substituted by the other 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, an aryl group and the like.
  • a halogen atom an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group
  • an acyloxy group an acyl group, an alkyl group, an aryl group and the like.
  • 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.
  • the substituent the above-mentioned substituents can be exemplified.
  • 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. As the substituent, the above-mentioned substituents can be exemplified.
  • the oxime compound containing a fluorine atom can also be used.
  • the oxime compound containing a fluorine atom compounds described in JP-A-2010-262028; Compounds 24 and 36 to 40 described in JP-A-2014-500852; and JP-A-2013-164471 Compounds (C-3); and the like. This content is incorporated herein.
  • 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 R 7 represents an arylalkyl group having 7 to 30 carbon atoms, and when R 1 and R 2 are phenyl groups, the phenyl groups may be bonded to form a fluorene group, and R 3 and R 4 are each independently 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, and X represents a direct bond or carbonyl Indicates 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
  • 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 4 to carbon atoms 20 heterocyclic groups
  • 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 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, or carbon And represents a heterocyclic group of 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 , -CSOR 6 , -CN, a halogen atom
  • 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 each independently 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 each independently 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, for example, compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated herein by reference.
  • oxime compound preferably used for the said curable composition is shown below.
  • the compounds described in Table 1 of WO 2015-036910 can also be used, and the above contents are incorporated herein.
  • the oxime compound preferably has a maximum absorption wavelength in a wavelength range of 350 to 500 nm, more preferably a maximum absorption wavelength in a wavelength range of 360 to 480 nm, and still more preferably a high absorbance at 365 nm and 405 nm.
  • the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, 5,000 to 200, More preferably, it is 000.
  • the molar absorptivity of the compound can be measured by a known method, for example, using an ethyl acetate solvent at a concentration of 0.01 g / L with an ultraviolet-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian). Is preferred. You may use a photoinitiator in combination of 2 or more types as needed.
  • the curable composition preferably contains a polymerization inhibitor.
  • the polymerization inhibitor is not particularly limited, and known polymerization inhibitors can be used.
  • the polymerization inhibitor include phenolic polymerization inhibitors (eg, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4-methoxynaphthol etc .; hydroquinone polymerization inhibitors (eg Hydroquinone, 2,6-di-tert-butyl hydroquinone, etc .; quinone type polymerization inhibitors (eg, benzoquinone etc.); free radical polymerization inhibitors (eg, 2,2,6,6-tetramethylpiperidine 1- Oxyl free radical, 4-hydroxy-2,2,6,6
  • the effect of the polymerization inhibitor is remarkable when used together with a resin containing a curable group.
  • the content of the polymerization inhibitor in the curable composition is not particularly limited, but is preferably 0.0001 to 0.5% by mass, and more preferably 0.001 to 0.2%, based on the total solid content of the curable composition. % By mass is more preferred.
  • the polymerization inhibitor may be used alone or in combination of two or more. When two or more polymerization inhibitors are used in combination, the total content is preferably within the above range.
  • the curable composition may contain a surfactant.
  • the surfactant contributes to the improvement of the coatability of the curable composition.
  • the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the curable composition.
  • the surfactant may be used alone or in combination of two or more. When two or more surfactants are used in combination, the total amount is preferably in the above range.
  • surfactant examples include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.
  • liquid properties (in particular, fluidity) of the curable composition are further improved. That is, in the case of forming a film using a curable composition containing a fluorine-based surfactant, the wettability to the surface to be coated is improved by reducing the interfacial tension between the surface to be coated and the coating liquid. The coating property on the surface to be coated is improved. For this reason, even in the case where a thin film of about several ⁇ m is formed with a small amount of liquid, it is effective in that film formation with uniform thickness with small thickness unevenness can be more suitably performed.
  • the content of fluorine in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 7 to 25% by mass.
  • the fluorine-based surfactant having a fluorine content in this range is effective in terms of the uniformity of the thickness of the coating film and / or the liquid saving property, and the solubility in the curable composition is also good. .
  • fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F44, R30, F437, F475, F479, and the like.
  • the same F482, the same F554, and the same F780 (above, DIC Corporation); Florard FC430, the same FC431, and the same FC171 (above, Sumitomo 3M Co., Ltd.); Surfron S-382, the same SC-101 , SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by Asahi Glass Co., Ltd.) And PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA Corporation).
  • a block polymer can also be used as the fluorine-based surfactant, and as a specific example, for example, compounds described in JP-A No.
  • the curable composition may contain a UV absorber.
  • a UV absorber UV absorbers of salicylate type, benzophenone type, benzotriazole type, substituted acrylonitrile type and triazine type can be used.
  • the compounds of paragraphs 0137 to 0142 of JP 2012-068418 A (corresponding to paragraphs 0251 to 0254 of corresponding US 2012/0068292) can be used, and the contents thereof can be incorporated and incorporated herein. .
  • diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by Daito Chemical Industries, trade name: UV-503) is preferably used.
  • the ultraviolet absorber include compounds exemplified in paragraphs [0134] to [0148] of JP-A-2012-32556.
  • the content of the UV absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, still more preferably 0.1 to 5% by mass, based on the total solid content of the curable composition. preferable.
  • the curable composition may contain a silane coupling agent.
  • the silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule.
  • hydrolysable groups such as an alkoxy group, are couple
  • the hydrolyzable group is a substituent which is directly bonded to a silicon atom and can form a siloxane bond by hydrolysis reaction and / or condensation reaction.
  • a hydrolysable group a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group are mentioned, for example.
  • the hydrolyzable group contains a carbon atom
  • the carbon number thereof is preferably 6 or less, more preferably 4 or less.
  • 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 cured film, so fluorine atoms and silicon atoms (but excluding silicon atoms to which a hydrolyzable group is bonded) It is preferable not to contain, and a fluorine atom, a silicon atom (but excluding a silicon atom to which a hydrolyzable group is bonded), an alkylene group substituted with a silicon atom, a linear alkyl group having 8 or more carbon atoms, It is desirable not to include a branched alkyl group having 3 or more carbon atoms.
  • the content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass, and more preferably 0.5 to 8% by mass, relative to the total solid content in the curable composition. 1.0 to 6% by mass is more preferable.
  • the said curable composition may contain the silane coupling agent individually by 1 type, and may contain 2 or more types. When a curable composition contains 2 or more types of silane coupling agents, the sum total should just be in the said range.
  • silane coupling agent for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, Vinyl trimethoxysilane, and vinyl triethoxysilane etc. are mentioned.
  • the curable composition preferably contains a solvent.
  • the solvent is not particularly limited and known solvents can be used. Although the content of the solvent in the curable composition is not particularly limited, it is preferably adjusted so that the solid content of the curable composition is 10 to 90% by mass, and is 15 to 90% by mass. It is more preferable to be adjusted.
  • the solvents may be used alone or in combination of two or more. When using 2 or more types of solvents together, it is preferable to adjust so that the total solid of a curable composition may become in the said range.
  • a solvent water and an organic solvent are mentioned, for example.
  • 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, 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 Ethyl ether, diethylene glycol monoethyl ether, diethylene glycol dio
  • the curable composition it is preferable to first prepare a dispersion composition in which a black pigment and a colorant are dispersed, and further mix the obtained dispersion composition with other components to obtain a curable composition.
  • the dispersion composition is preferably prepared by mixing a black pigment, a colorant, a resin (preferably a dispersant), and a solvent. It is also preferable to incorporate a polymerization inhibitor in the dispersion composition.
  • the dispersion 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 emulsifying device, a wet crusher, a wet dispersing machine or the like).
  • a known mixing method for example, a mixing method using a stirrer, a homogenizer, a high pressure emulsifying device, a wet crusher, a wet dispersing machine or the like.
  • each component may be blended at one time, or each component may be sequentially blended after being dissolved or dispersed in a solvent.
  • the order of introduction and working conditions at the time of blending are not particularly limited.
  • the curable composition is preferably filtered through a filter for the purpose of removing foreign matter and reducing defects.
  • a filter if it is a filter conventionally used for filtration applications etc., it can be used, without being limited in particular.
  • 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 ultrahigh molecular weight) such as polyethylene and polypropylene (PP) can be mentioned. .
  • 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 ultrahigh molecular weight) such as polyethylene and polypropylene (PP)
  • PP polypropylene
  • nylon are preferable.
  • the pore size of the filter is preferably 0.1 to 7.0 ⁇ m, more preferably 0.2 to 2.5 ⁇ m, still more preferably 0.2 to 1.5 ⁇ m, and particularly preferably 0.3 to 0.7 ⁇ m. By setting this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing filter clogging of the pigment (including the black pigment).
  • different filters may be combined. At this time, the filtering with the first filter may be performed only once or may be performed twice or more. When different filters are combined to perform filtering twice or more, it is preferable that the second and subsequent pore sizes be the same or larger than the pore size of the first filtering.
  • the pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, it is possible to select from, for example, various filters provided by Nippon Pall Co., Advantec Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., and the like.
  • the second filter can use a filter formed of the same material as the first filter described above.
  • the pore size of the second filter is preferably 0.2 to 10.0 ⁇ m, more preferably 0.2 to 7.0 ⁇ m, and still more preferably 0.3 to 6.0 ⁇ m.
  • the curable composition is preferably free of impurities such as metals, metal salts containing halogen, acids, alkalis and the like.
  • the content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially not including (less than detection limit of measuring device Is most preferred.
  • the above impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).
  • the curable composition layer (composition layer) formed using the above-mentioned photocurable composition can be cured to obtain a cured film in a pattern. More specifically, the production method of the present invention makes it possible to obtain an optical density A of 2.60 to 10.00 at a wavelength of 365 nm per 1.5 ⁇ m of film thickness using the above-described curable composition, and Forming a curable composition layer having an optical density B at a wavelength of 550 nm per 1.5 ⁇ m of 2.00 to 10.00 (curable composition layer forming step), Exposing the curable composition layer under conditions of an oxygen concentration of 30 to 50% by volume (exposure step); Developing the curable composition layer after the exposure to form a cured film (developing step); Contains Also, if desired, post-baking may be performed after the developing step.
  • each of the above steps will be described.
  • the curable composition layer forming step prior to exposure, the curable composition is applied on a support or the like to form a layer of the curable composition (curable 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 charge coupled device (CCD) or a complementary metal-oxide semiconductor (CMOS) is provided on a substrate (for example, a silicon substrate) it can.
  • CMOS complementary metal-oxide semiconductor
  • a subbing layer may be provided on the support for the purpose of improving adhesion with the upper layer, preventing diffusion of substances, flattening of the substrate surface, and the like.
  • the curable composition layer is preferably 0.1 to 10 ⁇ m, more preferably 0.2 to 5 ⁇ m, and still more preferably 0.2 to 3 ⁇ m. Drying (pre-baking) of the curable composition layer coated on the support can be carried out at a temperature of 50 to 140 ° C. for 10 to 300 seconds with a hot plate, an oven or the like.
  • the curable composition layer (preferably a dried (prebaked) curable composition layer or a naturally dried curable composition layer) has an optical density A of 2.60 to 10 It is preferably 2.00 to 4.00, and more preferably 2.90 to 3.50 from the viewpoint that the rectangularity of the cross-sectional shape of the resulting cured film is further improved.
  • the optical density B is from 2.00 to 10.00, and it is preferably 2.50 to 7.00, and 2.80 to 6 from the viewpoint that the rectangularity of the cross-sectional shape of the obtained cured film is more excellent. 50 is more preferred.
  • the ratio of optical density B to optical density A is preferably 0.3 to 3.5, more preferably 0.5 to 2.0, and 0.8 to 1.2. More preferable.
  • a curable composition layer dried on a glass substrate is formed, and a transmission densitometer (X-rite 361 T (visual) is provided.
  • the film thickness is also measured using a densitometer, and the optical density per 1.5 ⁇ m of film thickness is calculated.
  • the value measured with the transmission densitometer can be used as it is.
  • the curable composition layer may be exposed under conditions of an oxygen concentration of 30 to 50% by volume.
  • the curable composition may be through a mask having a predetermined mask pattern.
  • the aspect which pattern-exposes a layer is mentioned.
  • Examples of light at the time of exposure include light selected from g-rays, h-rays, i-rays, KrF rays (excimer laser rays), and ArF rays (excimer laser rays).
  • Irradiance is preferably 20000 ⁇ 50000W / m 2, more preferably 25000 ⁇ 40000W / m 2.
  • the exposure step is performed under the conditions of an oxygen concentration of 30 to 50% by volume.
  • an oxygen concentration of 30 to 50% by volume.
  • Control of this oxygen concentration can be performed by a usual method.
  • the apparatus chamber containing the exposure apparatus has a sealed structure, and oxygen gas and nitrogen gas in a desired ratio can be supplied to adjust the oxygen concentration in the room.
  • oxygen gas and nitrogen gas of predetermined flow rates may be circulated in the chamber of the exposure apparatus so that the exposure atmosphere has a predetermined oxygen concentration.
  • the optical density A is X
  • the oxygen concentration (volume fraction) at the time of exposure is Y
  • the irradiance (W / m 2 ) is Z
  • the value to be set is preferably 1.60 ⁇ 10 ⁇ 5 to 10.00 ⁇ 10 ⁇ 5, and more preferably 2.80 ⁇ 10 ⁇ 5 to 5.20 ⁇ 10 ⁇ 5 .
  • Curing if the value calculated by the equation (1) in which X, Y and Z are combined, which is closely related to the progress of curing of these curable composition layers, falls within the above-mentioned range
  • the rectangularity of the film is good.
  • the rectangularity of the cross-sectional shape of the cured film does not easily deteriorate.
  • the developing step is a step of developing the curable composition layer after exposure to form a cured film.
  • the curable composition layer in the non-light-irradiated portion in the exposure step is eluted, and only the light-cured portion remains, and a patterned cured film is obtained.
  • the type of developing solution used in the developing step is not particularly limited, but an alkaline developing solution which does not cause damage to the underlying imaging device and circuit is desirable.
  • the development temperature is, for example, 20 to 30.degree.
  • the developing time is, for example, 20 to 90 seconds. In order to remove more residue, it may be carried out for 120 to 180 seconds in recent years. Furthermore, in order to further improve the residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.
  • the alkaline developer is preferably an alkaline aqueous solution prepared by dissolving an alkaline compound in water so that the concentration is 0.001 to 10% by mass (preferably 0.01 to 5% by mass).
  • the alkaline compound is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium borate, sodium metaborate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl Ammonium hydroxide, tetrabutylammonium hydroxy, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo [5.4.0] -7-undecene etc. (of which the organic alkali is preferable.).
  • washing processing is generally performed by water after image development.
  • Post-bake After the exposure step, heat treatment (post-baking) is preferably performed.
  • Post-baking is a heat treatment after development to complete curing. 240 degrees C or less is preferable and, as for the heating temperature, 220 degrees C or less is more preferable. There is no particular lower limit, but in consideration of efficient and effective treatment, 50 ° C. or higher is preferable, and 100 ° C. or higher is more preferable.
  • Post-baking can be performed by a continuous system or a batch system using heating means, such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater.
  • the above post-baking is preferably performed in an atmosphere of 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, 3 volumes Most preferably, it is at most%. There is no particular lower limit, but 10 ppm by volume or more is practical.
  • the curable composition described above 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 by ordinary i-ray exposure.
  • UV curing agents include Ciba Irgacure 2959 (trade name).
  • the curable composition layer is preferably a material that cures at a wavelength of 340 nm or less.
  • the exposure dose of UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, and still more preferably 800 to 3500 mJ.
  • This UV curing step is preferably performed after the lithography step in order to perform low temperature curing more effectively.
  • the exposure light source is preferably an ozoneless mercury lamp.
  • the cured film obtained by the production method of the present invention preferably has an optical density at a wavelength of 365 nm per 1.5 ⁇ m of film thickness of 2.60 to 10.00, more preferably 2.80 to 4.00, 2.90 -3.50 is more preferable.
  • the optical density at a wavelength of 550 nm per 1.5 ⁇ m of film thickness of the cured film obtained by the production method of the present invention is preferably 2.00 to 10.00, more preferably 2.50 to 7.00, 2.80 To 6.50 is more preferable.
  • the cured film preferably has an optical density of more than 2.00 per 1.5 ⁇ m in the wavelength region of 400 to 1200 nm, since the cured film has better performance when used as a light shielding film described later. More than 3.00 is more preferable. Although the upper limit value is not particularly limited, it is preferably 10 or less. Such a cured film can be preferably used as a light shielding film.
  • a method of measuring the optical density of a cured film first, a cured film on a glass substrate is formed, and measurement is performed using a transmission densitometer (X-rite 361 T (visual) densitometer). The film thickness of the portion is also measured, and the optical density per predetermined film thickness is calculated.
  • an optical density of 1.5 ⁇ m or more in the wavelength range of 400 to 1200 nm means an optical density of 1.5 ⁇ m or more in the entire wavelength range of 400 to 1200 nm. Intended to be over 2.00.
  • the said cured film has a surface asperity structure.
  • the reflectance of the cured film can be reduced when the cured film is a light shielding film.
  • another layer may be provided on a cured film and a concavo-convex structure may be given.
  • the shape of the surface asperity structure is not particularly limited, but the surface roughness is preferably in the range of 0.55 ⁇ m to 1.5 ⁇ m. 5% or less is preferable, as for the reflectance of a cured film, 3% or less is more preferable, and 2% or less is still more preferable.
  • the method for producing the surface concavo-convex structure is not particularly limited, a method including an organic filler and / or an inorganic filler in a cured film or other layers, a lithography method using exposure and development, or an etching method, a sputtering method and nanoimprinting
  • the surface of the cured film or other layers may be roughened by a method or the like.
  • a method of providing a low refractive index layer on the cured film a method of providing a plurality of layers having different refractive indexes (for example, high refractive index layers), and a method of reducing the reflectance of the cured film And a method of forming a low optical density layer and a high optical density layer, as described in JP-A-2015-1654.
  • the cured film is a portable computer such as a personal computer, a tablet, a cellular phone, a smart phone, and a digital camera; a printer complex machine, an OA (Office Automation) equipment such as a scanner; a surveillance camera, a barcode reader, cash Industrial equipment such as an automated teller machine (ATM), a high speed camera, and a device having an identity authentication function using face image authentication; automotive camera devices; endoscopes, capsule endoscopes, And medical camera devices such as catheters; and bio-sensors, biosensors, cameras for military reconnaissance, cameras for stereoscopic maps, cameras for weather and ocean observation, land resource exploration cameras, astronomy for space and deep space targets Space equipment such as exploration cameras; etc.
  • Light blocking member and the light-shielding film of the optical filter and the module is used, yet is suitable for anti-reflection member and the antireflection film.
  • the said cured film can be used also for uses, such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode).
  • the said cured film is suitable for the member which provides a light shielding function or an antireflection function other than the optical filter and optical film which are used for micro LED and micro OLED.
  • micro LEDs and micro OLEDs include those described in JP-A-2015-500562 and JP-A-2014-533890.
  • the cured 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. Moreover, it is suitable as a member which provides a light shielding function and a reflection preventing function. Examples of the quantum dot sensor and the quantum dot solid-state imaging device include those described in U.S. Patent Application Publication 2012/37789 and WO 2008/131313.
  • a light shielding film is one of the preferable uses in the cured film obtained by the manufacturing method of this invention, Comprising:
  • the manufacturing method of the light shielding film of this invention is similarly the method demonstrated as the manufacturing method of the above-mentioned cured film. It can do. Specifically, the curable composition is applied to a substrate to form a curable composition layer, and the light shielding film can be produced by exposure and development.
  • a method of manufacturing a solid-state imaging device includes a step of manufacturing a cured film (light shielding film) through the above-described manufacturing method of the present invention, the solid-state imaging device having the cured film (light shielding film) It is a method of manufacturing.
  • the solid-state imaging device according to the manufacturing method of the present invention contains the cured film (light shielding film).
  • the form in which the solid-state imaging device contains a cured film (light-shielding film) is not particularly limited.
  • a plurality of photodiodes constituting the light receiving area of the solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) on a substrate And a light receiving element made of polysilicon or the like, and having a cured film on the light receiving element forming surface side of the support (for example, a portion other than the light receiving portion and / or a pixel for color adjustment) It can be mentioned.
  • the solid-state imaging device contains the above-described solid-state imaging device.
  • the solid-state imaging device 100 includes a rectangular solid-state imaging device 101, and a transparent cover glass 103 held above the solid-state imaging device 101 and sealing the solid-state imaging device 101. There is. Furthermore, on the cover glass 103, a lens layer 111 is provided so as to overlap via a spacer 104.
  • the lens layer 111 is composed of 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.
  • a light shielding film 114 is provided to shield the peripheral region of the lens layer 111 from light.
  • the cured film obtained by the manufacturing method of the present invention can also 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 serving as the light receiving surface and outputs the image as an image signal.
  • the solid-state imaging device 101 includes a laminated substrate 105 in which two substrates are laminated.
  • the laminated substrate 105 is composed of a rectangular chip substrate 106 and a circuit substrate 107 of 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 known materials can be used.
  • An imaging unit 102 is provided at the center of the surface of the chip substrate 106.
  • a dark current (noise) is generated from the circuit in the peripheral region, and the peripheral region is shielded by the light shielding film 115 provided.
  • the cured film obtained by the production method of the present invention is preferably used as the light shielding film 115.
  • a plurality of electrode pads 108 are provided at 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) (which may be a bonding wire) provided on the surface of the chip substrate 106.
  • each external connection terminal 109 is connected to the electrode pad 108 through the penetration electrode 110 which penetrates the lamination substrate 105 perpendicularly. Further, each external connection terminal 109 is connected to a control circuit that controls the 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, etc. It is done.
  • the imaging unit 102 includes components provided on the substrate 204 such as the light receiving element 201, the color filter 202, and the microlens 203.
  • the color filter 202 includes a blue pixel 205b, a red pixel 205r, a green pixel 205g, and a black matrix 205bm.
  • the cured film obtained by the production method of the present invention can also be used as a black matrix 205bm.
  • a material of the substrate 204 As a material of the substrate 204, the same material as the above-described chip substrate 106 can be used.
  • a p well layer 206 is formed on the surface of the substrate 204.
  • light receiving elements 201 which are n-type layers and generate and accumulate signal charges by photoelectric conversion are arranged and formed in a square lattice shape.
  • a vertical transfer path 208 formed of an n-type layer is formed on one side of the light receiving element 201 via the readout gate portion 207 on the surface layer of the p well layer 206. Further, 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 formed of a p-type layer.
  • the read gate unit 207 is a channel region for reading out the signal charge stored 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 on the gate insulating film 210 so as to cover the vertical transfer path 208, the read gate portion 207, and the element isolation region 209 almost immediately.
  • the vertical transfer electrode 211 functions as a drive electrode that drives the vertical transfer path 208 to perform charge transfer, and a read electrode that drives the read gate unit 207 to read a signal charge.
  • the signal charges are sequentially transferred from the vertical transfer path 208 to a horizontal transfer path and an output unit (floating diffusion amplifier) not shown, and then output as a voltage signal.
  • a light shielding film 212 is formed on the vertical transfer electrode 211 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 the other regions.
  • the cured film obtained by the manufacturing method of the present invention can also be used as the light shielding film 212.
  • a transparent intermediate layer formed of an insulating film 213 made of borophospho silicate glass (BPSG), an insulating film (passivation film) 214 made of P-SiN, and a planarizing film 215 made of a transparent resin or the like is provided on the light shielding film 212.
  • BPSG borophospho silicate glass
  • passivation film insulating film
  • planarizing film 215 made of a transparent resin or the like
  • the image display manufactured by the manufacturing method of this invention contains the cured film obtained by the manufacturing method of this invention.
  • a method of producing an image display device of the present invention is a method of producing an image display device having the above-mentioned cured film, including the step of producing a cured film through the above-mentioned production method of the present invention.
  • an image display apparatus has a cured film
  • a form in which a cured film is contained in a black matrix, and the color filter containing such a black matrix is used for an image display apparatus is mentioned, for example.
  • a black matrix and a color filter containing the black matrix will be described, and a liquid crystal display device containing such a color filter will be described as a specific example of the image display device.
  • the cured film obtained by the production method of the present invention is contained in a black matrix.
  • the black matrix may be contained in an image display device such as a color filter, a solid-state imaging device, and a liquid crystal display device.
  • an image display device such as a color filter, a solid-state imaging device, and a liquid crystal display device.
  • black matrix those already described above; black edges provided at the periphery of an image display device such as a liquid crystal display device; grids between red, blue and green pixels, and / or stripes Black portions; dot-like and / or linear black patterns for light shielding of TFT (thin film transistor); and the like.
  • the black matrix has a high light-shielding property (optical density OD) in order to improve the display contrast, and in the case of an active matrix drive liquid crystal display device using thin film transistors (TFTs), to prevent image quality deterioration due to light current leakage. It is preferable to have three or more.
  • the method for producing the black matrix is not particularly limited, but it can be produced by the same method as the method for producing a cured film described above.
  • a curable composition can be applied to a substrate to form a curable composition layer, exposed, and developed to produce a patterned cured film (black matrix).
  • the thickness of the cured film used as the black matrix is preferably 0.1 to 4.0 ⁇ m.
  • the material of the substrate is not particularly limited, but preferably has a transmittance of 80% or more to visible light (wavelength 400 to 800 nm).
  • a material specifically, for example, glass such as soda lime glass, non-alkali glass, quartz glass, and borosilicate glass; plastics such as polyester resin and polyolefin resin; From the viewpoint of chemical resistance and heat resistance, alkali-free glass, quartz glass and the like are preferable.
  • the cured film obtained by the production method of the present invention is contained in a color filter.
  • a color filter provided with a board
  • the color filter containing the black matrix (cured film) can be produced, for example, by the following method.
  • a coating (resin composition layer) of a resin composition containing a pigment corresponding to each colored pixel of a color filter is formed in the opening of a pattern-like black matrix formed on a substrate.
  • a resin composition for each color Although a well-known resin composition can be used, In the curable composition demonstrated in this specification, the black pigment was substituted to the coloring agent corresponding to each pixel It is preferred to use one.
  • the resin composition layer is exposed to light through a photomask having a pattern corresponding to the opening of the black matrix.
  • a color filter having red, green and blue pixels can be produced by performing a series of operations using, for example, resin compositions for each color containing red, green and blue pigments.
  • the cured film obtained by the production method of the present invention is contained in a liquid crystal display device.
  • the form in which the liquid crystal display device contains the cured film is not particularly limited, but the form containing the color filter containing the black matrix (cured film) described above can be mentioned.
  • liquid crystal display device As a liquid crystal display device concerning this embodiment, a form provided with a pair of substrates arranged facing, and a liquid crystal compound enclosed between those substrates is mentioned, for example.
  • the substrate is as described above for the black matrix.
  • liquid crystal display device for example, from the user side, polarizing plate / substrate / color filter / transparent electrode layer / alignment film / liquid crystal layer / alignment film / transparent electrode layer / TFT (Thin Film Transistor) A laminate including an element / substrate / polarizer / backlight unit in this order may be mentioned.
  • the liquid crystal display device is not limited to the above, and, for example, “Electronic display device (authored by Akio Sasaki, published by Industry Research Association 1990)”, “Display device (authored by Ibuki Osamu, Industrial Books (stock) The liquid crystal display device described in the Heisei 1st year publication etc. is mentioned. In addition, for example, a liquid crystal display device described in “Next-Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, Inc., Industrial Research Association, Inc. 1994)” may be mentioned.
  • the cured film obtained by the production method of the present invention is contained in an infrared sensor.
  • the infrared sensor according to the above embodiment will be described with reference to FIG.
  • reference numeral 310 denotes a solid-state imaging device.
  • the imaging region provided on the solid-state imaging device 310 is configured by combining the infrared absorption filter 311 and the color filter 312.
  • the infrared absorption filter 311 transmits light in the visible light range (for example, light with a wavelength of 400 to 700 nm) and light in the infrared range (for example, light with a wavelength of 800 to 1300 nm, preferably light with a wavelength of 900 to 1200 nm)
  • it is a film that shields light having a wavelength of 900 to 1000 nm, and a cured film containing an infrared ray absorbent (as described in the form of the infrared ray absorbent as described above) as a colorant 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, and for example, red (R), green (G), and blue (B) pixels are formed.
  • the 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 of the wavelength transmitted through the infrared transmission filter 313 is disposed between the infrared transmission filter 313 and the solid-state imaging device 310.
  • the infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared light of a specific wavelength, and is a colorant (for example, a perylene compound and / or bisbenzo) that absorbs light in the visible light range.
  • a cured film obtained by the production method of the present invention, which contains a furanone compound and the like) and an infrared absorber for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, and a polymethine compound
  • an infrared absorber for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, and a polymethine compound
  • the infrared transmission filter 313 shields light having a wavelength of 400 to 830 nm and transmit light having a wavelength of 900 to 1300 nm.
  • a microlens 315 is disposed on the incident light h ⁇ side of the color filter 312 and the infrared transmission filter 313.
  • a planarization film 316 is formed to cover the microlenses 315.
  • the resin film 314 is disposed in the embodiment shown in FIG. 3, the infrared transmission filter 313 may be formed instead of the resin film 314. That is, the infrared ray transmission filter 313 may be formed on the solid-state imaging device 310.
  • the film thickness of the color filter 312 and the film thickness of the infrared rays permeable filter 313 are the same, the film thickness of both may be different.
  • the color filter 312 is provided closer to the incident light h ⁇ than the infrared absorption filter 311, but the infrared absorption filter 311 and the color filter 312 are interchanged in order and the infrared absorption filter 311 may be provided closer to the incident light h ⁇ than the color filter 312.
  • 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 cured film obtained by the manufacturing method of the present invention can be used as a light shielding film for the edge and / or the side of the surface of the infrared absorption filter 311, and by using for the inner wall of the infrared sensor, internal reflection and / or light reception. Unintended light can be prevented from entering the unit and sensitivity can be improved.
  • this infrared sensor it is possible to simultaneously capture image information, so that it is possible to perform motion sensing in which an object whose motion is to be detected is recognized. Furthermore, since distance information can be acquired, it is also possible to capture an image including 3D information.
  • 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 in JP-A-2011-233983 can be referred to, and the contents thereof are incorporated in the present specification.
  • Dispersion Composition A dispersion composition was prepared which was used to prepare a curable composition. Table 1 below shows the composition ratio (parts by mass) of each component in each dispersion composition.
  • the dispersion compositions 1, 13 and 14 have the same composition.
  • ⁇ Pigment> The pigment shown below was used.
  • Ti, Zr, V, Nb, and CB, inorganic black pigment (A), inorganic black pigment (B), inorganic black pigment (C) are black pigments, and PG58 and PY185 are pigments other than black pigments. .
  • Ti titanium nitride-containing particles produced by the method for producing metal nitride-containing particles shown below.
  • metal nitride-containing particles titanium nitride-containing particles
  • the apparatus described in paragraph 0042 of JP-A-2005-343784 and FIG. 1 was used.
  • metal nitride is used with an apparatus (hereinafter referred to as “nanoparticle manufacturing apparatus”) in which the discharge vessel 1 in FIG. 1 of the above publication is a stainless steel vacuum chamber (manufactured by Fukushin Kogyo Co., Ltd.). Containing particles (titanium nitride containing particles) were produced.
  • the air in the vacuum chamber was exhausted by the exhaust pump.
  • a tungsten rod having a length of 500 mm, a diameter of 12 mm, and a rod shape of a hollow structure having a hollow diameter of 6 mm was used as a discharge electrode of the nano-particle production apparatus.
  • the arrangement of the discharge electrodes was the same as that of FIG. 1 of JP-A-2005-343784. Specifically, 12 discharge electrodes were arranged in two stages of six each. The distance between the upper and lower portions was about 160 mm.
  • the hollow discharge electrode was connected to the raw material supply device so that the raw material gas could be supplied into the vacuum chamber from the hollow portion of the discharge electrode.
  • the discharge starts in a state where the tips of the discharge electrodes are in contact with each other while applying an alternating current (voltage: 20 to 40 V, current: 70 to 100 A) having a phase difference to each discharge electrode.
  • an alternating current voltage: 20 to 40 V, current: 70 to 100 A
  • the tips of the discharge electrodes were moved outward so as to separate them, and the distance between the tips of the adjacent discharge electrodes was set to a position of 5 to 10 mm to continue the arc discharge .
  • the feed tank of the raw material feeder was heated to introduce the raw material gas into the vacuum chamber.
  • NH 3 gas liquefied ammonium ECOAN, manufactured by Showa Denko KK
  • H 2 gas hydrogen gas, Showa Denko gas products
  • Ar gas argon gas, Taiyo Nichi acid
  • the supply tank was heated to 210 ° C.
  • TiCl 4 gas TiCl 4 gas (TLT-1, manufactured by Toho Titanium Co., Ltd.) was introduced from the discharge electrode at 600 atm.
  • sulfur fine powder fine powder sulfur 325 mesh, manufactured by Tsurumi Chemical Industry Co., Ltd.
  • a powder supply device TP-99010 FDR manufactured by JEOL
  • the feed rate is determined by X-ray fluorescence analysis using the content by mass of sulfur atoms detected by X-ray photoelectron spectroscopy in the obtained metal nitride-containing particles (particles containing titanium nitride) as T E (mass%).
  • T E / T X The ratio (T E / T X ) of the two was set to be less than 1.1, where T X (mass%) was the content by mass of sulfur atoms detected by After introducing TiCl 4 gas and nitrogen gas mixed with sulfur fine powder into the vacuum chamber for 1 hour, voltage application from the AC power supply was stopped, and the supply of the gas was stopped. Next, particles attached to the inner wall of the vacuum chamber were recovered.
  • the obtained particles were placed in a closed vessel into which nitrogen (N 2 ) gas having an O 2 content and a water content controlled to 100 ppm or less, respectively, was introduced and allowed to stand for 24 hours.
  • nitrogen (N 2 ) gas having an O 2 content and a water content controlled to 100 ppm or less, respectively, was introduced and allowed to stand for 24 hours.
  • the particles obtained above were heated at 200 ° C. using a vacuum oven VAC-101P (manufactured by ESPEC) to obtain metal nitride-containing particles (titanium nitride-containing particles).
  • the internal pressure of the decompression oven during heating was 1.0 ⁇ 10 3 Pa.
  • zirconium powder zirconium powder manufactured by Wako Pure Chemical Industries, Ltd.
  • powder feeder TP-99010 FDR powder feeder TP-99010 FDR (manufactured by JEOL Ltd.) instead of Zr: TiCl 4 gas.
  • V Similar to the titanium nitride-containing particles described above, except that vanadium powder (Vanadium metal powder VHO manufactured by Taiyo Mining Co., Ltd.) was introduced by a powder supply device TP-99010FDR (manufactured by JEOL Ltd.) instead of the introduction of TiCl 4 gas. Vanadium nitride-containing particles produced by the method.
  • Niobium powder Niobium (powder) ⁇ 100-325 mesh> manufactured by Mitsuwa Chemical Co., Ltd.
  • niobium powder Niobium (powder) ⁇ 100-325 mesh> manufactured by Mitsuwa Chemical Co., Ltd.
  • a powder feeder TP-99010 FDR manufactured by JEOL Ltd.
  • TiCl 4 gas Niobium nitride-containing particles produced by the same method as titanium-containing particles.
  • T E / T X of each metal nitride containing particle (a titanium nitride containing particle, a zirconium nitride containing particle, a vanadium nitride containing particle, and a niobium nitride containing particle) mentioned above was measured by the following method.
  • Each metal nitride-containing particle was formed into a pellet by using a press to obtain a sample.
  • grains was measured on the following measurement conditions using a X-ray-photoelectron-spectroscopic-analysis apparatus and a fluorescent-X-ray-analysis apparatus.
  • X-ray photoelectron spectrometer Measurement of T E
  • Quantera-SXM (trade name) device manufactured by PHI
  • X-ray source monochromatized Al K ⁇ ray (1486.6 ev, 25 W, 15 kV, beam diameter 200 ⁇ m ⁇ )
  • Measurement area 200 ⁇ m ⁇
  • Measurement method The sample was set in the apparatus, and the photoelectron extraction angle was measured at 10 degrees.
  • X-ray fluorescence analyzer (measurement of T X ) Equipment Rigaku ZSM Primus II XRF X-ray Rh 30-50 kV, 48-80 mA Measurement area 10 ⁇ m ⁇ Measurement time 10-240 deg / min
  • transition metal atoms (titanium, zirconium, vanadium, or nitride) contained in each metal nitride-containing particle (titanium nitride-containing particle, zirconium nitride-containing particle, vanadium nitride-containing particle, and niobium nitride-containing particle) Containing atom number ratio X of content of nitrogen atom to content of niobium), contained atom number ratio Y of content of oxygen atom to content of transition metal atom contained in nitride, and transition contained in nitride
  • each metal nitride-containing particle as a sample was formed into a pellet by using a press, and the sample was measured using the fluorescent X-ray analyzer under the following conditions.
  • the average primary particle diameter of each of the metal nitride-containing particles was less than 80 nm.
  • PG58 and PY185 are used together to make it green as a whole.
  • Dispersant A (resin having no ethylenically unsaturated group): Synthesized by the method shown below.
  • Synthesis Example A1 Synthesis of Macromonomer A-1 In a three-necked flask with a volume of 3000 mL, ⁇ -caprolactone (1044.2 g), ⁇ -valerolactone (184.3 g), and 2-ethyl-1-hexanol (71.6 g) were introduced to obtain a mixture. The mixture was then stirred while blowing with nitrogen. Next, Disperbyk 111 (12.5 g, manufactured by Bick Chemie, phosphoric acid resin) was added to the mixture, and the resulting mixture was heated to 90 ° C. After 6 hours, the mixture was heated to 110 ° C.
  • Dispersant B (resin having an ethylenically unsaturated group): Synthesized by the method shown below.
  • V-601 (1.48 g) was added to the mixture. After further reacting for 2 hours, the mixture was heated to 90 ° C. and stirred for 3 hours. The polymerization reaction was completed by the above operation. After completion of the reaction, tetrabutylammonium bromide (TBAB, 7.5 g) and p-methoxyphenol (MEHQ, 0.13 g) were added under air, and then glycidyl methacrylate (hereinafter also referred to as "GMA", 66.1 g) ) was added dropwise. After completion of the dropwise addition, the reaction was continued under air for 7 hours, and the completion of the reaction was confirmed by acid value measurement. A 20% by mass solution of Dispersant B was obtained by adding PGMEA (643.6 g) to the obtained mixture. The weight average molecular weight of the resulting dispersant B was 35,000, and the acid value was 50 mg KOH / mg.
  • TBAB tetrabutylammonium bromide
  • MEHQ
  • Dispersant C (resin having an ethylenically unsaturated group): Synthesized by the method shown below.
  • C C number was calculated
  • Dispersion composition The dispersion composition prepared by the method described above was used. For each numbered curable composition, the corresponding numbered dispersion composition was used.
  • ⁇ A-1 (resin containing an ethylenically unsaturated group): Acrycure RD-F8, manufactured by Nippon Shokuhin Co., Ltd., solid content 40%, (solvent: propylene glycol monomethyl ether)
  • the alkali-soluble resin A-1 was used as a resin-containing solution (resin solution).
  • PGMEA Propylene glycol monomethyl ether acetate
  • An i-line stepper exposure apparatus FPA-3000i5 + (Canon Co., Ltd.) is used for the dried curable composition layer with a film thickness of 1.5 ⁇ m to form a 3.0 ⁇ m-square pattern at a wavelength of 365 nm. It exposed through an Island pattern mask.
  • the exposure was performed at the optimum exposure dose with the oxygen concentration at the time of exposure set in the range of 25 to 55% by volume and the irradiance set in the range of 15,000 to 55,000 W / m 2 . The exposure was performed within 10 minutes after prebaking.
  • the silicon wafer on which the curable composition layer that has been exposed is formed is placed on the horizontal rotation table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (organic alkali) Paddle development was carried out at 23 ° C. for 60 seconds using a developer, manufactured by Fujifilm Electronics Materials. In this way, a pattern (a cured film in the form of a square pixel pattern of 3.0 ⁇ m square) was formed on the undercoating silicon wafer.
  • DW-30 type manufactured by Chemitronics
  • CD-2000 (organic alkali) Paddle development was carried out at 23 ° C. for 60 seconds using a developer, manufactured by Fujifilm Electronics Materials.
  • a silicon wafer on which a pattern is formed is fixed to a horizontal rotation table by a vacuum chuck method, and while rotating this silicon wafer at a rotation speed of 50 rpm by a rotation device, pure water is showered from above the rotation center from a spray nozzle It was supplied and rinsed. Thereafter, the silicon wafer was dried. The obtained silicon wafer was further heated (post-baked) at 200 ° C. for 300 seconds to obtain a silicon wafer with a patterned cured film.
  • AA angle of side wall 80 ° to 100 °
  • A angle of side wall 75 ° to less than 80 °, or 100 ° to less than 105 °
  • B angle of side wall 70 ° to 75 °
  • C angle of sidewall 60 ° or more and less than 70 °, or 110 ° or more but less than 120 °
  • D angle of sidewall 50 ° or more and less than 60 ° or 120 ° or more and less than 130 °
  • E Sidewall angle is less than 50 ° or 130 ° or more
  • the column “Disperser Mill Peripheral Speed” means the mill peripheral speed when preparing the dispersion composition used to make the curable composition.
  • the column of “Expression (1) value” is a value obtained by applying each test condition to the above-mentioned Expression (1) (X ⁇ Y ⁇ Z). The calculation method is as described above.
  • a cured film (patterned cured film) excellent in rectangularity of the cross-sectional shape can be produced, and even in the case where the drawn curable composition layer is used.
  • the tendency to maintain excellent rectangularity (the evaluation of rectangularity is C or higher) was confirmed.
  • the drawing period should be Also in this case, it was confirmed that the rectangularity of the obtained pattern did not easily deteriorate (comparison of Example 10 with other Examples).
  • Example 1, 2 and 6 The tendency which can acquire the outstanding cured film was confirmed (result of Example 1, 2 and 6).
  • the irradiance at the time of exposure is from 20000 to 50000 W / m 2
  • a cured film having more rectangularity is obtained
  • the irradiance at the exposure is from 25000 to 40000 W / m 2
  • the cured film is more excellent in rectangularity.
  • Tend to be obtained Results of Examples 1, 4, 5, 11 and 12
  • inorganic black pigments (A), (B) and (C) were used as the black pigment, it was confirmed that a cured film having more excellent rectangularity could be obtained as in Example 1 (Example 1, 18, 19 and 20 results).
  • 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 substrate 108 ... electrode pad 109 ... external connection terminal 110 ... penetrating electrode 111 ... lens layer 112 ... lens material 113 ... support 114, 115 ... cured film 201 ... light receiving element 202: color filter 201: light receiving element 202: color filter 203: microlens 204: substrate 205b: blue pixel 205r: red pixel 205g: green pixel 205bm,. Black matrix 206 p well layer 207 read gate portion 208 vertical transfer path 209 element isolation region 210 Insulating film 211 ...

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Abstract

Provided are: a method for producing a cured film, by which a cured film having excellent cross-sectional squareness can be produced and excellent squareness can be maintained even in cases where an exposed curable composition layer is used; a method for producing a solid-state imaging element; and a method for producing an image display device. This method for producing a cured film includes: a step of forming a curable composition layer in which the optical density A at a wavelength of 365 nm per 1.5 µm of film thickness is 2.60-10.00 and the optical density B at a wavelength of 550 nm per 1.5 µm of film thickness is 2.00-10.00, the curable composition layer formed using a curable composition that contains a black pigment and a polymerizable compound; a step of exposing the curable composition layer to light at an oxygen concentration of 30-50 vol%; and a step of forming a cured film by developing the exposed curable composition layer.

Description

硬化膜の製造方法、固体撮像素子の製造方法、画像表示装置の製造方法Method of manufacturing cured film, method of manufacturing solid-state imaging device, method of manufacturing image display device
　本発明は、硬化膜の製造方法、固体撮像素子の製造方法、及び、画像表示装置の製造方法に関する。 The present invention relates to a method of manufacturing a cured film, a method of manufacturing a solid-state imaging device, and a method of manufacturing an image display device.
　固体撮像装置、及び、画像表示装置（例えば、液晶表示装置、及び、有機ＥＬ（ｅｌｅｃｔｒｏ　ｌｕｍｉｎｅｓｃｅｎｃｅ）装置等）に用いられる硬化膜の製造方法は、基板上に硬化性組成物層を形成した後に、これを硬化させる方法が一般的である。そこでは、所定のマスクパターンを介して硬化性組成物層に光を照射し、その後、現像処理を行うのが典型的である。
　また、形成する硬化膜の性能改善のために、特定の波長に対する硬化性組成物層の光学濃度（ＯＤ：Ｏｐｔｉｃａｌ　Ｄｅｎｓｉｔｙ）を所定の範囲に調整する場合がある。 The method for producing a cured film used for a solid-state imaging device and an image display device (for example, a liquid crystal display device, an organic EL (electro luminescence) device, etc.) is carried out after forming a curable composition layer on a substrate The method of hardening this is common. Here, it is typical that the curable composition layer is irradiated with light through a predetermined mask pattern and then developed.
Moreover, in order to improve the performance of the cured film to be formed, the optical density (OD: Optical Density) of the curable composition layer with respect to a specific wavelength may be adjusted within a predetermined range.
　例えば、特許文献１には、着色感光性組成物を用いて、乾燥後の膜厚が２．０μｍの膜を製膜した際に、膜の波長３６５ｎｍにおける光学濃度が１．５以上である着色感光性組成物が開示されている（請求項１）。 For example, Patent Document 1 discloses that when a film having a thickness of 2.0 μm after drying is formed using a colored photosensitive composition, the film has an optical density of 1.5 or more at a wavelength of 365 nm. A photosensitive composition is disclosed (Claim 1).
国際公開２０１６／１５８１１４号公報International publication 2016/158114 gazette
　本発明者らは、特許文献１に記載された着色感光性組成物について検討したところ、この着色感光性組成物を用いて形成される硬化膜の断面形状の矩形性について改善の余地があることを知見した。
　また、多様な製造条件に対して、安定した品質の硬化膜を製造できることが求められており、硬化性組成物層を形成した後、露光するまで期間（例えば１週間）が空いた場合であっても、得られる硬化膜の断面形状の矩形性が良好であることも求められている。
　以下、特定の工程を経た処理対象物が、次の工程まで待機させられることを「引き置き」ともいう。 The present inventors examined the colored photosensitive composition described in Patent Document 1, and there is room for improvement in rectangularity of the cross-sectional shape of a cured film formed using this colored photosensitive composition. Found out.
In addition, it is required that a cured film of stable quality can be produced under various production conditions, and after a curable composition layer is formed, a period (for example, one week) until exposure is left. However, it is also required that the rectangularity of the cross-sectional shape of the obtained cured film be good.
Hereinafter, the fact that the object to be treated which has undergone a specific process can be made to stand by until the next process is also referred to as "retention."
　そこで、本発明は、断面形状の矩形性が優れる硬化膜を製造でき、引き置きされた硬化性組成物層を用いた場合でも優れた矩形性を維持できる硬化膜の製造方法を提供することを課題とする。また、本発明は、固体撮像素子の製造方法、及び、画像表示装置の製造方法を提供することも課題とする。 Therefore, the present invention can provide a method for producing a cured film capable of producing a cured film excellent in rectangularity of the cross-sectional shape and maintaining excellent rectangularity even when using a drawn curable composition layer. It will be an issue. Another object of the present invention is to provide a method of manufacturing a solid-state imaging device and a method of manufacturing an image display device.
　〔１〕　黒色顔料及び重合性化合物を含有する硬化性組成物を用いて、膜厚１．５μｍあたりの波長３６５ｎｍにおける光学濃度Ａが２．６０～１０．００となり、かつ、膜厚１．５μｍあたりの波長５５０ｎｍにおける光学濃度Ｂが２．００～１０．００となる硬化性組成物層を形成する工程と、上記硬化性組成物層を、酸素濃度が３０～５０体積％の条件下で露光する工程と、上記露光後の上記硬化性組成物層を現像して硬化膜を形成する工程と、を含有する、硬化膜の製造方法。
　〔２〕　上記黒色顔料が、第４族の金属元素の窒化物若しくは酸窒化物、第５族の金属元素の窒化物若しくは酸窒化物、又は、カーボンブラックである、〔１〕に記載の硬化膜の製造方法。
　〔３〕　上記黒色顔料が、チタンの窒化物若しくは酸窒化物、ジルコニウムの窒化物若しくは酸窒化物、バナジウムの窒化物若しくは酸窒化物、ニオブの窒化物若しくは酸窒化物、又は、カーボンブラックである、〔１〕又は〔２〕に記載の硬化膜の製造方法。
　〔４〕　上記黒色顔料が、チタンの窒化物若しくは酸窒化物、ジルコニウムの窒化物若しくは酸窒化物、バナジウムの窒化物若しくは酸窒化物、又は、ニオブの窒化物又は酸窒化物である、〔１〕～〔３〕のいずれかに記載の硬化膜の製造方法。
　〔５〕　上記黒色顔料が、チタンの窒化物若しくは酸窒化物、又は、ジルコニウムの窒化物若しくは酸窒化物である、〔１〕～〔４〕のいずれかに記載の硬化膜の製造方法。
　〔６〕　上記露光における、放射照度が２００００～５００００Ｗ／ｍ２である、〔１〕～〔５〕のいずれかに記載の硬化膜の製造方法。
　〔７〕　上記露光における、放射照度が２５０００～４００００Ｗ／ｍ２である、〔１〕～〔６〕のいずれかに記載の硬化膜の製造方法。
　〔８〕　上記光学濃度Ａが２．８０～４．００となり、かつ、上記光学濃度Ｂが２．５０～７．００となる、〔１〕～〔７〕のいずれかに記載の硬化膜の製造方法。
　〔９〕　上記光学濃度Ａに対する上記光学濃度Ｂの比が０．５～２．０である、〔１〕～〔８〕のいずれかに記載の硬化膜の製造方法。
　〔１０〕　上記硬化性組成物が、更に、樹脂を含有し、上記樹脂が、エチレン性不飽和基を含有する樹脂を含有し、上記樹脂の合計質量に対する、上記エチレン性不飽和基の含有量が、０．１０～３．００ｍｍｏｌ／ｇである、〔１〕～〔９〕のいずれかに記載の硬化膜の製造方法。
　〔１１〕　上記硬化性組成物が、更に、重合開始剤を含有する、〔１〕～〔１０〕のいずれかに記載の硬化膜の製造方法。
　〔１２〕　上記硬化性組成物が、更に、重合禁止剤を含有する、〔１〕～〔１１〕のいずれかに記載の硬化膜の製造方法。
　〔１３〕　上記光学濃度ＡをＸ、上記露光時の酸素濃度をＹ、上記放射照度をＺとした場合に、後述する式（１）で計算される値が２．８０×１０－５～５．２０×１０－５となる、〔１〕～〔１２〕のいずれかに記載の硬化膜の製造方法。
　〔１４〕　上記硬化膜が遮光膜である、〔１〕～〔１３〕のいずれかに記載の硬化膜の製造方法。
　〔１５〕　〔１〕～〔１４〕のいずれかに記載の製造方法を介して、硬化膜を有する固体撮像素子の製造を行う、固体撮像素子の製造方法。
　〔１６〕　〔１〕～〔１４〕のいずれかに記載の製造方法を介して、硬化膜を有する画像表示装置の製造を行う、画像表示装置の製造方法。 [1] Using a curable composition containing a black pigment and a polymerizable compound, the optical density A at a wavelength of 365 nm per 1.5 μm of film thickness is 2.60 to 10.00, and the film thickness of 1.5 μm Forming a curable composition layer having an optical density B of 2.00 to 10.00 at a wavelength of 550 nm, and exposing the curable composition layer under conditions of an oxygen concentration of 30 to 50% by volume A method for producing a cured film, comprising the steps of: developing the curable composition layer after the exposure to form a cured film.
[2] The cured material according to [1], wherein the black pigment is a nitride or oxynitride of a metal element of Group 4, a nitride or oxynitride of a metal element of Group 5 or carbon black Method of producing a membrane
[3] The black pigment is a nitride or oxynitride of titanium, a nitride or oxynitride of zirconium, a nitride or oxynitride of vanadium, a nitride or oxynitride of niobium, or carbon black The manufacturing method of the cured film as described in [1] or [2].
[4] The black pigment is a nitride or oxynitride of titanium, a nitride or oxynitride of zirconium, a nitride or oxynitride of vanadium, or a nitride or oxynitride of niobium [1] ] The manufacturing method of the cured film in any one of-[3].
[5] The method for producing a cured film according to any one of [1] to [4], wherein the black pigment is a nitride or oxynitride of titanium, or a nitride or oxynitride of zirconium.
[6] The method for producing a cured film according to any one of [1] to [5], wherein the irradiance is from 20000 to 50000 W / m 2 in the exposure.
[7] The method for producing a cured film according to any one of [1] to [6], wherein the irradiance is 25000 to 40000 W / m 2 in the exposure.
[8] The cured film according to any one of [1] to [7], wherein the optical density A is 2.80 to 4.00, and the optical density B is 2.50 to 7.00. Production method.
[9] The method for producing a cured film according to any one of [1] to [8], wherein the ratio of the optical density B to the optical density A is 0.5 to 2.0.
[10] The curable composition further contains a resin, and the resin contains a resin containing an ethylenically unsaturated group, and the content of the ethylenically unsaturated group with respect to the total mass of the resin Of from 0.10 to 3.00 mmol / g. The method for producing a cured film according to any one of [1] to [9].
[11] The method for producing a cured film according to any one of [1] to [10], wherein the curable composition further contains a polymerization initiator.
[12] The method for producing a cured film according to any one of [1] to [11], wherein the curable composition further contains a polymerization inhibitor.
[13] Assuming that the above optical density A is X, the oxygen concentration at the above exposure is Y, and the above irradiance is Z, the value calculated by the equation (1) described later is 2.80 × 10 −5 to 5 The method for producing a cured film according to any one of [1] to [12], which results in 20 × 10 −5 .
[14] The method for producing a cured film according to any one of [1] to [13], wherein the cured film is a light shielding film.
[15] A manufacturing method of a solid-state imaging device, which manufactures a solid-state imaging device having a cured film through the manufacturing method according to any one of [1] to [14].
[16] A manufacturing method of an image display device, which manufactures an image display device having a cured film through the manufacturing method according to any one of [1] to [14].
　本発明によれば、断面形状の矩形性が優れる硬化膜を製造でき、引き置きされた硬化性組成物層を用いた場合でも優れた矩形性を維持できる硬化膜の製造方法を提供できる。
　また、本発明によれは、固体撮像素子の製造方法、及び、画像表示装置の製造方法も提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the cured film which is excellent in the rectangularity of cross-sectional shape can be manufactured, and the manufacturing method of the cured film which can maintain excellent rectangularity even when using the curable composition layer drawn can be provided.
The present invention can also provide a method of manufacturing a solid-state imaging device and a method of manufacturing an image display device.
固体撮像装置の構成例を示す概略断面図である。It is a schematic sectional drawing which shows the structural example of a solid-state imaging device. 図１の撮像部を拡大して示す概略断面図である。It is a schematic sectional drawing which expands and shows the imaging part of FIG. 赤外線センサの構成例を示す概略断面図である。It is a schematic sectional drawing which shows the structural example of an infrared sensor.
　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ことがあるが、本発明はそのような実施態様に限定されるものではない。
　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む範囲を意味する。 Hereinafter, the present invention will be described in detail.
Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments.
In the present specification, a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
　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 groups (atomic groups) in the present specification, the notation not describing substitution and non-substitution also includes a group containing a substituent together with a group not containing a substituent. For example, the "alkyl group" includes not only an alkyl group containing no substituent (unsubstituted alkyl group) but also an alkyl group containing 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 addition, “active light” or “radiation” in the present specification means, for example, far ultraviolet, extreme ultraviolet (EUV), X-ray, electron beam and the like. In the present specification, light means actinic rays and radiation. Unless otherwise specified, the "exposure" in the present specification includes not only exposure by far ultraviolet rays, X-rays, EUV light and the like but also drawing by 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。また、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。また、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。また、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。また、本明細書中において、「単量体」と「モノマー」とは同義である。 Also, as used herein, "(meth) acrylate" represents acrylate and methacrylate. Moreover, in this specification, "(meth) acryl" represents an acryl and a methacryl. Also, as used herein, “(meth) acryloyl” represents acryloyl and methacryloyl. Also, as used herein, "(meth) acrylamide" refers to acrylamide and methacrylamide. Moreover, in this specification, "monomer" and "monomer" are synonymous.
　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 polystyrene conversion value by GPC (Gel Permeation Chromatography) method.
In this specification, GPC method uses HLC-8020GPC (made by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ 2000 (made by Tosoh Corp., 4.6 mm ID × 15 cm) as columns, and THF (tetrahydrofuran as the eluent Based on the method using
　本発明の製造方法は、黒色顔料及び重合性化合物を含有する硬化性組成物を用いて、膜厚１．５μｍあたりの波長３６５ｎｍにおける光学濃度Ａが２．６０～１０．００となり、かつ、膜厚１．５μｍあたりの波長５５０ｎｍにおける光学濃度Ｂが２．００～１０．００となる硬化性組成物層を形成する工程と、上記硬化性組成物層を、酸素濃度が３０～５０体積％の条件下で露光する工程と、上記露光後の上記硬化性組成物層を現像して硬化膜を形成する工程と、を含有する。 In the production method of the present invention, the optical density A at a wavelength of 365 nm per film thickness of 1.5 μm is 2.60 to 10.00 using a curable composition containing a black pigment and a polymerizable compound, and a film A step of forming a curable composition layer having an optical density B at a wavelength of 550 nm per 1.5 μm of 2.00 to 10.00, and the curable composition layer having an oxygen concentration of 30 to 50% by volume And exposing the curable composition layer after the exposure to form a cured film.
　着色剤（特に黒色顔料）を含有する硬化性組成物を用いて形成された硬化性組成物層を露光してパターン状の硬化膜を得ようとする場合、硬化性組成物層の表層部と下層部とで光の当たり方が異なり、得られるパターン状硬化膜の形状が劣化する問題があった。より具体的には、表層部に対して下層部において光が浸透しにくく、下層部において硬化が進行しづらくなり、結果として、パターン状硬化膜の断面形状の矩形性が劣化する問題があった。
　これに対して、本発明の製造方法を用いることで、断面形状の矩形性が優れる硬化膜（パターン状の硬化膜）を得られる理由は必ずしも定かではないが、本発明者らは次のように考えている。つまり、特定の波長に対して所定の光学濃度を示す硬化性組成物層に対して、高酸素濃度下で露光を行うことで、酸素が表層部における硬化反応を適度に阻害し、硬化性組成物層の表層部と下層部とでバランス良く硬化を進行できるためであると考えている。また、上述のようにバランス良く硬化を進行できることにより、形成してから期間（例えば１週間）が空いた硬化性組成物層を使用した場合にいても、得られる硬化膜の良好な矩形性を維持できていると考えている。
　更に、本発明の製造方法で使用される硬化性組成物層は、光学濃度Ａおよび光学濃度Ｂが所定の範囲であるのが、硬化膜の断面形状の矩形性改善に寄与していると考えている。 When exposing a curable composition layer formed using a curable composition containing a colorant (in particular, a black pigment) to obtain a cured film in the form of a pattern, the surface layer portion of the curable composition layer and There is a problem that the way of hitting light is different in the lower layer portion, and the shape of the obtained patterned cured film is deteriorated. More specifically, light is less likely to penetrate to the surface layer portion in the lower layer portion, and curing is less likely to progress in the lower layer portion, and as a result, there is a problem that the rectangularity of the cross-sectional shape of the patterned cured film is deteriorated. .
On the other hand, the reason why the cured film (patterned cured film) excellent in the rectangularity of the cross-sectional shape can be obtained by using the production method of the present invention is not necessarily clear, but the present inventors are as follows. I am thinking about it. That is, by exposing the curable composition layer exhibiting a predetermined optical density to a specific wavelength under high oxygen concentration, oxygen appropriately inhibits the curing reaction in the surface layer portion, and the curable composition It is believed that this is because curing can proceed in a well-balanced manner in the surface layer portion and the lower layer portion of the object layer. In addition, since curing can proceed in a well-balanced manner as described above, good rectangularity of the resulting cured film can be obtained even when using a curable composition layer having a period (for example, one week) after formation. I think that I can maintain it.
Furthermore, in the curable composition layer used in the production method of the present invention, it is considered that the optical density A and the optical density B being within the predetermined range contributes to the improvement of the rectangularity of the cross-sectional shape of the cured film. ing.
　本発明の製造方法では、上述の通り、特定の成分を含有し所定の光学濃度を示す硬化性組成物層を、一定の酸素濃度下において露光することで硬化膜を製造する。
　本明細書においては、まず、本発明の製造方法に用いられる硬化性組成物について説明する。次いで、この硬化性組成物を用いて硬化性組成物層を形成し、上記硬化性組成物層を露光して硬化膜を製造する方法について説明する。
　その後、本発明の製造方法を用いて得られる硬化膜の用途について説明する。 In the production method of the present invention, as described above, the curable composition layer containing a specific component and exhibiting a predetermined optical density is exposed under a constant oxygen concentration to produce a cured film.
In the present specification, first, a curable composition used in the production method of the present invention will be described. Subsequently, a curable composition layer is formed using this curable composition, and the method of exposing the said curable composition layer and manufacturing a cured film is demonstrated.
Then, the use of the cured film obtained using the manufacturing method of this invention is demonstrated.
［硬化性組成物］
　次に、本発明の製造方法で使用される硬化性組成物について説明する。
　本発明の製造方法に使用される硬化性組成物が含有する成分について説明する。 [Curable composition]
Next, the curable composition used by the manufacturing method of this invention is demonstrated.
The component which the curable composition used for the manufacturing method of this invention contains is demonstrated.
＜黒色顔料＞
　硬化性組成物は、黒色顔料を含有する。黒色顔料は、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。
　黒色の無機顔料としては、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む、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。無機顔料には、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を併せ持つ表面処理剤で表面修飾処理が施された無機粒子が挙げられ、「ＫＴＰ－０９」シリーズ（信越化学工業社製）などが挙げられる。また、金属酸化物、金属窒化物、及び金属酸窒化物は、更に他の原子が混在した粒子として使用してもよい。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として使用されてもよい。
　黒色顔料としては、カーボンブラックも挙げられる。カーボンブラックの具体例としては、市販品である、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。 <Black pigment>
The curable composition contains a black pigment. As the black pigment, various known black pigments can be used. The black pigment may be an inorganic pigment or an organic pigment.
Examples of black 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), chromium Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and one or two selected from the group consisting of silver (Ag) Examples thereof include metal oxides, metal nitrides, metal oxynitrides, and the like containing a metal element of a kind or more. The inorganic pigment may be subjected to surface modification treatment. Examples include inorganic particles that have been surface-modified with a surface treatment agent having both a silicone group and an alkyl group, such as the “KTP-09” series (manufactured by Shin-Etsu Chemical Co., Ltd.). In addition, metal oxides, metal nitrides, and metal oxynitrides may be used as particles in which other atoms are mixed. For example, it may be used as a metal nitride-containing particle further containing an atom (preferably an oxygen atom and / or a sulfur atom) selected from periodic table elements 13-17.
The black pigment also includes carbon black. Specific examples of carbon black include C.I. I. Organic pigments such as C.I. pigment black 1; I. And inorganic pigments such as CI pigment black 7.
　なかでも、黒色顔料としては、第４族の金属元素の窒化物若しくは酸化物、第５族の金属元素の窒化物若しくは酸窒化物、又は、カーボンブラックが好ましく、チタンの窒化物若しくは酸窒化物、ジルコニウムの窒化物若しくは酸窒化物、バナジウムの窒化物若しくは酸窒化物、ニオブの窒化物若しくは酸窒化物、又は、カーボンブラックがより好ましく、チタンの窒化物若しくは酸窒化物、ジルコニウムの窒化物若しくは酸窒化物、バナジウムの窒化物若しくは酸窒化物、又は、ニオブの窒化物又は酸窒化物が更に好ましく、チタンの窒化物若しくは酸窒化物、又は、ジルコニウムの窒化物又は酸窒化物が特に好ましい。
　なお、チタンの窒化物とは窒化チタンであり、ジルコニウムの窒化物とは窒化ジルコニウムであり、バナジウムの窒化物とは窒化バナジウムであり、ニオブの窒化物とは窒化ニオブである。また、チタンの酸窒化物とは酸窒化チタンであり、ジルコニウムの酸窒化物とは酸窒化ジルコニウムであり、バナジウムの酸窒化物とは酸窒化バナジウムであり、ニオブの酸窒化物とは酸窒化ニオブである。
　また、黒色顔料として、市販品である「ＮＩＴＲＢＬＡＣＫ（ナイトブラック）ＵＢ－１」（三菱マテリアル社製、特開２０１７－２２２５５９号公報に記載の窒化ジルコニウム粉末、及び、特許第４９３１０１１号公報に記載の微粒子低次酸化ジルコニウム・窒化ジルコニウム複合体等の黒色顔料も挙げられる。 Among them, as the black pigment, nitrides or oxides of Group 4 metal elements, nitrides or oxynitrides of Group 5 metal elements, or carbon black are preferable, and titanium nitride or oxynitride , Zirconium nitride or oxynitride, vanadium nitride or oxynitride, niobium nitride or oxynitride, or carbon black is more preferable, titanium nitride or oxynitride, zirconium nitride or Oxynitrides, nitrides or oxynitrides of vanadium, or nitrides or oxynitrides of niobium are more preferable, and nitrides or oxynitrides of titanium, or nitrides or oxynitrides of zirconium are particularly preferable.
The nitride of titanium is titanium nitride, the nitride of zirconium is zirconium nitride, the nitride of vanadium is vanadium nitride, and the nitride of niobium is niobium nitride. The titanium oxynitride is titanium oxynitride, the zirconium oxynitride is zirconium oxynitride, the vanadium oxynitride is vanadium oxynitride, and the niobium oxynitride is oxynitride. It is niobium.
In addition, as a black pigment, a commercially available product "NITRBLACK (night black) UB-1" (manufactured by Mitsubishi Materials Co., Ltd., zirconium nitride powder described in JP-A-2017-222559, and JP-A-4931011) There may also be mentioned black pigments such as particulate low-order zirconium oxide-zirconium nitride composites.
　また、本発明の製造方法において、黒色顔料として、チタンの窒化物又は酸窒化物、ジルコニウムの窒化物又は酸窒化物、バナジウムの窒化物又は酸窒化物、又は、ニオブの窒化物又は酸窒化物を使用する場合、驚くべきことに、硬化性組成物を使用して硬化性組成物層を形成した後、露光するまで期間（例えば１週間）が空いた場合であっても、得られる硬化膜の断面形状の矩形性の劣化をより抑制できる。 In the production method of the present invention, as the black pigment, nitrides or oxynitrides of titanium, nitrides or oxynitrides of zirconium, nitrides or oxynitrides of vanadium, or nitrides or oxynitrides of niobium In the case of using the composition, it is surprising that, after the curable composition is used to form the curable composition layer, the resulting cured film is obtained even if there is a period (eg 1 week) until exposure. Deterioration of the rectangularity of the cross-sectional shape of can be further suppressed.
　黒色顔料は、なるべく細かいものが好ましい。ハンドリング性をも考慮すると、黒色顔料の平均一次粒子径は、０．０１～０．１μｍが好ましく、０．０１～０．０５μｍがより好ましい。 The black pigment is preferably as fine as possible. In consideration of handling properties as well, the average primary particle size of the black pigment is preferably 0.01 to 0.1 μm, and more preferably 0.01 to 0.05 μm.
　なお、黒色顔料の平均一次粒子径は、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電子顕微鏡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を粒子径とする。この方法で１００個の粒子の粒子径を測定し、その算術平均値を平均粒子径として、黒色顔料の平均一次粒子径とする。 The average primary particle size of the black pigment can be measured using a transmission electron microscope (TEM). As a transmission electron microscope, for example, a transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
Maximum length of particle image obtained using transmission electron microscope (Dmax: maximum length at two points on the contour of particle image), and maximum vertical length (DV-max: two straight lines parallel to the maximum length When the image is sandwiched, the shortest length connecting two straight lines vertically is measured, and the geometric mean value (Dmax × DV-max) 1/2 is defined as the particle diameter. The particle diameter of 100 particles is measured by this method, and the arithmetic mean value is taken as an average particle diameter to obtain an average primary particle diameter of the black pigment.
　なお、本明細書において、窒化チタンとは、ＴｉＮを意図し、製造上不可避な酸素原子（例えば、ＴｉＮの粒子の表面が意図せず酸化したもの、等）を含有してもよい。
　本明細書において、窒化チタンとは、ＣｕＫα線をＸ線源とした場合の（２００）面に由来するピークの回折角２θが４２．５°～４２．８°である化合物を意図する。
　また、本明細書において、酸窒化チタンとは、ＣｕＫα線をＸ線源とした場合の（２００）面に由来するピークの回折角２θが４２．８°超の化合物を意図する。酸窒化チタンの上記回折角２θの上限値としては特に制限されないが、４３．５°以下が好ましい。
　酸窒化チタンとしては、例えば、チタンブラック等が挙げられ、より具体的には、例えば、ＴｉＯ２、ＴｉｎＯ２ｎ－１（１≦ｎ≦２０）で表せる低次酸化チタン、及び／又は、ＴｉＮｘＯｙ（０＜ｘ＜２．０，０．１＜ｙ＜２．０）で表せる酸窒化チタンを含有する形態が挙げられる。以下の説明では、窒化チタン（上記回折角２θが４２．５°～４２．８°）、及び、酸窒化チタン（上記回折角２θが４２．８°超）を併せてチタン窒化物といい、その形態について説明する。
　また、チタン窒化物は、更に他の原子が混在した粒子として使用してもよい。例えば、チタン窒化物は、更に周期表１３～１７族元素から選択される原子（好ましくは、硫黄原子）を含有する、チタン窒化物含有粒子として使用されてもよい。なお、その他の金属窒化物においても同様で、窒化金属と酸窒化金属を併せていう金属窒化物は、更に他の原子が混在した粒子として使用してもよい。例えば、金属窒化物は、更に周期表１３～１７族元素から選択される原子（好ましくは、硫黄原子）を含有する、金属窒化物含有粒子として使用されてもよい。 In the present specification, titanium nitride is intended to be TiN, and may contain unavoidable oxygen atoms in production (for example, unintentional oxidation of the surface of TiN particles, etc.).
In the present specification, titanium nitride means a compound having a diffraction angle 2θ of 42.5 ° to 42.8 ° of a peak derived from the (200) plane when a CuKα ray is used as an X-ray source.
Further, in the present specification, titanium oxynitride means a compound having a diffraction angle 2θ of a peak derived from the (200) plane in the case of using CuKα radiation as an X-ray source over 42.8 °. The upper limit value of the above-mentioned diffraction angle 2θ of titanium oxynitride is not particularly limited, but 43.5 ° or less is preferable.
The titanium nitride, for example, include titanium black or the like, more specifically, for example, low-order titanium oxide represented by TiO 2, Ti n O 2n- 1 (1 ≦ n ≦ 20), and / or, forms containing TiN x O y titanium oxynitride represented by (0 <x <2.0,0.1 <y <2.0) can be mentioned. In the following description, titanium nitride (the diffraction angle 2θ is 42.5 ° to 42.8 °) and titanium oxynitride (the diffraction angle 2θ is more than 42.8 °) are collectively referred to as titanium nitride, The form will be described.
In addition, titanium nitride may be used as particles in which other atoms are further mixed. For example, titanium nitride may be used as titanium nitride-containing particles further containing atoms (preferably, sulfur atoms) selected from Periodic Table Group 13-17 elements. The same applies to the other metal nitrides, and the metal nitride which is a combination of metal nitride and metal oxynitride may be used as particles in which other atoms are mixed. For example, the metal nitride may be used as a metal nitride-containing particle further containing an atom (preferably, a sulfur atom) selected from elements of periodic table 13-17.
　ＣｕＫα線をＸ線源としてチタン窒化物のＸ線回折スペクトルを測定した場合において、最も強度の強いピークとしてＴｉＮは（２００）面に由来するピークが２θ＝４２．５°近傍に、ＴｉＯは（２００）面に由来するピークが２θ＝４３．４°近傍に観測される。一方、最も強度の強いピークではないがアナターゼ型ＴｉＯ２は（２００）面に由来するピークは２θ＝４８．１°近傍に、ルチル型ＴｉＯ２は（２００）面に由来するピークは２θ＝３９．２°近傍に観測される。よって、酸窒化チタンが酸素原子を多く含有するほどピーク位置は４２．５°に対して高角度側にシフトする。 When the X-ray diffraction spectrum of titanium nitride is measured using CuKα radiation as an X-ray source, the peak with the highest intensity is as follows: TiN has a peak derived from the (200) plane in the vicinity of 2θ = 42.5 °; A peak derived from the 200) plane is observed in the vicinity of 2θ = 43.4 °. On the other hand, although not the strongest peak, anatase-type TiO 2 has a peak derived from the (200) plane near 2θ = 48.1 °, and a rutile TiO 2 has a peak derived from the (200) plane 2θ = 39 . Observed near 2 °. Therefore, the peak position shifts to the high angle side with respect to 42.5 ° as the titanium oxynitride contains more oxygen atoms.
　チタン窒化物が、酸化チタンＴｉＯ２を含有する場合、最も強度の強いピークとしてアナターゼ型ＴｉＯ２（１０１）に由来するピークが２θ＝２５．３°近傍に、ルチル型ＴｉＯ２（１１０）に由来するピークが２θ＝２７．４°近傍に見られる。しかし、ＴｉＯ２は白色であり、硬化性組成物を硬化して得られる遮光膜の遮光性を低下させる要因となるため、ピークとして観察されない程度に低減されているのが好ましい。 When titanium nitride contains titanium oxide TiO 2 , the peak derived from anatase type TiO 2 (101) as the strongest peak is derived from rutile type TiO 2 (110) in the vicinity of 2θ = 25.3 ° Peak is observed near 2θ = 27.4 °. However, TiO 2 is white and is a factor to reduce the light shielding property of the light shielding film obtained by curing the curable composition, and therefore, it is preferable to be reduced to such an extent that it is not observed as a peak.
　上記のＸ線回折スペクトルの測定により得られたピークの半値幅から、チタン窒化物を構成する結晶子サイズを求めることができる。結晶子サイズの算出はシェラーの式を用いて行うことができる。 The crystallite size of titanium nitride can be determined from the half width of the peak obtained by the measurement of the X-ray diffraction spectrum described above. The crystallite size can be calculated using Scheller's equation.
　チタン窒化物を構成する結晶子サイズとしては、５０ｎｍ以下が好ましく、２０ｎｍ以上が好ましい。結晶子サイズが２０～５０ｎｍであると、硬化性組成物を用いて形成される硬化膜は、紫外線（特にｉ線（波長３６５ｎｍ））透過率がより高くなりやすく、より感光性が高い硬化性組成物が得られる。 As a crystallite size which constitutes titanium nitride, 50 nm or less is preferable and 20 nm or more is preferable. When the crystallite size is 20 to 50 nm, the cured film formed using the curable composition is likely to have a higher transmittance of ultraviolet light (especially i-line (wavelength 365 nm)), and the photosensitivity is higher. A composition is obtained.
　チタン窒化物の比表面積については特に制限されないが、ＢＥＴ（Ｂｒｕｎａｕｅｒ，Ｅｍｍｅｔｔ，Ｔｅｌｌｅｒ）法により求めることができる。チタン窒化物の比表面積は、５～１００ｍ２／ｇが好ましく、１０～６０ｍ２／ｇがより好ましい。 The specific surface area of titanium nitride is not particularly limited, but can be determined by the BET (Brunauer, Emmett, Teller) method. The specific surface area of the titanium nitride is preferably 5 ~ 100m 2 / g, more preferably 10 ~ 60m 2 / g.
　黒色顔料の製造方法としては特に制限されず、公知の製造方法を使用でき、例えば、気相反応法が挙げられる。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、粒子径が揃いやすく、また、生産性が高い点で、熱プラズマ法が好ましい。
　熱プラズマ法において、熱プラズマを発生させる方法としては、特に制限されず、直流アーク放電、多層アーク放電、高周波（ＲＦ）プラズマ、及び、ハイブリッドプラズマ等が挙げられ、電極からの不純物の混入が少ない高周波プラズマがより好ましい。
　熱プラズマ法による黒色顔料の具体的な製造方法としては、特に制限されないが、例えば、チタン窒化物の製造方法として、プラズマ炎中で四塩化チタンとアンモニアガスを反応させる方法（特開平２－２２１１０号公報）、チタン粉末を高周波熱プラズマにより蒸発させ窒素をキャリアーガスとして導入し冷却過程にて窒化させ合成する方法（特開昭６１－１１１４０号公報）、及び、プラズマの周縁部にアンモニアガスを吹き込む方法（特開昭６３－８５００７号）等が挙げられる。
　ただし、黒色顔料の製造方法としては、上記に制限されるものではなく、所望とする物性を有する黒色顔料が得られれば、製造方法は制限されない。 It does not restrict | limit especially as a manufacturing method of a black pigment, A well-known manufacturing method can be used, for example, a gas phase reaction method is mentioned. Examples of the gas phase reaction method include an electric furnace method and a thermal plasma method, but the thermal plasma method is preferable from the viewpoint that the mixing of impurities is small, the particle diameter is easy to be uniform, and the productivity is high.
In the thermal plasma method, the method of generating thermal plasma is not particularly limited, and direct current arc discharge, multilayer arc discharge, radio frequency (RF) plasma, hybrid plasma, etc. may be mentioned, and contamination with impurities from the electrode is small. High frequency plasma is more preferred.
A specific method for producing a black pigment by a thermal plasma method is not particularly limited. For example, as a method for producing a titanium nitride, a method of reacting titanium tetrachloride and ammonia gas in a plasma flame (Japanese Patent Laid-Open No. 2-22110) Gazette), a method of evaporating titanium powder by high-frequency thermal plasma, introducing nitrogen as a carrier gas, nitriding it in the cooling process (JP-A-61-11140), and ammonia gas at the periphery of plasma And the like (Japanese Patent Application Laid-Open No. 63-85007) and the like.
However, the method for producing a black pigment is not limited to the above, and the production method is not limited as long as a black pigment having desired physical properties is obtained.
　黒色顔料は、その表面に、ケイ素を含有する化合物（以下「含ケイ素化合物」という。）の層を含有してもよい。すなわち、上記金属原子の（酸）窒化物を含ケイ素化合物で被覆し、黒色顔料としてもよい。
　金属原子の（酸）窒化物を被覆する方法としては、特に制限されず、公知の方法を使用でき、例えば、特開昭５３－３３２２８号公報の２頁右下～４頁右上に記載された方法（チタン酸化物に代えて、金属原子の（酸）窒化物を用いる）、特開２００８－６９１９３の段落００１５～００４３段落に記載された方法（微粒子二酸化チタンに代えて、金属原子の（酸）窒化物を用いる）、特開２０１６－７４８７０号公報の００２０段落、及び、０１２４～０１３８段落に記載された方法（金属酸化物微粒子に代えて、金属原子の（酸）窒化物を用いる）が挙げられ、上記の内容は本明細書に組み込まれる。 The black pigment may contain a layer of a silicon-containing compound (hereinafter referred to as "silicon-containing compound") on its surface. That is, the (acid) nitride of the metal atom may be coated with a silicon-containing compound to form a black pigment.
The method for coating the (acid) nitride of the metal atom is not particularly limited, and any known method can be used. For example, it is described in JP-A-53-33228, page 2, lower right to page 4, upper right Method (in place of titanium oxide, (acidic nitride of metal atom is used), the method described in paragraph 0015 to 0043 of JP-A 2008-69193 (in place of fine particle titanium dioxide, (acid of metal atom The method described in paragraphs 0020 and 0124 to 0138 of JP-A-2016-74870) (using (oxide) nitride of metal atom in place of metal oxide fine particles) The contents of which are incorporated herein by reference.
　硬化性組成物中の黒色顔料の含有量は、硬化性組成物の全固形分に対して、４０～７０質量％が好ましく、４５～７０質量％がより好ましく、５０～６５質量％が更に好ましい。
　このような範囲の含有量とすることで、硬化性組成物から形成される硬化性組成物層の光学濃度を所望の範囲に設定しやすい。
　黒色顔料は１種を単独で用いても、２種以上を併用してもよい。２種以上の黒色顔料を併用する場合には、合計含有量が上記範囲内であるのが好ましい。 40 to 70 mass% is preferable with respect to the total solid of a curable composition, as for content of the black pigment in a curable composition, 45 to 70 mass% is more preferable, and 50 to 65 mass% is still more preferable. .
By setting the content in such a range, the optical density of the curable composition layer formed from the curable composition can be easily set in a desired range.
The black pigment may be used alone or in combination of two or more. When two or more types of black pigments are used in combination, the total content is preferably in the above range.
＜着色剤＞
　上記硬化性組成物は、黒色顔料以外の着色剤を含有してもよい。着色剤としては特に制限されず、公知の着色剤を使用できる。着色剤としては、各種公知の顔料（着色顔料）、及び、染料（着色染料）等を使用できる。
　硬化性組成物中における着色剤の含有量としては特に制限されないが、硬化性組成物の全固形分に対して、２０～９９質量％が好ましく、２０～８０質量％がより好ましい。
　着色剤は１種を単独で用いても、２種以上を併用してもよい。２種以上の着色剤を併用する場合には、合計含有量が上記範囲内であるのが好ましい。 <Colorant>
The curable composition may contain a colorant other than the black pigment. The colorant is not particularly limited, and known colorants can be used. As the colorant, various known pigments (colored pigments), dyes (colored dyes) and the like can be used.
The content of the colorant in the curable composition is not particularly limited, but is preferably 20 to 99% by mass, and more preferably 20 to 80% by mass, with respect to the total solid content of the curable composition.
The colorant may be used alone or in combination of two or more. When two or more colorants are used in combination, the total content is preferably within the above range.
　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に記載の着色剤も使用できる。また、黒色染料を使用できる。
　着色顔料としては、例えば、Ｒ（レッド）、Ｇ（グリーン）、及び、Ｂ（ブルー）等の有彩色系の顔料（有彩色顔料）も使用できる。 Examples of colored dyes include, in addition to colored dyes such as R (red), G (green) and B (blue) (chromatic dyes), those described in paragraphs 0027 to 0200 of JP-A 2014-42375. Colorants can also be used. Also, black dyes can be used.
As the color pigment, for example, chromatic color pigments (chromatic color pigments) such as R (red), G (green), and B (blue) can also be used.
（顔料）
　着色剤として使用される顔料は、無機顔料であっても有機顔料であってもよい。 (Pigment)
The pigment used as a colorant may be an inorganic pigment or an organic pigment.
・無機顔料
　無機顔料としては、特に制限されず、公知の無機顔料を使用できる。
　無機顔料としては、例えば、亜鉛華、鉛白、リトポン、酸化チタン、酸化クロム、酸化鉄、沈降性硫酸バリウム及びバライト粉、鉛丹、酸化鉄赤、黄鉛、亜鉛黄（亜鉛黄１種、亜鉛黄２種）、ウルトラマリン青、プロシア青（フェロシアン化鉄カリ）ジルコングレー、プラセオジムイエロー、クロムチタンイエロー、クロムグリーン、ピーコック、ビクトリアグリーン、紺青（プルシアンブルーとは無関係）、バナジウムジルコニウム青、クロム錫ピンク、陶試紅、並びに、サーモンピンク等が挙げられる。
　無機顔料は表面修飾処理がなされていてもよい。例えば、シリコーン基とアルキル基を併せ持つ表面処理剤で表面修飾処理が施された無機顔料が挙げられ、「ＫＴＰ－０９」シリーズ（信越化学工業社製）などが挙げられる。 Inorganic pigment The inorganic pigment is not particularly limited, and known inorganic pigments can be used.
Examples of inorganic pigments include zinc flower, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead, zinc yellow (zinc yellow 1 type, Zinc yellow 2), ultramarine blue, Prussian blue (ferrous iron potassium) zircon gray, praseodymium yellow, chromium titanium yellow, chromium green, peacock, Victoria green, bitumen blue (independent of Prussian blue), vanadium zirconium blue Chrome tin pink, pottery test pink, and salmon pink etc. are mentioned.
The inorganic pigment may be surface-modified. Examples thereof include inorganic pigments that have been surface-modified with a surface treatment agent having both a silicone group and an alkyl group, such as the “KTP-09” series (manufactured by Shin-Etsu Chemical Co., Ltd.).
　赤外線吸収性を有する顔料も使用できる。
　赤外線吸収性を有する顔料としては、タングステン化合物、及び、金属ホウ化物等が好ましく、なかでも、赤外領域の波長における遮光性に優れる点から、タングステン化合物が好ましい。特に露光による硬化効率に関わるオキシム系重合開始剤の光吸収波長領域と、可視光領域の透光性に優れる観点からタングステン化合物が好ましい。 Pigments having infrared absorptivity can also be used.
As the pigment having infrared absorptivity, tungsten compounds, metal borides and the like are preferable. Among them, tungsten compounds are preferable from the viewpoint of being excellent in the light shielding property at the wavelength in the infrared region. In particular, a tungsten compound is preferable from the viewpoint of the excellent light absorption wavelength region of the oxime polymerization initiator related to the curing efficiency by exposure and the light transmittance of the visible light region.
　これらの顔料は、２種以上併用してもよく、また、後述する染料と併用してもよい。色味を調整するため、及び、所望の波長領域の遮光性を高めるため、例えば、黒色、又は赤外線遮光性を有する顔料に、赤色、緑色、黄色、オレンジ色、紫色、及びブルーなどの有彩色顔料若しくは後述する染料を混ぜる形態が挙げられる。赤外線遮光性を有する顔料に、赤色顔料若しくは染料、又は、紫色顔料若しくは染料を混合するのが好ましく、赤外線遮光性を有する顔料に赤色顔料を混合するのがより好ましい。
　更に、後述する赤外線吸収剤を加えてもよい。 These pigments may be used in combination of two or more, and may be used in combination with the dyes described later. In order to adjust the color tone and to enhance the light shielding property of a desired wavelength range, for example, pigments having black color or infrared ray shielding property such as red, green, yellow, orange, purple, and blue The form which mixes a pigment or the dye mentioned later is mentioned. It is preferable to mix a red pigment or dye, or a violet pigment or dye, with the pigment having infrared light shielding properties, and more preferable to mix a red pigment with the pigment having infrared light shielding properties.
Furthermore, an infrared absorber described later may be added.
・有機顔料
　有機顔料としては、例えば、カラーインデックス（Ｃ．Ｉ．）ピグメントイエロー１，２，３，４，５，６，１０，１１，１２，１３，１４，１５，１６，１７，１８，２０，２４，３１，３２，３４，３５，３５：１，３６，３６：１，３７，３７：１，４０，４２，４３，５３，５５，６０，６１，６２，６３，６５，７３，７４，７７，８１，８３，８６，９３，９４，９５，９７，９８，１００，１０１，１０４，１０６，１０８，１０９，１１０，１１３，１１４，１１５，１１６，１１７，１１８，１１９，１２０，１２３，１２５，１２６，１２７，１２８，１２９，１３７，１３８，１３９，１４７，１４８，１５０，１５１，１５２，１５３，１５４，１５５，１５６，１６１，１６２，１６４，１６６，１６７，１６８，１６９，１７０，１７１，１７２，１７３，１７４，１７５，１７６，１７７，１７９，１８０，１８１，１８２，１８５，１８７，１８８，１９３，１９４，１９９，２１３，２１４等、
　Ｃ．Ｉ．ピグメントオレンジ　２，５，１３，１６，１７：１，３１，３４，３６，３８，４３，４６，４８，４９，５１，５２，５５，５９，６０，６１，６２，６４，７１，７３等、
　Ｃ．Ｉ．ピグメントレッド　１，２，３，４，５，６，７，９，１０，１４，１７，２２，２３，３１，３８，４１，４８：１，４８：２，４８：３，４８：４，４９，４９：１，４９：２，５２：１，５２：２，５３：１，５７：１，６０：１，６３：１，６６，６７，８１：１，８１：２，８１：３，８３，８８，９０，１０５，１１２，１１９，１２２，１２３，１４４，１４６，１４９，１５０，１５５，１６６，１６８，１６９，１７０，１７１，１７２，１７５，１７６，１７７，１７８，１７９，１８４，１８５，１８７，１８８，１９０，２００，２０２，２０６，２０７，２０８，２０９，２１０，２１６，２２０，２２４，２２６，２４２，２４６，２５４，２５５，２６４，２７０，２７２，２７９等；
　Ｃ．Ｉ．ピグメントグリーン　７，１０，３６，３７，５８，５９等；
　Ｃ．Ｉ．ピグメントバイオレット　１，１９，２３，２７，３２，３７，４２等；
　Ｃ．Ｉ．ピグメントブルー　１，２，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，６０，６４，６６，７９，８０等；
が挙げられる。なお、顔料は１種を単独で用いても、２種以上を併用してもよい。 -Organic pigment As an organic pigment, color index (CI) pigment yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,18, for example. 20, 24, 31, 32, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37, 1, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 16 7, 168, 169, 170, 171, 172, 173, 174, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc.
C. I. Pigment orange 2, 5, 13, 16, 17: 1, 13, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ,
C. I. Pigment red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 25: 2, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 208, 209, 210, 216, 220, 224, 226, 246, 254, 255, 264, 270, 272, 279, etc .;
C. I. Pigment green 7, 10, 36, 37, 58, 59, etc .;
C. I. Pigment violet 1,19,23,27,32,37,42 etc;
C. I. Pigment blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc .;
Can be mentioned. The pigments may be used alone or in combination of two or more.
（染料）
　染料としては、例えば特開昭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、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号公報等に開示されている色素を使用できる。化学構造として区分すると、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、又は、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、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。 (dye)
Examples of the dyes include, for example, JP-A 64-90403, JP-A 64-91102, JP-A 1-94301, JP-A 6-11614, JP-B 2592 207, and US Pat. No. 4,808,501. U.S. Pat. No. 5,667,920, U.S. Pat. No. 5,505,950, Japanese Patent Application Laid-Open Nos. 5-333207, 6-35183, 6-51115, and 6-194828. The disclosed dyes can be used. When classified as a chemical structure, pyrazole azo compounds, pyrromethene compounds, anilino azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, or pyrrolopyrazole azomethines Compounds etc. can be used. In addition, as the dye, a dye multimer may be used. Examples of the dye multimer include the compounds described in JP-A-2011-213925 and JP-A-2013-041097. Moreover, you may use the polymeric dye which has a polymerizability in a molecule | numerator, As a commercial item, Wako Pure Chemical Industries Ltd. RDW series by which it is mentioned are mentioned, for example.
（赤外線吸収剤）
　上記着色剤は、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 colorant may further contain an infrared absorber.
The infrared absorber means a compound having absorption in a wavelength range of infrared range (preferably, wavelength of 650 to 1300 nm). The infrared absorber is preferably a compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm.
Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squalilium compounds, naphthalocyanine compounds, quaterrylene A compound, a dithiol metal complex type compound, and a croconium compound etc. are mentioned.
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-2010-111750 may be used, and the contents of this specification are as described herein. Incorporated into the book. The cyanine compound can be referred to, for example, "Functional pigment, Shin Ookawara / Ken Matsuoka / Keijiro Kitao / Tsunehiro Hiraiso, 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を含む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。 As colorants having the above spectral characteristics, 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, JP-A 2011-164583 It is also possible to use near-infrared absorbing particles consisting of crystallites of oxides containing Cu and / or P disclosed in paragraphs 0034 to 0067 of the gazette and having a number average aggregate particle diameter of 5 to 200 nm.
　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であるのが好ましく、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００４９～００６２段落を参酌でき、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００２２～００６３段落、国際公開２０１４／０３０６２８号公報の００５３～０１１８段落、特開２０１４－５９５５０号公報の００２８～００７４段落、国際公開２０１２／１６９４４７号公報の００１３～００９１段落、特開２０１５－１７６０４６号公報の００１９～００３３段落、特開２０１４－６３１４４号公報の００５３～００９９段落、特開２０１４－５２４３１号公報の００８５～０１５０段落、特開２０１４－４４３０１号公報の００７６～０１２４段落、特開２０１２－８５３２号公報の００４５～００７８段落、特開２０１５－１７２１０２号公報の００２７～００６７段落、特開２０１５－１７２００４号公報の００２９～００６７段落、特開２０１５－４０８９５号公報の００２９～００８５段落、特開２０１４－１２６６４２号公報の００２２～００３６段落、特開２０１４－１４８５６７号公報の００１１～００１７段落、特開２０１５－１５７８９３号公報の００１０～００２５段落、特開２０１４－０９５００７号公報の００１３～００２６段落、特開２０１４－８０４８７号公報の００１３～００４７段落、及び、特開２０１３－２２７４０３号公報の０００７～００２８段落等を参酌でき、この内容は本明細書に組み込まれる。 The compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is preferably at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, and naphthalocyanine compounds.
The infrared absorber is preferably a compound soluble in water at 25 ° C. in 1% by mass or more, and more preferably a compound soluble in water at 25 ° C. in 10% by mass or more. The solvent resistance is improved by using such a compound.
The pyrrolopyrrole compounds can be referred to paragraphs 0049 to 0062 of JP-A-2010-222557, the contents of which are incorporated herein. Cyanine compounds and squarylium compounds are disclosed in paragraphs 0022 to 0063 in WO 2014/088063, 0053 to 0118 in WO 2014/030628, 0028 to 0074 in JP 2014-59550, WO 2012 / JP-A-2015-147, JP-A-2015-176046, JP-A-2014-63144, JP-A-2014-63144, JP-A-2014-52431, JP-A-2014-523, paragraph Paragraphs 0076 to 0124 of 2014-44301, paragraphs 0045 to 0078 of JP 2012-8532, 0027 to 0067 of JP 2015-172102, 0029 ... JP 2015-172004 Paragraph 067, 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, JP-A-2015-157893 Paragraphs 0010 to 0025, paragraphs 0013 to 0026 of JP 2014-095007, paragraphs 0013 to 0047 of JP 2014-80487, and paragraphs 0007 to 0028 of JP 2013-227403 can be referred to. This content is incorporated herein.
＜重合性化合物＞
　硬化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図し、後述する、分散剤及びアルカリ可溶性樹脂とは異なる成分を意図する。 <Polymerizable compound>
The curable composition contains a polymerizable compound. In the present specification, the term "polymerizable compound" is intended to mean a compound which is polymerized under the action of a polymerization initiator described later, and intends a component different from the dispersant and the alkali-soluble resin described later.
　硬化性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、硬化性組成物の全固形分に対して、５～３０質量％が好ましい。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のが好ましい。
　重合性化合物の分子量は２０００以下であるのが好ましい。 The content of the polymerizable compound in the curable composition is not particularly limited, but it is preferably 5 to 30% by mass with respect to the total solid content of the curable composition. The polymerizable compounds may be used alone or in combination of two or more. When two or more types of polymerizable compounds are used in combination, the total content is preferably in the above range.
The molecular weight of the polymerizable compound is preferably 2000 or less.
　重合性化合物は、エチレン性不飽和結合を含有する基（以下単に「エチレン性不飽和基」ともいう）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。 The polymerizable compound is preferably a compound containing one or more groups containing an ethylenic unsaturated bond (hereinafter, also simply referred to as "ethylenically unsaturated group"), more preferably a compound containing two or more, and three or more. The compound to contain is further more preferable, and the compound which contains 5 or more is especially preferable. The upper limit is, for example, 15 or less. As an ethylenically unsaturated group, a vinyl group, a (meth) allyl group, and a (meth) acryloyl group etc. are mentioned, for example.
　重合性化合物としては、例えば、特開２００８－２６０９２７号公報の００５０段落、及び、特開２０１５－６８８９３号公報の００４０段落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, compounds described in paragraph 0050 of JP-A 2008-260927 and paragraph 0040 of JP-A 2015-68893 can be used, and the above contents are incorporated in the present specification. Be
　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であるのが好ましく、３～６官能の（メタ）アクリレート化合物であるのがより好ましい。 The polymerizable compound may be, for example, any of chemical forms such as monomers, prepolymers, oligomers, and mixtures thereof, and multimers thereof.
The polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 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。 The polymerizable compound is also preferably a compound having one or more ethylenically unsaturated groups and having a boiling point of 100 ° C. or more under normal pressure. For example, the compounds described in paragraph 0227 of JP-A-2013-29760 and paragraphs 0254 to 0257 of JP-A-2008-292970 can be referred to, the contents of which 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；日本化薬社製、Ａ－ＤＰＨ－１２Ｅ；新中村化学社製）、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、新中村化学社製）、及び、ＫＡＹＡＲＡＤ　ＲＰ－１０４０（日本化薬社製）等を使用することもできる。
　以下に好ましい重合性化合物の態様を示す。 The polymerizable compound is dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), Pentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH- 12E; Shin-Nakamura Chemical Co., Ltd.) and structures in which these (meth) acryloyl groups are mediated by ethylene glycol residue or propylene glycol residue (for example, SR454, SR499 commercially available from Sartmar) are preferable. . These oligomer types can also be used. In addition, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), and KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) can also be used.
The aspect of a preferable polymeric compound is shown below.
　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ものが更に好ましい。市販品としては、例えば、東亜合成社製の、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 containing an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a nonaromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to produce an acid. A polymerizable compound having a group is more preferable, and in this ester, one in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol is more preferable. Examples of commercially available products include ALONIX TO-2349, M-305, M-510, and M-520 manufactured by Toa Gosei 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 containing an acid group is preferably 0.1 to 40 mg KOH / g, and more preferably 5 to 30 mg KOH / g. When the acid value of the polymerizable compound is 0.1 mg KOH / g or more, the developing dissolution property is good, and when it is 40 mg KOH / g or less, it is advantageous in terms of 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限定されるものではないが、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することにより得られる、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。なかでも下記式（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。 As the polymerizable compound, a compound having a caprolactone structure is also a preferred embodiment.
The compound having a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentacene. Ε-caprolactone modified polyfunctional (meth) obtained by esterifying a polyhydric alcohol such as erythritol, tripentaerythritol, glycerin, diglycerol or trimethylolmelamine with (meth) acrylic acid and ε-caprolactone ) Acrylates. Among them, compounds having a caprolactone structure represented by the following formula (Z-1) are preferable.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　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 R's are a group represented by the following formula (Z-2), or 1 to 5 of the six R's are the following formula (Z-2) And the remainder is a group represented by the following formula (Z-3).
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　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、「＊」は結合手であることを示す。 In formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（Ｚ－３）中、Ｒ１は水素原子又はメチル基を示し、「＊」は結合手であることを示す。） 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。 For example, a polymerizable compound containing a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and DPCA-20 (in the above formulas (Z-1) to (Z-3), m = 1, -2) the number of groups represented by 2 = 2, a compound wherein all R 1 s are hydrogen atoms, DPCA-30 (the same formula, m = 1, the number of groups represented by the formula (Z-2) = 3 , A compound wherein all R 1 s are hydrogen atoms, DPCA-60 (the same formula, m = 1, the number of groups represented by formula (Z-2) = 6, a compound wherein all R 1 s are hydrogen atoms), And DPCA-120 (in the formula, m = 2, the number of groups represented by formula (Z-2) = 6, and a compound in which all R 1 are hydrogen atoms), and the like.
　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-C000004
Figure JPOXMLDOC01-appb-C000004
　式（Ｚ－４）及び（Ｚ－５）中、Ｅは、それぞれ独立に、－（（ＣＨ２）ｙＣＨ２Ｏ）－、又は（（ＣＨ２）ｙＣＨ（ＣＨ３）Ｏ）－を表し、ｙは、それぞれ独立に０～１０の整数を表し、Ｘは、それぞれ独立に、（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はそれぞれ独立に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はそれぞれ独立に０～１０の整数を表し、各ｎの合計は０～６０の整数である。 Wherein (Z-4) and (Z-5), E are each independently, - ((CH 2) y CH 2 O) -, or ((CH 2) y CH ( CH 3) O) - a And y each independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
In formula (Z-4), the total of (meth) acryloyl groups is three or four, m each independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40.
In formula (Z-5), the total of (meth) acryloyl groups is five or six, n independently represents an integer of 0 to 10, and the sum 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.
The total of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and still more preferably an integer of 4 to 8.
In the formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.
Further, the formula (Z-4) or formula (Z-5) in the - ((CH 2) y CH 2 O) - , or ((CH 2) y CH ( CH 3) O) - , the oxygen atom side A form in which the end 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。このような構成とすることにより、現像性をより向上できる。 The compounds represented by Formula (Z-4) or Formula (Z-5) may be used alone or in combination of two or more. In particular, in a form in which all six X's are an acryloyl group in the formula (Z-5), a compound in which all six X's are an acryloyl group in the formula (Z-5), and A preferred embodiment is a mixture with a compound in which at least one hydrogen atom is present. With such a configuration, 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なかでも、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 Formula (Z-4) or 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 Formula (Z-4) or Formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives 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、限定されないが、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）で除した値を意図する）は５．０ｍｍｏｌ／ｇ以上であるのが好ましい。上限は特に制限されないが、一般に、２０．０ｍｍｏｌ／ｇ以下である。
　なお、硬化性組成物中が、複数種類の重合性化合物を含有し、それぞれの二重結合当量が同一ではない場合は、全重合性化合物中における各重合性化合物の質量比と、各重合性化合物の二重結合当量との積を、それぞれ合計した値が、上記範囲内にあるのが好ましい。 In addition, the polymerizable compound may contain a cardo skeleton.
The polymerizable compound containing a cardo skeleton is preferably a polymerizable compound containing a 9,9-bisarylfluorene skeleton.
Examples of the polymerizable compound containing a cardo skeleton include, but are not limited to, On Coat EX series (manufactured by Nagase Sangyo Co., Ltd.) and ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).
The polymerizable compound is also preferably a compound containing an isocyanuric acid skeleton as a central core. As an example of such a polymerizable compound, for example, NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.) can be mentioned.
The content of the ethylenically unsaturated group in the polymerizable compound (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 / It is preferably g or more. Although the upper limit is not particularly limited, it is generally 20.0 mmol / g or less.
In the case where the curable composition contains a plurality of types of polymerizable compounds and the respective double bond equivalents are not the same, the mass ratio of each polymerizable compound in all the polymerizable compounds and the respective polymerizability It is preferable that the sum of the products of the compounds and the double bond equivalents be in the above range.
＜樹脂＞
　硬化性組成物は樹脂を含有するのが好ましい。樹脂としては例えば、分散剤及びアルカリ可溶性樹脂等が挙げられる。
　硬化性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、硬化性組成物の全固形分に対して、３～６０質量％が好ましく、５～４０質量％がより好ましい。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。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のが好ましい。
　樹脂の分子量は２０００超である。なお、樹脂の分子量が多分散である場合、重量平均分子量が２０００超である。 <Resin>
The curable composition preferably contains a resin. Examples of the resin include dispersants and alkali-soluble resins.
The content of the resin in the curable composition is not particularly limited, but is preferably 3 to 60% by mass, and more preferably 5 to 40% by mass, with respect to the total solid content of the curable composition. The resins may be used alone or in combination of two or more. When two or more resins are used in combination, the total content is preferably in the above range.
The molecular weight of the resin is greater than 2000. When the molecular weight of the resin is polydispersed, the weight average molecular weight is more than 2000.
（分散剤）
　硬化性組成物は分散剤を含有するのが好ましい。なお、本明細書において、分散剤とは、後述するアルカリ可溶性樹脂とは異なる化合物を意図する。
　硬化性組成物中における分散剤の含有量としては特に制限されないが、硬化性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％がより好ましい。
　分散剤は、１種を単独で用いても、２種以上を併用してもよい。２種以上の分散剤を併用する場合には、合計含有量が上記範囲内であるのが好ましい。 (Dispersant)
The curable composition preferably contains a dispersant. In the present specification, the dispersant is intended to be a compound different from the alkali-soluble resin described later.
The content of the dispersant in the curable composition is not particularly limited, but is preferably 2 to 40% by mass, and more preferably 5 to 30% by mass, relative to the total solid content of the curable composition.
The dispersant may be used alone or in combination of two or more. When two or more dispersants are used in combination, the total content is preferably in the above range.
　分散剤としては、例えば、公知の分散剤を適宜選択して使用できる。なかでも、高分子化合物が好ましい。
　分散剤としては、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 a dispersing agent, a well-known dispersing agent can be used selecting it suitably, for example. Among these, high molecular compounds are preferable.
As the dispersant, polymer dispersants [for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type Copolymers, naphthalenesulfonic acid formalin condensates], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, and pigment derivatives.
The polymer compounds can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers according to their structures.
・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」ともいう）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 polymer compound is adsorbed on the surface of a material to be dispersed, such as a black pigment and other pigments optionally used in combination (hereinafter, the black pigment and other pigments are collectively referred to simply as “pigments”) , Acts to prevent reaggregation of the material to be dispersed. Therefore, terminal modified polymers, grafted polymers (containing polymer chains), or block polymers containing anchor sites on the pigment surface are preferred.
　上記高分子化合物は硬化性基を含有してもよい。
　硬化性基としては、例えば、エチレン性不飽和基（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。
　なかでも、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い。エチレン性不飽和基は（メタ）アクリロイル基がより好ましい。 The polymer compound may contain a curable group.
Examples of the curable group include ethylenically unsaturated groups (eg, (meth) acryloyl group, vinyl group, and styryl group), and cyclic ether groups (eg, epoxy group, oxetanyl group etc.), etc. But not limited to.
Among them, an ethylenically unsaturated group is preferable as the curable group in that polymerization can be controlled by a radical reaction. The ethylenically unsaturated group is more preferably a (meth) acryloyl group.
　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種を含有するのが好ましい。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のがより好ましい。 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, and as described later, when the resin contains a structural unit containing a graft chain, the above polymer The chain may contain a polyester structure and / or a polyether structure.
As said resin, it is more preferable that the said polymeric chain contains 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のが好ましい。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）に優れるものである。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であるのが好ましく、水素原子を除いた原子数が５０～２０００であるのがより好ましく、水素原子を除いた原子数が６０～５００であるのが更に好ましい。
　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 the present specification, “structural unit” is synonymous with “repeating unit”.
The polymer compound containing a structural unit containing such a graft chain has an affinity to a solvent by the graft chain, and thus the dispersibility of the pigment etc. and the dispersion stability after aging (stability over time) Excellent. Further, due to the presence of the graft chain, the polymer compound containing a structural unit containing a graft chain has an affinity to a polymerizable compound or other usable resin and the like. As a result, alkaline development is less likely to produce a residue.
The longer the graft chain, the higher the steric repulsion effect and the better the dispersibility of the pigment and the like. On the other hand, when the graft chain is too long, the adsorptive power to the pigment and the like decreases, and the dispersibility of the pigment and the like tends to decrease. For this reason, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and more than 40 atoms excluding hydrogen atoms. More preferably, it is 60 to 500.
Here, the graft chain means 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 end 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のが好ましく、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のが好ましく、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のがより好ましい。 The graft chain preferably contains a polymer structure, and as such a polymer structure, for example, poly (meth) acrylate structure (eg, poly (meth) acrylic structure), polyester structure, polyurethane structure, polyurea structure, polyamide And polyether structures and the like.
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, thereby enhancing the dispersibility of the pigment etc. It is preferable that it is a graft chain containing at least one, more preferably a graft chain containing 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、特に限定されないが、反応性二重結合性基を含有するマクロモノマーを好適に使用できる。 The macromonomer containing such a graft chain (a monomer having a polymer structure and being bonded to the main chain of the copolymer to constitute the graft chain) is not particularly limited, but a reactive double bondable group may be used. The macromonomer contained can be used suitably.
　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（商品名、東亜合成社製）、ＡＡ－１０（商品名、東亜合成社製）、ＡＢ－６（商品名、東亜合成社製）、ＡＳ－６（商品名、東亜合成社製）、ＡＮ－６（商品名、東亜合成社製）、ＡＷ－６（商品名、東亜合成社製）、ＡＡ－７１４（商品名、東亜合成社製）、ＡＹ－７０７（商品名、東亜合成社製）、ＡＹ－７１４（商品名、東亜合成社製）、ＡＫ－５（商品名、東亜合成社製）、ＡＫ－３０（商品名、東亜合成社製）、ＡＫ－３２（商品名、東亜合成社製）、ブレンマーＰＰ－１００（商品名、日油社製）、ブレンマーＰＰ－５００（商品名、日油社製）、ブレンマーＰＰ－８００（商品名、日油社製）、ブレンマーＰＰ－１０００（商品名、日油社製）、ブレンマー５５－ＰＥＴ－８００（商品名、日油社製）、ブレンマーＰＭＥ－４０００（商品名、日油社製）、ブレンマーＰＳＥ－４００（商品名、日油社製）、ブレンマーＰＳＥ－１３００（商品名、日油社製）、又は、ブレンマー４３ＰＡＰＥ－６００Ｂ（商品名、日油社製）等が用いられる。このなかでも、ＡＡ－６（商品名、東亜合成社製）、ＡＡ－１０（商品名、東亜合成社製）、ＡＢ－６（商品名、東亜合成社製）、ＡＳ－６（商品名、東亜合成社製）、ＡＮ－６（商品名、東亜合成社製）、又は、ブレンマーＰＭＥ－４０００（商品名、日油社製）が好ましい。 Commercially available macromonomers suitable for use in the synthesis of a polymer compound, corresponding to the structural units containing a graft chain contained in the polymer compound, include AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (Trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, produced by Toa Gosei Co., Ltd.), AS-6 (trade name, produced by Toa Gosei Co., Ltd.), AN-6 (trade name, produced by Toa Gosei Co., Ltd.), AW -6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, produced by Toa Gosei Co., Ltd.), AY-707 (trade name, produced by Toa Gosei Co., Ltd.), AY-714 (trade name, produced by Toa Gosei Co., Ltd. AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-30 (trade name, Toa Gosei Co., Ltd.), AK-32 (trade name, Toa Gosei Co., Ltd.), Blenmer PP-100 (trade name, NOF Corporation) Brenmer PP-500 (trade name, manufactured by NOF Corporation), Brenmer PP-800 Product name, manufactured by NOF Corporation, BLEMMER PP-1000 (trade name, manufactured by NOF Corporation), BLEMMER 55-PET-800 (trade name, manufactured by NOF Corporation), BLEMMER PME-4000 (trade name, manufactured by NOF Corporation) Blemmer PSE-400 (trade name, manufactured by NOF Corporation), Blemmer PSE-1300 (trade name, manufactured by NOF Corporation), or Blemmer 43PAPE-600B (trade name, manufactured by NOF Corporation), etc. are used. Among them, AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, Toa Gosei Co., Ltd.), AB-6 (trade name, produced by Toa Gosei Co., Ltd.), AS-6 (trade name, Preferably, Toa Gosei Co., Ltd., AN-6 (trade name, Toa Gosei Co., Ltd.), or Blenmer PME-4000 (trade name, NOF Corporation).
　上記分散剤は、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のが好ましく、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のがより好ましく、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のが更に好ましい。分散剤は、一の分散剤中に上記構造を単独で含有する分散剤であってもよいし、一の分散剤中にこれらの構造を複数含有する分散剤であってもよい。
　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剤の具体例としては、下記式（１）及び下記式（２）におけるｊ及びｋが５である分散剤が挙げられる。また、ポリバレロラクトン構造を含有する分散剤の具体例としては、下記式（１）及び下記式（２）におけるｊ及びｋが４である分散剤が挙げられる。
　ポリアクリル酸メチル構造を含有する分散剤の具体例としては、下記式（４）におけるＸ５が水素原子であり、Ｒ４がメチル基である分散剤が挙げられる。また、ポリメタクリル酸メチル構造を含有する分散剤の具体例としては、下記式（４）におけるＸ５がメチル基であり、Ｒ４がメチル基である分散剤が挙げられる。 The dispersant preferably contains at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate and cyclic or chain polyester, and is preferably polymethyl acrylate or polymethacrylic acid. It is more preferable to contain at least one structure selected from the group consisting of methyl and linear polyesters, and a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure More preferably, it contains at least one structure selected from the group consisting of The dispersing agent may be a dispersing agent containing the above structure alone in one dispersing agent, or may be a dispersing agent containing a plurality of these structures in one dispersing agent.
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.
As a specific example of the dispersing agent containing a polycaprolactone structure, the dispersing agent whose j and k in a following formula (1) and a following formula (2) are 5 is mentioned. Moreover, as a specific example of the dispersing agent containing a polyvalerolactone structure, the dispersing agent whose j and k in following formula (1) and following formula (2) are 4 is mentioned.
Examples of dispersants containing polymethyl acrylate structure, X 5 in formula (4) is a hydrogen atom, R 4 can be cited dispersants are methyl groups. Specific examples of dispersants containing polymethyl methacrylate structure, X 5 in formula (4) is a methyl group, R 4 can be cited dispersants are methyl groups.
・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のが好ましく、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のがより好ましい。 -Structural unit containing a graft chain The polymer compound preferably contains, as a structural unit containing a graft chain, a structural unit represented by any one of the following formulas (1) to (4), and the following formula It is more preferable to contain the structural unit represented by either of (1A), following formula (2A), following formula (3A), following formula (3B), and 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は酸素原子であるのが好ましい。
　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としては、合成上の制約の観点からは、それぞれ独立に、水素原子又は炭素数（炭素原子数）１～１２のアルキル基であるのが好ましく、それぞれ独立に、水素原子又はメチル基であるのがより好ましく、メチル基が更に好ましい。 In 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 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. Each of X 1 , X 2 , X 3 , X 4 and X 5 independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (number of carbon atoms), from the viewpoint of the restriction on synthesis And each independently preferably represents a hydrogen atom or a methyl group, more preferably a methyl group.
　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）の連結基等が例として挙げられる。下記に示した構造において、Ａ、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）であるのがより好ましい。 In the 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 restricted 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) and the like. Be In the structures shown below, A and B respectively indicate bonding sites to the left end group and the right end group in the formulas (1) to (4). Among the structures shown below, (Y-2) or (Y-13) is more preferable in terms of easiness 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、特に限定されないが、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。これらのなかでも、Ｚ１、Ｚ２、Ｚ３、及び、Ｚ４で表される有機基としては、特に分散性向上の観点から、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、そのなかでも、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 Etc. 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 the dispersibility, and each of them independently has carbon number An alkyl group or alkoxy group of 5 to 24 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 having 5 to 24 carbon atoms is particularly independently of each other. Groups are 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観点から、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、分散剤が、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. J and k in the formulas (1) and (2) are preferably integers of 4 to 6, and more preferably 5 from the viewpoint of the temporal stability and developability of the composition.
In the formulas (1) and (2), n and m are preferably integers of 10 or more, and more preferably 20 or more. When the dispersant contains a polycaprolactone structure and a polyvalerolactone structure, the sum of the repeating number of the polycaprolactone structure and the repeating number of the polyvalerolactone is preferably an integer of 10 or more, 20 or more An integer is 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価の有機基としては特に構造上限定はされない。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 formula (3), R 3 represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, plural R 3 s may be the same as or different from each other.
In Formula (4), R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. 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, the alkyl group may be a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. The linear alkyl group having 1 to 20 carbon atoms is more preferable, and the 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 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。 In addition, the polymer compound can contain a graft chain-containing structural unit in which two or more kinds of structures are different. That is, structural units represented by formulas (1) to (4) having mutually different structures may be contained in the molecule of the polymer compound, and n, m, p in formulas (1) to (4) And q each represents an integer of 2 or more, in the formulas (1) and (2), j and k may contain structures different from each other in the side chain, and formulas (3) and (4) In the above, R 3 , R 4 and X 5 which are present in plural in the molecule may be the same as or different from each other.
　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観点から、下記式（１Ａ）で表される構造単位であるのがより好ましい。
　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観点から、下記式（２Ａ）で表される構造単位であるのがより好ましい。 The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of the temporal stability of the composition and the developability.
Moreover, as a structural unit represented by Formula (2), it is more preferable that it is a structural unit represented by following formula (2A) from a time-lapse stability of a composition, and a developability.
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 are synonymous with 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観点から、下記式（３Ａ）又は式（３Ｂ）で表される構造単位であるのがより好ましい。 Moreover, as a structural unit represented by Formula (3), it is more preferable that it is a structural unit represented by a following formula (3A) or Formula (3B) from a time-lapse stability of a composition, and a developability viewpoint. .
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のがより好ましい。 The polymer compound more preferably 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）は、質量換算で、高分子化合物の総質量に対し２～９０質量％の範囲で含まれるのが好ましく、５～３０質量％の範囲で含まれるのがより好ましい。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、硬化膜を形成する際の現像性が良好である。 In the polymer compound, structural units containing a graft chain (for example, structural units represented by the above formulas (1) to (4)) are 2 to 90% by mass in terms of mass relative to the total mass of the polymer compound Is preferably contained in the range of 5 to 30% by mass, and more preferably in the range of 5 to 30% by mass. When the structural unit containing a graft chain is contained in this range, the dispersibility of the pigment is high, and the developability at the time of forming a cured film 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のが好ましい。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 which is different from the structural unit containing a graft chain (that is, not corresponding to a structural unit containing a 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, etc.).
　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）構造単位であるのが好ましく、ＣｌｏｇＰ値が１．２～８の化合物に由来する構造単位であるのがより好ましい。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 (corresponding) structural unit derived from a compound (monomer) having a C log P value of 1.2 or more, and is a structural unit derived from a compound having a C log P value of 1.2 to 8. Is more preferable. Thereby, the effects of the present invention can be more reliably exhibited.
　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寄与分を合計することにより化合物の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 from Daylight Chemical Information System, Inc. Is a value calculated by the program "CLOGP" available from This program provides the value of "computed logP" calculated by the fragment approach of Hansch, Leo (see the following document). The fragment approach is based on the chemical structure of the compound, dividing the chemical structure into substructures (fragments) and estimating the logP value of the compound by summing the logP contributions assigned to the fragment. The details are described in the following documents. The ClogP value calculated by the program CLOGP v4.82 is used herein.
A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P .; G. Sammnens, J.J. B. Taylor and C. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. 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.
　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すことを意味し、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。 log P means the common logarithm of partition coefficient P (Partition Coefficient), and it quantitatively determines how an organic compound is distributed in the equilibrium of oil (generally 1-octanol) and water. Is a physical property value represented as a 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 logP value becomes larger than 0, the oil solubility increases, and when it is negative and the absolute value increases, the water solubility increases, which has a negative correlation with the water solubility of the organic compound, and the affinity of the organic compound is negative. It is widely used as a parameter to estimate water quality.
　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のが好ましい。 The polymer compound preferably contains, as a hydrophobic structural unit, one or more structural units 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、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。
　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のが好ましく、水素原子又はメチル基であるのがより好ましい。Ｒ２及びＲ３は、水素原子であるのが更に好ましい。
　Ｘは、酸素原子（－Ｏ－）又はイミノ基（－ＮＨ－）を表し、酸素原子であるのが好ましい。 In the above formulas (i) to (iii), R 1 , R 2 and R 3 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom etc.), or a carbon number Represents an alkyl group of 1 to 6 (eg, a methyl group, an ethyl group, a propyl group, etc.).
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 hydrogen atoms.
X represents an oxygen atom (-O-) or an imino group (-NH-), 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. As the divalent linking group, a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group), a divalent aromatic group (for example, an arylene group) , substituted arylene group), a divalent heterocyclic group an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR 31 -, wherein R 31 And examples thereof include aliphatic groups, aromatic groups or heterocyclic groups), carbonyl groups (—CO—), and combinations 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、飽和脂肪族基であるのが好ましい。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. 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 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. Also, 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員環を含有するのが好ましい。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. The heterocycle may be fused to another heterocycle, an aliphatic ring or an aromatic ring. 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), and a substituted imino group (= N-R 32 , wherein R 32 is aliphatic) 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価の連結基であるのが好ましい。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であるのがより好ましい。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の整数であるのがより好ましい。 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. In addition, L may contain a polyoxyalkylene structure containing an oxyalkylene structure repeated two or more times. As a polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by-(OCH 2 CH 2 ) n-, and n is preferably an integer of 2 or more, 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、又は、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。 As Z, an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (for example, an aryl group, a substituted aryl group, an arylene group, a substituted arylene group) And heterocyclic groups or combinations thereof. These groups an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR 31 -, wherein R 31 is an aliphatic group, an aromatic A group or a heterocyclic group) or a carbonyl group (-CO-) may be included.
　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-aggregated hydrocarbon group and a crosslinked cyclic hydrocarbon group, and examples of the ring-aggregated hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and And-include cyclohexylphenyl and the like. As the bridged cyclic hydrocarbon ring, for example, pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) 2 Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredane, adamantane, tricyclo [5.2.1.0 2,6 ] decane, and tricyclo [4.3.1.1 2,5 ] undecane rings And tetracyclo [4.4.0.1 2,5 . [1 7,10 ] dodecane and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring and the like can be mentioned. In addition, as the crosslinked cyclic hydrocarbon ring, a fused cyclic hydrocarbon ring, for example, perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and Also included are fused rings in which a plurality of 5- to 8-membered cycloalkane rings such as perhydrophenalene rings are fused.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of substituents include halogen atoms, aromatic groups and heterocyclic groups. 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 carbon number of the aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. Also, the aromatic group may have a substituent. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups and heterocyclic groups. 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員環を含有するのが好ましい。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. The heterocycle may be fused to another heterocycle, an aliphatic ring or an aromatic ring. 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), and a substituted imino group (= N-R 32 , wherein R 32 is aliphatic) And aromatic groups or heterocyclic groups), aliphatic groups, aromatic groups, and heterocyclic groups. 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、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、プロピル基等）、Ｚ、又は、Ｌ－Ｚを表す。ここでＬ及びＺは、上記におけるものと同義である。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 an alkyl group having 1 to 6 carbon atoms (Eg, methyl group, ethyl group, propyl group etc.), Z or LZ. Here, L and Z are as defined above. 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若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 a monomer represented by the said Formula (i), R < 1 >, R < 2 > and R < 3 > are a hydrogen atom or a methyl group, Comprising: L contains a single bond or an alkylene group or an oxyalkylene structure. Compounds in which X is an oxygen atom or an imino group and Z is an aliphatic group, a heterocyclic group or an aromatic group are preferable.
Further, as the monomer represented by the above formula (ii), an R 1 is hydrogen atom or a methyl group, L is an alkylene group, Z is an aliphatic group, a heterocyclic group, or an aromatic Compounds which are groups are preferred. Further, as the monomer represented by the above formula (iii), R 4, R 5, and, R 6 is a hydrogen atom or a methyl group, Z is an aliphatic group, a heterocyclic group, or an aromatic Compounds which 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 representative compounds represented by the formulas (i) to (iii) include radically polymerizable compounds selected from acrylic esters, methacrylic esters, styrenes and the like.
In addition, as an example of a typical compound represented by Formula (i)-(iii), the compound as described in stage 0089-0093 of Unexamined-Japanese-Patent No. 2013-249417 can be referred, and these contents are described in this specification. Incorporated into
　高分子化合物において、疎水性構造単位は、質量換算で、高分子化合物の総質量に対し１０～９０％の範囲で含まれるのが好ましく、２０～８０％の範囲で含まれるのがより好ましい。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 hydrophobic structural unit is preferably contained in a range of 10 to 90%, and more preferably in a range of 20 to 80%, based on the total mass of the polymer compound, in terms of mass. Sufficient pattern formation is obtained in the above range of content.
・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のが好ましい。
　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のが好ましい。
　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ることで、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ることで、上記組成物は、顔料等の分散に寄与する分散剤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、露光部の遮光性に優れたものとなり、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ることにより、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 group capable of forming an interaction with a pigment etc. The polymer compound can introduce a functional group capable of forming an interaction with the pigment etc. Here, the polymer compound preferably further contains a structural unit containing 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 and the like include an acid group, a basic group, a coordinating group, and a functional group having reactivity.
When the polymer compound contains an acid group, a basic group, a coordinating group, or a functional group having reactivity, a structural unit containing an acid group, a structural unit containing a basic group, It is preferable to contain a structural unit containing a reactive group or a structural unit having reactivity.
In particular, when the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, the polymer compound can be provided with developability for pattern formation by alkali development.
That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound as the dispersant contributing to the dispersion of the pigment etc. contains alkali solubility by the composition described above. A composition containing such a polymer compound is excellent in the light shielding property of the exposed area, and the alkali developability of the unexposed area is improved.
In addition, when the polymer compound contains a structural unit containing an acid group, the polymer compound tends to be compatible with the solvent, and the coatability tends to be improved.
This is because the acid group in the structural unit containing the 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 in which the pigment and the like are dispersed decreases. It is presumed that the polymer compound itself is also 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-mentioned structural unit containing a graft chain, or may be a different structural unit, but an alkali as an acid group The structural unit containing a soluble group is a structural unit different from the above-mentioned hydrophobic structural unit (that is, it 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、又は、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種であるのが好ましく、カルボン酸基が更に好ましい。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のが好ましい。 Examples of the acid group that is a functional group capable of forming an interaction with a pigment and the like include, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group. And at least one of phosphoric acid groups is preferable, and a carboxylic acid group is more preferable. The carboxylic acid group has good adsorptivity to pigments and the like, and has 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、質量換算で、高分子化合物の総質量に対して、５～８０質量％であるのが好ましく、アルカリ現像による画像強度のダメージ抑制という観点から、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 when it is contained, the content of the structural unit containing an acid group is the total mass of the polymer compound in terms of mass. On the other hand, the content is preferably 5 to 80% by mass, and more preferably 10 to 60% by mass from the viewpoint of suppressing damage to the image strength due to alkaline 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観点から、０．０１～３０質量％がより好ましい。 As a basic group which is a functional group capable of forming an interaction with a pigment etc., for example, a primary amino group, a secondary amino group, a tertiary amino group, a heterocycle containing N atom, and an amide The preferred basic group is a tertiary amino group in that it has a group etc. and is preferable in that it has good adsorptivity to pigments etc and 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 the total of the polymer compound in terms of mass. The content is preferably 0.01 to 50% by mass, and more preferably 0.01 to 30% by mass from the viewpoint of development inhibition inhibition.
　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観点から、２０～６０質量％がより好ましい。 As a coordinating group which is a functional group capable of forming an interaction with a pigment or the like, and as a functional group having reactivity, for example, acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, and acidification Things etc. The preferred functional group is an acetylacetoxy group in that it has good adsorptivity to pigments and the like and high dispersibility of 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 functional group having reactivity, but when it is contained, the content of these structural units In terms of mass, 10 to 80% by mass is preferable based on the total mass of the polymer compound, and 20 to 60% by mass is more preferable from the viewpoint of development inhibition inhibition.
　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限定はされないが、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のが好ましい。 When the above-mentioned polymer compound contains a functional group capable of forming an interaction with a pigment or the like in addition to the graft chain, the polymer compound may contain a functional group capable of forming an interaction with the various pigments described above, There is no particular limitation on how these functional groups are introduced, but the polymer compound is selected from structural units derived from monomers represented by the following formulas (iv) to (vi). It is preferred to contain more than species of 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、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は、それぞれ独立に水素原子、又は炭素数が１～３のアルキル基であるのが好ましく、それぞれ独立に水素原子又はメチル基であるのがより好ましい。一般式（ｉｖ）中、Ｒ１２及びＲ１３は、それぞれ水素原子であるのが更に好ましい。 In 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, etc.) or a carbon number of 1 to 6 represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.).
In formulas (iv) to (vi), R 11 , R 12 and R 13 each independently represent preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently represents a hydrogen atom or methyl More preferred is a group. In General Formula (iv), each of R 12 and R 13 is more preferably a hydrogen atom.
　式（ｉｖ）中のＸ１は、酸素原子（－Ｏ－）又はイミノ基（－ＮＨ－）を表し、酸素原子であるのが好ましい。
　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-), preferably an oxygen atom.
Moreover, Y in 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。 In addition, L 1 in 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 formula (i) described above.
　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価の連結基であるのが好ましい。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であるのがより好ましい。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の整数であるのがより好ましい。 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. L 1 may also include a polyoxyalkylene structure containing an oxyalkylene structure repeated two or more times. As a polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by-(OCH 2 CH 2 ) n-, and n is preferably an integer of 2 or more, 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、及び、第３級アミノ基であるのが好ましく、カルボン酸基であるのがより好ましい。 In formulas (iv) to (vi), Z 1 represents a functional group capable of forming an interaction with a pigment or the like in addition to the graft chain, and is preferably a carboxylic acid group or a tertiary amino group, More preferred is an acid group.
　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、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、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。Ｒ１
４、Ｒ１５、及び、Ｒ１６としては、それぞれ独立に水素原子、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 formula (vi), R 14 , R 15 and R 16 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like), or an alkyl group having 1 to 6 carbon atoms for example, a methyl group, an ethyl group, a propyl group, etc.), - Z 1, or an L 1 -Z 1. Wherein L 1 and Z 1 are the same meaning as L 1 and Z 1 in the above, it is the preferable examples. R 1
As 4 , R 15 and R 16 , each independently, 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 a monomer represented by Formula (iv), R 11 , R 12 and R 13 each independently represent a hydrogen atom or a methyl group, and L 1 is a divalent having an alkylene group or an oxyalkylene structure. Compounds in which X 1 is an oxygen atom or an imino group and Z 1 is a carboxylic acid group are preferable.
Further, as a 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 Compounds which are are preferred.
Furthermore, as the monomer represented by the formula (vi), R 14 , R 15 and R 16 each independently represent a hydrogen atom or a methyl group, and L 1 represents 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, representative examples of the monomers (compounds) represented by the formulas (iv) to (vi) are shown.
Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, and the reaction of succinic anhydride with a compound having an addition-polymerizable double bond and hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate). , A reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with a phthalic anhydride, a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule, and tetrahydroxyphthalic anhydride , A reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with trimellitic anhydride, a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule, and pyromellitic anhydride Of acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 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観点から、高分子化合物の全質量に対して、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 the total mass of the polymer compound from the viewpoint of the interaction with the pigment or the like, the temporal stability, and the permeability to the developer. On the other hand, 0.05 to 90% by mass is preferable, 1.0 to 80% by mass is more preferable, and 10 to 70% by mass is more preferable.
・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％以下がより好ましい。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 is a structural unit containing a graft chain, a hydrophobic structural unit, and a pigment as long as the effects of the present invention are not impaired for the purpose of improving various performances such as image strength. And other structural units having various functions (eg, structural units containing a functional group having an affinity for a solvent described later, etc.) different from the structural unit containing a functional group capable of forming an interaction with etc. Furthermore, you may have.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles and methacrylonitriles and the like.
As the polymer compound, one or more of these other structural units can be used, and the content thereof is preferably 0 to 80% by mass with respect to the total mass of the polymer compound in terms of mass, 60 mass% or less is more preferable. Sufficient pattern formability is maintained in the above range of content.
・高分子化合物の物性
　高分子化合物の酸価は、０ｍｇ～２５０ｍｇＫＯＨ／ｇの範囲であるのが好ましく、１０～２００ｍｇＫＯＨ／ｇの範囲がより好ましく、２０～１２０ｍｇＫＯＨ／ｇの範囲が更に好ましい。
　高分子化合物の酸価が１６０ｍｇＫＯＨ／ｇ以下であれば、硬化膜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 Compound The acid value of the polymer compound is preferably in the range of 0 mg to 250 mg KOH / g, more preferably in the range of 10 to 200 mg KOH / g, and still more preferably in the range of 20 to 120 mg KOH / g.
When the acid value of the polymer compound is 160 mg KOH / g or less, pattern peeling during development when forming a cured film can be more effectively suppressed. When the acid value of the polymer compound is 10 mg KOH / g or more, the alkali developability becomes better. In addition, when the acid value of the polymer compound is 20 mg KOH / g or more, sedimentation of the pigment and the like can be further suppressed, the number of coarse particles can be further reduced, and the temporal stability 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ることで所望の酸価を有する樹脂を得ることができる。 In the present specification, the acid value can be calculated, for example, from the average content of acid groups in a compound. Moreover, resin which has a desired acid value can be obtained by changing content of the structural unit containing the acidic radical which is a structural component of resin.
　高分子化合物の重量平均分子量は、４，０００～３００，０００であるのが好ましく、５，０００～２００，０００であるのがより好ましく、６，０００～１００，０００であるのが更に好ましく、１０，０００～５０，０００であるのが特に好ましい。
　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 4,000 to 300,000, more preferably 5,000 to 200,000, and still more preferably 6,000 to 100,000. Particular preference is given to 10,000 to 50,000.
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、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 Kushimoto Chemical Co., Ltd., “Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (acid group-containing copolymer” manufactured by BYK Chemie ), 111 (phosphate based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer), “BYK-P104, P105 (high molecular weight non-polymer)” Saturated polycarboxylic acid) ", EFKA 4047, 4050 to 4010 to 4165 (polyurethane based), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (manufactured by EFKA) High molecular weight polycarboxylate), 6220 (fatty acid polyaceta) Ter), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) "," ADISPAR PB 821, PB 822, PB 880, PB 881 "manufactured by Ajinomoto Fine Techno Co.," Flower TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co., Ltd. No. 50E, No. 300 (acrylic copolymer), manufactured by Kushimoto Chemical Co., Ltd. “Disparone KS-860, 873 SN, 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyether ester), DA -703-50, DA-705, DA-725 "Kao Corporation" Demol RN, N (Naphtalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) " , "Homogenol L-18 (polymeric polycarboxylic acid)", "Emulgen 92" 930, 935, 985 (polyoxyethylene nonyl phenyl ether) "," Acetamine 86 (stearylamine acetate) ", manufactured by Nippon Lubrizol" Sorsparse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine) , 3000, 12000, 17000, 20000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft copolymer), manufactured by Nikko Chemicals Co., Ltd. "NIKKOL T106 (polyoxyethylene sorbitan Monooleate), MYS-IEX (polyoxyethylene monostearate) ", Hinoac T-8000 E, etc., manufactured by Kawaken Fine Chemicals Co., Ltd., Shin-Etsu Chemical Co., Ltd., organosiloxane polymer, KP-341, Yusho "W 001: cationic surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene Nonionic surfactants such as glycol distearate, sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", "Morita Sangyo" "EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100" , EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 ", San Nopco" Dispers Aid 6, Dispers Aid 8, Dispers Aid 15, De Polymeric dispersants such as Sparse Aid 9100, "ADEKA PLURONIC L 31, F 38, L 42, L 44, L 61, L 64, L 68, L 72, P 72, P 77, P 84, P 87, P 94, L 101, P 103, F 108, L 121, ADEKA" P-123 "and" Ionette (trade name) S-20 "manufactured by Sanyo Chemical Industries, Ltd. 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のも好ましい。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 preferred 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 mg KOH / g or more and an amine value of 5 mg KOH / g or more.
As a commercial item of the amphoteric resin, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK-2001, DISPERBYK-2010, manufactured by BIC Chemie Examples include DISPERBYK-2012, DISPERBYK-2025, BYK-9076, and Ajisame Fine Techno Co., Ltd. Ajisper PB 821, Ajisper PB 822, and Ajisper PB 881 and the like.
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 examples of specific examples of the polymer compound, reference can be made to the polymer compounds described in paragraphs “0127” to “0129” of JP 2013-249417 A, the contents of which are incorporated herein.
　また、分散剤としては、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 dispersant, in addition to the above-mentioned polymer compounds, graft copolymers of paragraphs 0037 to 0115 of JP 2010-106268 A (columns 0075 to 0133 of corresponding US 2011/0124824) can be used. The contents of are incorporated herein by reference.
Moreover, it contains the side chain structure which the acidic group of Unexamined-Japanese-Patent No.2011-153283, Paragraph 0028-0084 (Correspondence US2011 / 02729759 corresponding column 0075-0133 column) joins via a coupling group besides the above. Polymer compounds containing the following components can be used, the contents of which can be incorporated and incorporated herein.
　また、分散剤としては、特開２０１６－１０９７６３号公報の００３３～００４９段落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 dispersant, resins described in paragraphs 0033 to 0049 of JP-A-2016-109763 can also be used, and the contents thereof are incorporated in the present specification.
（アルカリ可溶性樹脂）
　硬化性組成物は、アルカリ可溶性樹脂を含有するのが好ましい。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）を含有する樹脂を意図し、既に説明した分散剤とは異なる樹脂を意図する。
　硬化性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、硬化性組成物の全固形分に対して、１～３０質量％が好ましく、１～１５質量％がより好ましい。
　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のが好ましい。 (Alkali-soluble resin)
The curable composition preferably contains an alkali soluble resin. In the present specification, an alkali-soluble resin is intended to be a resin containing a group that promotes alkali solubility (alkali-soluble group), and is intended to be a resin different from the dispersant described above.
The content of the alkali-soluble resin in the curable composition is not particularly limited, but is preferably 1 to 30% by mass, and more preferably 1 to 15% by mass with respect to the total solid content of the curable composition.
The alkali-soluble resin may be used alone or in combination of two or more. When using 2 or more types of alkali-soluble resin together, it is preferable that total content is in the said 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 the molecule, such as polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide resin, (meth) Acrylic / (meth) acrylamide copolymer resin, an epoxy resin, and a polyimide resin etc. are mentioned.
　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体が挙げられる。
　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、フマル酸などのジカルボン酸、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 copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds.
The unsaturated carboxylic acid is not particularly limited, but monocarboxylic acids such as (meth) acrylic acid, crotonic acid and vinyl acetic acid; itaconic acid, maleic acid and dicarboxylic acids such as fumaric acid or acid anhydride thereof And monohydric carboxylic acid monoesters such as phthalic acid mono (2- (meth) acryloyloxyethyl); 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００２７段落、及び、特開２０１５－６８８９３号公報の００３６～００３７段落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 and the like. Further, the compounds described in paragraph 0027 of JP-A-2010-97210 and in paragraphs 0036 to 0037 of JP-A-2015-68893 can also be used, and the above contents are 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ることができる。 Moreover, it is an ethylenically unsaturated compound which can be copolymerized, Comprising: You may use combining the compound containing an ethylenically unsaturated group in a side chain. 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. You can get it.
　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.
As the said curable group, the curable group which the above-mentioned high molecular compound may contain is mentioned similarly, A preferable range is also the same.
As an alkali-soluble resin containing a curable group, an alkali-soluble resin having a curable group in a side chain is preferable. As an alkali-soluble resin containing a curable group, Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (containing COOH containing polyurethane acrylic oligomer. Diamond Shamrock Co., Ltd.), Biscoat R-264, KS resist 106 All of them are Osaka Organic Chemical Industry Co., Ltd., Cyclomer P series (for example, ACA 230 AA), Plaxcel CF 200 series (all of which are manufactured by Daicel), Ebecryl 3800 (manufactured by Daicel Ornex), And the like.
　アルカリ可溶性樹脂としては、例えば、特開昭５９－４４６１５号、特公昭５４－３４３２７号、特公昭５８－１２５７７号、特公昭５４－２５９５７号、特開昭５４－９２７２３号、特開昭５９－５３８３６号、及び、特開昭５９－７１０４８号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、欧州特許第１２０４０００号、及び、特開２００１－３１８４６３号等の各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号に記載のポリイミド樹脂；等を使用できる。 As the alkali-soluble resin, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-54-92723, JP-A-59- Radical polymers containing a carboxylic acid group in the side chain as described in JP-A-59-3836 and JP-A-59-71048; European Patent No. 993966, European Patent No. 1204000, and JP-A No. 2001-318463 Acetal-modified polyvinyl alcohol-based binder resin containing an alkali-soluble group described in each publication such as U.S. et al .; polyvinyl pyrrolidone; polyethylene oxide; alcohol-soluble nylon, and 2,2-bis- (4-hydroxyphenyl) -propane Polyethers, etc., which are reactants with epichlorohydrin; It can be used, and the like; polyimide resin described in Patent Publication No. 2008/123097.
　アルカリ可溶性樹脂としては、例えば、特開２０１６－７５８４５号公報の０２２５～０２４５段落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 contents are 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することにより得られる樹脂を意図する。
　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ことがある。 A polyimide precursor can also be used as an alkali soluble resin. The polyimide precursor intends a resin obtained by the addition polymerization reaction of a compound containing an acid anhydride group and a diamine compound at 40 to 100 ° C.
As a polyimide precursor, resin containing the repeating unit represented by Formula (1) is mentioned, for example. Examples of the structure of the polyimide precursor include an amic acid structure represented by the following formula (2), a following formula (3) in which the amic acid structure is partially imide ring-closed, and a following formula (4) in which all imide ring closure The polyimide precursor containing the imide structure shown by these) is mentioned.
In the present 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００１１～００３１段落に記載の化合物、特開２０１６－１２２１０１号公報の００２２～００３９段落に記載の化合物、及び、特開２０１６－６８４０１号公報の００６１～００９２段落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。 As specific examples of the polyimide precursor, for example, compounds described in paragraphs 0011 to 0031 of JP 2008-106250 A, compounds described in paragraphs 0022 to 0039 of JP 2016-122101 A, and JP The compounds described in paragraphs [0061] to [0092] of 2016-68401, and the like are included, and the above contents are incorporated in the present specification.
　アルカリ可溶性樹脂は、硬化性組成物を用いて得られるパターン状の硬化膜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。
　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００５０段落に記載された樹脂、特開２０１５－１８７６７６号公報の００５８段落に記載された樹脂、及び、特開２０１４－１０６３２６号公報の００１２～００１３段落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 alkali-soluble resin contains at least one selected from the group consisting of a polyimide resin and a polyimide precursor in that the pattern shape of the cured film in a pattern obtained by using the curable composition is more excellent. Is also preferred.
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. The resins described in the paragraphs [0012] to [0013] and the like are mentioned, and the above contents are incorporated in the present specification.
（エチレン性不飽和基を含有する樹脂）
　得られる硬化膜の断面形状の矩形性がより優れる点から、本発明の製造方法に用いられる硬化性組成物は、エチレン性不飽和基を含有する樹脂を含有するのが好ましい。エチレン性不飽和基を含有する樹脂は、分散剤であってもよくアルカリ可溶性樹脂であってもよい。また、分散剤又はアルカリ可溶性樹脂以外の樹脂であってもよい。
　硬化性組成物中のエチレン性不飽和基を含有する樹脂の含有量の下限は、硬化性組成物が含有する樹脂全体の質量に対して、４０質量％以上が好ましく、４５質量％以上がより好ましく、５０質量％以上が更に好ましい。
　硬化性組成物中のエチレン性不飽和基を含有する樹脂の含有量の上限は、硬化性組成物が含有する樹脂全体の質量に対して、１００質量％以下が好ましい。
　なお、エチレン性不飽和基を含有する樹脂とは、１分子の中にエチレン性不飽和基を１個以上含有する樹脂をいう。 (Resin containing an ethylenically unsaturated group)
It is preferable that the curable composition used for the manufacturing method of this invention contains resin containing an ethylenically unsaturated group from the point which the rectangularity of the cross-sectional shape of the cured film obtained is more excellent. The resin containing an ethylenically unsaturated group may be a dispersant or an alkali soluble resin. Moreover, resin other than a dispersing agent or alkali-soluble resin may be sufficient.
The lower limit of the content of the resin having an ethylenically unsaturated group in the curable composition is preferably 40% by mass or more, more preferably 45% by mass or more based on the mass of the entire resin contained in the curable composition. Preferably, 50% by mass or more is more preferable.
The upper limit of the content of the resin containing an ethylenically unsaturated group in the curable composition is preferably 100% by mass or less based on the total mass of the resin contained in the curable composition.
In addition, resin containing an ethylenically unsaturated group means resin which contains one or more ethylenically unsaturated groups in 1 molecule.
　エチレン性不飽和基を含有する樹脂の含有量は原料の仕込み量から計算してもよい。 The content of the resin containing an ethylenically unsaturated group may be calculated from the amount of raw materials charged.
　また、樹脂全質量に対する、エチレン性不飽和基の含有量としては、特に制限されないが、０．００１～５．００ｍｍｏｌ／ｇが好ましく、０．１０～３．００ｍｍｏｌ／ｇがより好ましく、０．２６～２．５０ｍｍｏｌ／ｇが更に好ましい。エチレン性不飽和基含有量が、０．１０～３．００ｍｍｏｌ／ｇの範囲内であると、硬化性組成物を用いて得られる硬化膜の断面形状の矩形性がより優れる。
　なお、上記樹脂全質量とは、硬化性組成物に含まれる樹脂の合計質量を意図し、例えば、エチレン性不飽和基を含有する樹脂とエチレン性不飽和基を含有しない樹脂とを硬化性組成物が含有する場合、両者の合計質量が上記樹脂の合計質量に該当する。
　したがって、上記エチレン性不飽和基の含有量は、樹脂全質量に対する、エチレン性不飽和基を含有する樹脂中のエチレン性不飽和基の含有量を表す。
　また、樹脂とは、硬化性組成物中に溶解している成分であって、重量平均分子量が２０００超である成分を意図する。 In addition, the content of the ethylenically unsaturated group is not particularly limited, but is preferably 0.001 to 5.00 mmol / g, more preferably 0.10 to 3.00 mmol / g, and the like. More preferred is 26 to 2.50 mmol / g. When the content of the ethylenically unsaturated group is in the range of 0.10 to 3.00 mmol / g, the rectangularity of the cross-sectional shape of a cured film obtained using the curable composition is more excellent.
In addition, the said resin total mass intends the total mass of resin contained in a curable composition, for example, curable composition of resin containing an ethylenically unsaturated group, and resin which does not contain an ethylenically unsaturated group When the substance contains, the total mass of both corresponds to the total mass of the above-mentioned resin.
Therefore, the content of the above-mentioned ethylenically unsaturated group represents the content of the ethylenically unsaturated group in the resin containing the ethylenically unsaturated group with respect to the total mass of the resin.
Moreover, resin is a component which is melt | dissolving in a curable composition, Comprising: The component whose weight average molecular weight is more than 2000 is intended.
　本明細書において、エチレン性不飽和基含有量のことを「Ｃ＝Ｃ価」という場合がある。
　本明細書において、エチレン性不飽和基含有量（Ｃ＝Ｃ価）は、以下の方法により測定される値を意図する。なお、エチレン性不飽和基を含有する樹脂を合成する場合、原料の仕込み量から計算することにより、測定に代えることができる。
　また、硬化性組成物が複数種類の樹脂を含有しており、かつ、各樹脂のＣ＝Ｃ価が明らかである場合、各樹脂の配合比から、硬化性組成物が含有する樹脂全質量としてのＣ＝Ｃ価を計算して求めてもよい。 In the present specification, the content of the ethylenically unsaturated group may be referred to as “C = C value”.
In the present specification, the ethylenically unsaturated group content (C = C number) is intended to be a value measured by the following method. In addition, when synthesize | combining resin containing an ethylenically unsaturated group, it can replace with measurement by calculating from the preparation amount of a raw material.
In addition, when the curable composition contains a plurality of resins, and the C = C value of each resin is clear, the total weight of the resin contained in the curable composition is determined from the compounding ratio of each resin. You may calculate and obtain | require C = C number of.
　樹脂のエチレン性不飽和基含有量を測定する方法としては、エチレン性不飽和基が（メタ）アクリロイル基である場合、以下の方法により測定する。
　まず、遠心分離法によって硬化性組成物中の固体成分（黒色顔料等）を沈殿させて残った液体成分を分取する。更に、得られた液体成分から、ＧＰＣ法で重量平均分子量が２０００超である成分を分取し、これを測定対象の樹脂とする。
　次に、測定対象となる樹脂０．２５ｍｇをＴＨＦ（ｔｅｔｒａｈｙｄｒｏｆｕｒａｎ）５０ｍＬに溶解させ、更にメタノール１５ｍＬを添加し、溶液を作製する。
　作製した溶液に、４Ｎ　水酸化ナトリウム水溶液を１０ｍＬ加え、混合液を得る。次に、上記混合液を液温４０℃で２時間撹拌する。更に、混合液に４Ｎ　メタンスルホン酸水溶液を１０．２ｍＬ添加し、撹拌する。更に、混合液に脱塩水を５ｍＬ添加し、続けてメタノール２ｍＬを添加し、測定溶液を調製する。
　測定溶液中の（メタ）アクリル酸の含有量を、ＨＰＬＣ（ｈｉｇｈ　ｐｅｒｆｏｒｍａｎｃｅ　ｌｉｑｕｉｄ　ｃｈｒｏｍａｔｏｇｒａｐｈｙ）法（絶対検量線法）により測定し、エチレン性不飽和基含有量を計算する。
ＨＰＬＣ測定条件カラム：Ｐｈｅｎｏｍｅｎｅｘ製Ｓｙｎｅｒｇｉ　４μ　Ｐｏｌａｒ－ＲＰ　８０Ａ（４．６ｍｍ×２５０ｍｍ）
カラム温度：４０℃
流速：１．０ｍＬ／ｍｉｎ
検出器波長：２１０ｎｍ
溶離液：ＴＨＦ（テトラヒドロフラン、ＨＰＬＣ用）５５／バッファー水　４５＊バッファー水…０．２％－リン酸、０．２％－トリエチルアミン水溶液注入量：５μＬ As a method of measuring the ethylenically unsaturated group content of the resin, when the ethylenically unsaturated group is a (meth) acryloyl group, it is measured by the following method.
First, solid components (black pigment and the like) in the curable composition are precipitated by centrifugation, and the remaining liquid component is separated. Further, from the obtained liquid component, a component having a weight average molecular weight of more than 2000 is separated by a GPC method, and this is used as a resin to be measured.
Next, 0.25 mg of a resin to be measured is dissolved in 50 mL of THF (tetrahydrofuran), and 15 mL of methanol is further added to prepare a solution.
To the prepared solution, 10 mL of 4N aqueous sodium hydroxide solution is added to obtain a mixture. Next, the mixture is stirred at a liquid temperature of 40 ° C. for 2 hours. Further, 10.2 mL of 4 N aqueous methanesulfonic acid solution is added to the mixture and stirred. Furthermore, 5 mL of demineralized water is added to the mixture, followed by 2 mL of methanol to prepare a measurement solution.
The content of (meth) acrylic acid in the measurement solution is measured by a high performance liquid chromatography (HPLC) method (absolute calibration method) to calculate the ethylenically unsaturated group content.
HPLC measurement conditions Column: Phenomenex Synergi 4μ Polar-RP 80A (4.6 mm × 250 mm)
Column temperature: 40 ° C
Flow rate: 1.0 mL / min
Detector wavelength: 210 nm
Eluent: THF (tetrahydrofuran, for HPLC) 55 / buffer water 45 * buffer water ... 0.2%-phosphoric acid, 0.2%-triethylamine aqueous solution injection amount: 5 μL
　樹脂のエチレン性不飽和基含有量を測定する方法としては、エチレン性不飽和基が（メタ）アクリロイル基以外、又は、（メタ）アクリロイル基と、（メタ）アクリロイル基以外の基との併用である場合、上述の方法で分取した測定対象の樹脂について臭素化を測定する方法が挙げられる。臭素価は、ＪＩＳ　Ｋ２６０５：１９９６に準拠して測定する。
　なお、ここで、エチレン性不飽和基含有量は、上記臭素価で得られた測定する樹脂１００ｇに対して付加した臭素（Ｂｒ２）のグラム数（ｇＢｒ２／１００ｇ）から、樹脂１ｇ当たりの付加した臭素（Ｂｒ２）のモル数に変換した値である。 As a method of measuring the ethylenically unsaturated group content of the resin, the ethylenically unsaturated group is a combination of a (meth) acryloyl group other than (meth) acryloyl group and a group other than a (meth) acryloyl group and a (meth) acryloyl group In some cases, a method of measuring the bromination of the resin to be measured that has been separated by the above-mentioned method may be mentioned. The bromine number is measured in accordance with JIS K2605: 1996.
Here, ethylenically unsaturated group content, bromine was added to the resin 100g of measurements obtained in bromine number (Br 2) grams of (gBr 2 / 100g), the resin per 1g It is a value converted to the number of moles of added bromine (Br 2 ).
＜重合開始剤＞
　硬化性組成物は、重合開始剤を含有するのが好ましい。
　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。
　硬化性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、硬化性組成物の全固形分に対して０．５～２０質量％が好ましい。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のが好ましい。 <Polymerization initiator>
The curable composition preferably contains a polymerization initiator.
The polymerization initiator is not particularly limited, and known polymerization initiators can be used. As a polymerization initiator, a photoinitiator, a thermal-polymerization initiator etc. are mentioned, for example, A photoinitiator is preferable. In addition, as a polymerization initiator, what is called a radical polymerization initiator is preferable.
The content of the polymerization initiator in the curable composition is not particularly limited, but it is preferably 0.5 to 20% by mass with respect to the total solid content of the curable composition. The polymerization initiator may be used alone or in combination of two or more. When two or more polymerization initiators are used in combination, the total content is preferably in 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などを挙げられる。 (Thermal polymerization initiator)
As a thermal polymerization initiator, for example, 2,2′-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismaleonitrile, and dimethyl- (2,2 ′)-azobis (2) Azo compounds such as -methyl propionate) [V-601], and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
Specific examples of the polymerization initiator include, for example, the polymerization initiators described on pages 65 to 148 of "UV Curing System" (Senior Technology Center Co., Ltd., published by General Technology Center, Inc.) published by Seiji Kato .
（光重合開始剤）
　上記硬化性組成物は光重合開始剤を含有するのが好ましい。
　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種含有しているのが好ましい。 (Photopolymerization initiator)
The curable composition preferably contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as polymerization of the polymerizable compound can be initiated, and known photopolymerization initiators can be used. As the photopolymerization initiator, for example, a photopolymerization initiator having photosensitivity to an ultraviolet light region to a visible light region is preferable. In addition, it may be an activator that produces an action with photoexcited sensitizers to generate active radicals, and may be an initiator that initiates cationic polymerization depending on the type of the polymerizable compound.
The photopolymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least 50 in the range of 300 to 800 nm (more preferably 330 to 500 nm).
　硬化性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、硬化性組成物の全固形分に対して、０．５～２０質量％が好ましい。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のが好ましい。 The content of the photopolymerization initiator in the curable composition is not particularly limited, but it is preferably 0.5 to 20% by mass with respect to the total solid content of the curable composition. The photopolymerization initiator may be used singly or in combination of two or more. When using 2 or more types of photoinitiators together, it is preferable that total content is in the said 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もの、オキサジアゾール骨格を含有するもの、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。 As the photopolymerization initiator, for example, a halogenated hydrocarbon derivative (for example, one containing a triazine skeleton, one containing an oxadiazole skeleton, etc.), an acylphosphine compound such as an 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 in the present specification.
　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、又は、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、又は、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-based initiator described in Japanese Patent No. 4225898 can also 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 Corporation) can be used.
As the aminoacetophenone compound, for example, commercially available products IRGACURE-907, IRGACURE-369, or IRGACURE-379EG (trade name: all manufactured by BASF Corp.) 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 wave light source having a wavelength of 365 nm or a wavelength of 405 nm can also be used.
As an acyl phosphine compound, IRGACURE-819 which is a commercial item, or IRGACURE-TPO (trade name: all manufactured by BASF Corporation) 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、硬化性組成物中における黒色顔料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号公報記載の化合物、特開２０００－８００６８号公報記載の化合物、又は、特開２００６－３４２１６６号公報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号公報の各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 compound As a photoinitiator, an oxime ester-type polymerization initiator (oxime compound) is more preferable. In particular, oxime compounds are preferable because they have high sensitivity and high polymerization efficiency, and the black pigment content in the curable composition is easily designed to be high.
As specific examples of the oxime compound, compounds described in JP-A-2001-233842, compounds described in JP-A-2000-80068, or compounds described in JP-A-2006-342166 can be used.
Examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 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 Examples include carbonyloxyimino-1-phenylpropan-1-one and the like.
Also, J.J. C. S. Perkin II (1979) pp. 1653-1660), J.F. 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, and compounds described in JP-A-2000-80068, JP-A-2004-534797, and JP-A-2006-342166, etc. are also listed. Be
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. In addition, TR-PBG-304 (made by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Akuls NCI-831, Adeka Ark's NCI-930 (made by ADEKA), or N-1919 (carbazole oxime ester skeleton containing light) An initiator (made by 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号記載の化合物；国際公開特許２００９－１３１１８９号公報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号公報に記載の化合物；４０５ｎｍに吸収極大を有し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。 Further, as oxime compounds other than those described above, compounds described in JP-A-2009-519904 in which an oxime is linked to the carbazole N-position; compounds described in US Pat. Compounds described in JP-A-2010-15025 and U.S. Patent Publication 2009-292039 in which a nitro group is introduced at a dye site; a ketoxime compound described in WO 2009-131189; and a triazine skeleton and an oxime skeleton The compound described in US Pat. No. 7,556,910 contained in the same molecule; the compound described in JP-A 2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source; etc. Good.
For example, paragraphs 0274 to 0275 of JP-A-2013-29760 can be referred to, the contents of which are incorporated herein.
Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferable. Whether the N-O bond of the oxime compound is an oxime compound of (E) form, an oxime compound of (Z) form, or a mixture of (E) form and (Z) form Good.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　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価の非金属原子団であるのが好ましい。
　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 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 Formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetal atomic group.
Examples of the monovalent nonmetal atom 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. Also, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by the other 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, an aryl group and the like.
In the 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. As the substituent, the above-mentioned substituents can be exemplified.
In the 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. As the substituent, the above-mentioned substituents can be exemplified.
　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号公報記載の化合物；特表２０１４－５００８５２号公報記載の化合物２４、３６～４０；及び、特開２０１３－１６４４７１号公報記載の化合物（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。 As a photoinitiator, the oxime compound containing a fluorine atom can also be used. As specific examples of the oxime compound containing a fluorine atom, compounds described in JP-A-2010-262028; Compounds 24 and 36 to 40 described in JP-A-2014-500852; and JP-A-2013-164471 Compounds (C-3); 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。 Compounds represented by the following general formulas (1) to (4) can also be used as the photopolymerization initiator.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　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 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 R 7 represents an arylalkyl group having 7 to 30 carbon atoms, and when R 1 and R 2 are phenyl groups, the phenyl groups may be bonded to form a fluorene group, and R 3 and R 4 are each independently 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, and X represents a direct bond or carbonyl Indicates 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 , 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 4 to carbon atoms 20 heterocyclic groups, 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 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, or carbon And represents a heterocyclic group of 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 , -CSOR 6 , -CN, a halogen atom, Or 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 And 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、それぞれ独立に、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、それぞれ独立に、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００７６～００７９段落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こととする。 In the above formulas (1) and (2), R 1 and R 2 are each independently 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 each independently 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, for example, compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated herein by reference.
　上記硬化性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。また、オキシム化合物としては、国際公開第２０１５－０３６９１０号の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。 The specific example of the oxime compound preferably used for the said curable composition is shown below. In addition, as the oxime compound, the compounds described in Table 1 of WO 2015-036910 can also be used, and the above contents are incorporated herein.
Figure JPOXMLDOC01-appb-C000018
 
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000018
 
Figure JPOXMLDOC01-appb-C000019
　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のが好ましく、３６０～４８０ｎｍの波長領域に極大吸収波長を有するのがより好ましく、３６５ｎｍ及び４０５ｎｍの波長の吸光度が高いのが更に好ましい。
　オキシム化合物の３６５ｎｍ又は４０５ｎｍにおけるモル吸光係数は、感度の観点から、１，０００～３００，０００であるのが好ましく、２，０００～３００，０００であるのがより好ましく、５，０００～２００，０００であるのが更に好ましい。
　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、酢酸エチル溶媒を用い、０．０１ｇ／Ｌの濃度で測定するのが好ましい。
　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 range of 350 to 500 nm, more preferably a maximum absorption wavelength in a wavelength range of 360 to 480 nm, and still more preferably a high absorbance at 365 nm and 405 nm. .
From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, 5,000 to 200, More preferably, it is 000.
The molar absorptivity of the compound can be measured by a known method, for example, using an ethyl acetate solvent at a concentration of 0.01 g / L with an ultraviolet-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian). Is preferred.
You may use a photoinitiator in combination of 2 or more types as needed.
　また、光重合開始剤としては、特開第２００８－２６０９２７号公報の００５２段落、特開第２０１０９７２１０号公報の００３３～００３７段落、特開第２０１５－６８８９３号公報の００４４段落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。 Further, as the photopolymerization initiator, compounds described in paragraph 0052 of JP-A-2008-260927, paragraphs 0033 to 0037 of JP-A-201097210, and paragraph 0044 of JP-A-2015-68893 are also used. The above content is incorporated herein.
＜重合禁止剤＞
　硬化性組成物は、重合禁止剤を含有するのが好ましい。
　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。
　なかでも、硬化性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 curable composition preferably contains a polymerization inhibitor.
The polymerization inhibitor is not particularly limited, and known polymerization inhibitors can be used. Examples of the polymerization inhibitor include phenolic polymerization inhibitors (eg, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4-methoxynaphthol etc .; hydroquinone polymerization inhibitors (eg Hydroquinone, 2,6-di-tert-butyl hydroquinone, etc .; quinone type polymerization inhibitors (eg, benzoquinone etc.); 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.
Among them, a phenol type polymerization inhibitor or a free radical type polymerization inhibitor is preferable in that the curable composition has more excellent effects.
　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。
　硬化性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、硬化性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のが好ましい。 The effect of the polymerization inhibitor is remarkable when used together with a resin containing a curable group.
The content of the polymerization inhibitor in the curable composition is not particularly limited, but is preferably 0.0001 to 0.5% by mass, and more preferably 0.001 to 0.2%, based on the total solid content of the curable composition. % By mass is more preferred. The polymerization inhibitor may be used alone or in combination of two or more. When two or more polymerization inhibitors are used in combination, the total content is preferably within the above range.
＜界面活性剤＞
　硬化性組成物は、界面活性剤を含有してもよい。界面活性剤は、硬化性組成物の塗布性向上に寄与する。
　上記硬化性組成物が、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、硬化性組成物の全固形分に対して、０．００１～２．０質量％が好ましい。
　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のが好ましい。 <Surfactant>
The curable composition may contain a surfactant. The surfactant contributes to the improvement of the coatability of the curable composition.
When the curable composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the curable composition.
The surfactant may be used alone or in combination of two or more. When two or more surfactants are used in combination, the total amount is preferably in 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 fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.
　例えば、硬化性組成物がフッ素系界面活性剤を含有することで、硬化性組成物の液特性（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硬化性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ることにより、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 curable composition contains a fluorine-based surfactant, liquid properties (in particular, fluidity) of the curable composition are further improved. That is, in the case of forming a film using a curable composition containing a fluorine-based surfactant, the wettability to the surface to be coated is improved by reducing the interfacial tension between the surface to be coated and the coating liquid. The coating property on the surface to be coated is improved. For this reason, even in the case where a thin film of about several μm is formed with a small amount of liquid, it is effective in that film formation with uniform thickness with small thickness unevenness can be more suitably performed.
　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％がさらに好ましい。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、硬化性組成物中における溶解性も良好である。 The content of fluorine in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 7 to 25% by mass. The fluorine-based surfactant having a fluorine content in this range is effective in terms of the uniformity of the thickness of the coating film and / or the liquid saving property, and the solubility in the curable composition is also good. .
　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）製）；フロラードＦＣ４３０、同ＦＣ４３１、及び、同ＦＣ１７１（以上、住友スリーエム（株）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）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 fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F44, R30, F437, F475, F479, and the like. The same F482, the same F554, and the same F780 (above, DIC Corporation); Florard FC430, the same FC431, and the same FC171 (above, Sumitomo 3M Co., Ltd.); Surfron S-382, the same SC-101 , SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by Asahi Glass Co., Ltd.) And PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA Corporation).
A block polymer can also be used as the fluorine-based surfactant, and as a specific example, for example, compounds described in JP-A No. 2011-89090 can be mentioned.
＜紫外線吸収剤＞
　硬化性組成物は、紫外線吸収剤を含有してもよい。これにより、硬化膜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）など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、硬化性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。 <UV absorber>
The curable composition may contain a UV absorber. Thereby, the shape of the pattern of a cured film can be made more excellent (fine) shape.
As a UV absorber, UV absorbers of salicylate type, benzophenone type, benzotriazole type, substituted acrylonitrile type and triazine type can be used. As specific examples thereof, the compounds of paragraphs 0137 to 0142 of JP 2012-068418 A (corresponding to paragraphs 0251 to 0254 of corresponding US 2012/0068292) can be used, and the contents thereof can be incorporated and incorporated herein. .
In addition, diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by Daito Chemical Industries, trade name: UV-503) is preferably used.
Examples of the ultraviolet absorber include compounds exemplified in paragraphs [0134] to [0148] of JP-A-2012-32556.
The content of the UV absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, still more preferably 0.1 to 5% by mass, based on the total solid content of the curable composition. preferable.
＜シランカップリング剤＞
　硬化性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以下であるのが好ましく、４以下であるのがより好ましい。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。
　また、基板上に硬化膜を形成する場合、シランカップリング剤は基板と硬化膜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）を含まないのが好ましく、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のが望ましい。 <Silane coupling agent>
The curable composition may contain a silane coupling agent.
The silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule. In addition, hydrolysable groups, such as an alkoxy group, are couple | bonded with the silicon atom.
The hydrolyzable group is a substituent which is directly bonded to a silicon atom and can form a siloxane bond by hydrolysis reaction and / or condensation reaction. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group are mentioned, for example. When the hydrolyzable group contains a carbon atom, the carbon number thereof is preferably 6 or less, more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
When a cured film is formed on a substrate, the silane coupling agent improves the adhesion between the substrate and the cured film, so fluorine atoms and silicon atoms (but excluding silicon atoms to which a hydrolyzable group is bonded) It is preferable not to contain, and a fluorine atom, a silicon atom (but excluding a silicon atom to which a hydrolyzable group is bonded), an alkylene group substituted with a silicon atom, a linear alkyl group having 8 or more carbon atoms, It is desirable not to include a branched alkyl group having 3 or more carbon atoms.
　上記硬化性組成物中におけるシランカップリング剤の含有量は、硬化性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。
　上記硬化性組成物は、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。硬化性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 curable composition is preferably 0.1 to 10% by mass, and more preferably 0.5 to 8% by mass, relative to the total solid content in the curable composition. 1.0 to 6% by mass is more preferable.
The said curable composition may contain the silane coupling agent individually by 1 type, and may contain 2 or more types. When a curable composition contains 2 or more types of silane coupling agents, the sum total should just be in the said 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。 As a silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, Vinyl trimethoxysilane, and vinyl triethoxysilane etc. are mentioned.
＜溶剤＞
　硬化性組成物は、溶剤を含有するのが好ましい。
　溶剤としては特に制限されず公知の溶剤を使用できる。
　硬化性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、硬化性組成物の固形分が１０～９０質量％となるように調整されるのが好ましく、１５～９０質量％となるように調整されるのがより好ましい。
　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、硬化性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のが好ましい。 <Solvent>
The curable composition preferably contains a solvent.
The solvent is not particularly limited and known solvents can be used.
Although the content of the solvent in the curable composition is not particularly limited, it is preferably adjusted so that the solid content of the curable composition is 10 to 90% by mass, and is 15 to 90% by mass. It is more preferable to be adjusted.
The solvents may be used alone or in combination of two or more. When using 2 or more types of solvents together, it is preferable to adjust so that the total solid of a curable composition may become in the said range.
　溶剤としては、例えば、水、及び、有機溶剤が挙げられる。
　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、これらに限定されない。 As a solvent, water and an organic solvent are mentioned, for example.
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, 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 Ethyl 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, butyl acetate, Examples thereof include, but are not limited to, methyl lactate, N-methyl-2-pyrrolidone, and ethyl lactate.
〔硬化性組成物の製造方法〕
　硬化性組成物は、まず、黒色顔料及び着色剤を分散させた分散組成物を製造し、得られた分散組成物を更にその他の成分と混合して硬化性組成物とするのが好ましい。
　分散組成物は、黒色顔料、着色剤、樹脂（好ましくは分散剤）、及び、溶剤を混合して調製するのが好ましい。また、分散組成物に重合禁止剤を含有させるのも好ましい。 [Method of producing curable composition]
In the curable composition, it is preferable to first prepare a dispersion composition in which a black pigment and a colorant are dispersed, and further mix the obtained dispersion composition with other components to obtain a curable composition.
The dispersion composition is preferably prepared by mixing a black pigment, a colorant, a resin (preferably a dispersant), and a solvent. It is also preferable to incorporate a polymerization inhibitor in the dispersion composition.
　上記分散組成物は、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 dispersion 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 emulsifying device, a wet crusher, a wet dispersing machine or the like).
　硬化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 the preparation of the curable composition, each component may be blended at one time, or each component may be sequentially blended after being dissolved or dispersed in a solvent. In addition, the order of introduction and working conditions at the time of blending are not particularly limited.
　硬化性組成物は、異物の除去及び欠陥の低減などの目的で、フィルタで濾過するのが好ましい。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限定されることなく使用できる。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。この範囲とすることにより、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など、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。
　硬化性組成物は、金属、ハロゲンを含む金属塩、酸、アルカリ等の不純物を含まないのが好ましい。これら材料に含まれる不純物の含有量としては、１ｐｐｍ以下が好ましく、１ｐｐｂ以下がより好ましく、１００ｐｐｔ以下が更に好ましく、１０ｐｐｔ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 curable composition is preferably filtered through a filter for the purpose of removing foreign matter and reducing defects. As a filter, if it is a filter conventionally used for filtration applications etc., it can be used, without being limited in particular. 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 ultrahigh molecular weight) such as polyethylene and polypropylene (PP) can be mentioned. . Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The pore size of the filter is preferably 0.1 to 7.0 μm, more preferably 0.2 to 2.5 μm, still more preferably 0.2 to 1.5 μm, and particularly preferably 0.3 to 0.7 μm. By setting this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing filter clogging of the pigment (including the black pigment).
When using filters, different filters may be combined. At this time, the filtering with the first filter may be performed only once or may be performed twice or more. When different filters are combined to perform filtering twice or more, it is preferable that the second and subsequent pore sizes be the same or larger than the pore size of the first filtering. Moreover, you may combine the 1st filter of the hole diameter which is different within the range mentioned above. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, it is possible to select from, for example, various filters provided by Nippon Pall Co., Advantec Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., and the like.
The second filter can use a filter formed of the same material as the first filter described above. The pore size of the second filter is preferably 0.2 to 10.0 μm, more preferably 0.2 to 7.0 μm, and still more preferably 0.3 to 6.0 μm.
The curable composition is preferably free of impurities such as metals, metal salts containing halogen, acids, alkalis and the like. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially not including (less than detection limit of measuring device Is most preferred.
The above impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).
［硬化膜の製造方法］
　上記光硬化性組成物を用いて形成された硬化性組成物層（組成物層）を硬化してパターン状の硬化膜を得ることができる。
　より具体的には、本発明の製造方法は、上述の硬化性組成物を用いて、膜厚１．５μｍあたりの波長３６５ｎｍにおける光学濃度Ａが２．６０～１０．００となり、かつ、膜厚１．５μｍあたりの波長５５０ｎｍにおける光学濃度Ｂが２．００～１０．００となる硬化性組成物層を形成する工程（硬化性組成物層形成工程）と、
　上記硬化性組成物層を酸素濃度が３０～５０体積％の条件下で露光する工程（露光工程）と、
　上記露光後の上記硬化性組成物層を現像して硬化膜を形成する工程（現像工程）と、
　を含有する。
　また、所望により現像工程の後にポストベークを行ってもよい。
　以下、上記の各工程について説明する。 [Method of producing a cured film]
The curable composition layer (composition layer) formed using the above-mentioned photocurable composition can be cured to obtain a cured film in a pattern.
More specifically, the production method of the present invention makes it possible to obtain an optical density A of 2.60 to 10.00 at a wavelength of 365 nm per 1.5 μm of film thickness using the above-described curable composition, and Forming a curable composition layer having an optical density B at a wavelength of 550 nm per 1.5 μm of 2.00 to 10.00 (curable composition layer forming step),
Exposing the curable composition layer under conditions of an oxygen concentration of 30 to 50% by volume (exposure step);
Developing the curable composition layer after the exposure to form a cured film (developing step);
Contains
Also, if desired, post-baking may be performed after the developing step.
Hereinafter, each of the above steps will be described.
〔硬化性組成物層形成工程〕
　硬化性組成物層形成工程においては、露光に先立ち、支持体等の上に、硬化性組成物を付与して硬化性組成物の層（硬化性組成物層）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。 [Curable Composition Layer Forming Step]
In the curable composition layer forming step, prior to exposure, the curable composition is applied on a support or the like to form a layer of the curable composition (curable composition layer). As a support, for example, a substrate for a solid-state imaging device in which an imaging device (light receiving device) such as a charge coupled device (CCD) or a complementary metal-oxide semiconductor (CMOS) is provided on a substrate (for example, a silicon substrate) it can. In addition, if necessary, a subbing layer may be provided on the support for the purpose of improving adhesion with the upper layer, preventing diffusion of substances, flattening of the substrate surface, and the like.
　支持体上への硬化性組成物の適用方法としては、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、又は、スクリーン印刷法等の各種の塗布方法を適用できる。硬化性組成物層の膜厚としては、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硬化性組成物層の乾燥（プリベーク）は、ホットプレート、オーブン等で５０～１４０℃の温度で１０～３００秒で行うことができる。 As a method of applying the curable composition on the support, various coating methods such as a slit coating method, an inkjet method, a spin coating method, a cast coating method, a roll coating method, or a screen printing method can be applied. The thickness of the curable composition layer is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and still more preferably 0.2 to 3 μm. Drying (pre-baking) of the curable composition layer coated on the support can be carried out at a temperature of 50 to 140 ° C. for 10 to 300 seconds with a hot plate, an oven or the like.
＜硬化性組成物層＞
　本発明の製造方法において、硬化性組成物層（好ましくは乾燥（プリベーク）された硬化性組成物層、又は、自然乾燥された硬化性組成物層）は、光学濃度Ａが２．６０～１０．００であり、得られる硬化膜の断面形状の矩形性がより優れる点から、２．８０～４．００であるのが好ましく、２．９０～３．５０であるのがより好ましい。
　同様に、光学濃度Ｂは、２．００～１０．００であり、得られる硬化膜の断面形状の矩形性がより優れる点から、２．５０～７．００が好ましく、２．８０～６．５０がより好ましい。
　また、光学濃度Ａに対する光学濃度Ｂの比（光学濃度Ｂ／光学濃度Ａ）は０．３～３．５が好ましく、０．５～２．０がより好ましく、０．８～１．２が更に好ましい。 <Curable composition layer>
In the production method of the present invention, the curable composition layer (preferably a dried (prebaked) curable composition layer or a naturally dried curable composition layer) has an optical density A of 2.60 to 10 It is preferably 2.00 to 4.00, and more preferably 2.90 to 3.50 from the viewpoint that the rectangularity of the cross-sectional shape of the resulting cured film is further improved.
Similarly, the optical density B is from 2.00 to 10.00, and it is preferably 2.50 to 7.00, and 2.80 to 6 from the viewpoint that the rectangularity of the cross-sectional shape of the obtained cured film is more excellent. 50 is more preferred.
The ratio of optical density B to optical density A (optical density B / optical density A) is preferably 0.3 to 3.5, more preferably 0.5 to 2.0, and 0.8 to 1.2. More preferable.
　なお、本明細書において、光学濃度Ａ及び光学濃度Ｂの測定方法としては、まず、ガラス基板上に乾燥された硬化性組成物層を形成して、透過濃度計（Ｘ－ｒｉｔｅ　３６１Ｔ（ｖｉｓｕａｌ）ｄｅｎｓｉｔｏｍｅｔｅｒ）を用いて測定し、測定箇所の膜厚も測定し、膜厚１．５μｍあたりの光学濃度を算出する。
　なお、硬化性組成物層の膜厚が１．５μｍである場合、透過濃度計で測定した値をそのまま使用できる。 In the present specification, as a method of measuring the optical density A and the optical density B, first, a curable composition layer dried on a glass substrate is formed, and a transmission densitometer (X-rite 361 T (visual) is provided. The film thickness is also measured using a densitometer, and the optical density per 1.5 μm of film thickness is calculated.
In addition, when the film thickness of a curable composition layer is 1.5 micrometers, the value measured with the transmission densitometer can be used as it is.
〔露光工程〕
　露光工程では、硬化性組成物層を酸素濃度が３０～５０体積％の条件下で露光できればよく、例えば、ステッパー等の露光装置を用い、所定のマスクパターンを有するマスクを介して硬化性組成物層をパターン露光する態様が挙げられる。
　露光の際の光としては、ｇ線、ｈ線、ｉ線、ＫｒＦ線（エキシマレーザー線）、及びＡｒＦ線（エキシマレーザー線）から選ばれる光が挙げられる。
　放射照度は、２００００～５００００Ｗ／ｍ２が好ましく、２５０００～４００００Ｗ／ｍ２がより好ましい。 [Exposure process]
In the exposure step, the curable composition layer may be exposed under conditions of an oxygen concentration of 30 to 50% by volume. For example, using an exposure apparatus such as a stepper, the curable composition may be through a mask having a predetermined mask pattern. The aspect which pattern-exposes a layer is mentioned.
Examples of light at the time of exposure include light selected from g-rays, h-rays, i-rays, KrF rays (excimer laser rays), and ArF rays (excimer laser rays).
Irradiance is preferably 20000 ~ 50000W / m 2, more preferably 25000 ~ 40000W / m 2.
　露光工程は、酸素濃度が３０～５０体積％の条件下で行う。
　このような条件下で露光を行うことで、得られる硬化膜の断面形状の矩形性が良好となる。
　この酸素濃度の制御は、通常の手法によって行うことができる。例えば、露光装置を内包した装置室内を密閉構造として、所望の割合の酸素ガスと窒素ガスとを供給して、室内の酸素濃度を調節できる。または、露光装置の室内に所定流量の酸素ガスと窒素ガスとを流通させ、露光雰囲気が所定の酸素濃度とするようにしてもよい。 The exposure step is performed under the conditions of an oxygen concentration of 30 to 50% by volume.
By performing exposure under such conditions, the rectangularity of the cross-sectional shape of the obtained cured film is improved.
Control of this oxygen concentration can be performed by a usual method. For example, the apparatus chamber containing the exposure apparatus has a sealed structure, and oxygen gas and nitrogen gas in a desired ratio can be supplied to adjust the oxygen concentration in the room. Alternatively, oxygen gas and nitrogen gas of predetermined flow rates may be circulated in the chamber of the exposure apparatus so that the exposure atmosphere has a predetermined oxygen concentration.
　ここで、本発明の製造方法では光学濃度ＡをＸ、露光時の酸素濃度（体積分率）をＹ、放射照度（Ｗ／ｍ２）をＺとした場合に、下記式（１）で計算される値が、１．６０×１０－５～１０．００×１０－５となるのが好ましく、２．８０×１０－５～５．２０×１０－５となるのがより好ましい。
式（１）　Ｘ×Ｙ÷Ｚ Here, in the manufacturing method of the present invention, when the optical density A is X, the oxygen concentration (volume fraction) at the time of exposure is Y, and the irradiance (W / m 2 ) is Z, calculation is performed by the following formula (1) The value to be set is preferably 1.60 × 10 −5 to 10.00 × 10 −5, and more preferably 2.80 × 10 −5 to 5.20 × 10 −5 .
Formula (1) X × Y ÷ Z
　式（１）中の、光学濃度ＡであるＸが大きい場合、露光工程において照射される光が硬化性組成物層の表層部で遮断されやすく、下層部での硬化反応が進行しにくくなる。
　露光時の酸素濃度であるＹが大きい場合、硬化性組成物層の表層部での硬化反応が酸素によって抑制されやすくなる。
　放射照度（Ｗ／ｍ２）であるＺが大きい場合、硬化性組成物層の表層部と下層部の両方において硬化反応を促進する。
　これらの硬化性組成物層の硬化の進行に密接に関連した、Ｘ、Ｙ、及び、Ｚが組み合わされた式（１）で計算される値が、上述のような範囲内に収まる場合、硬化膜の矩形性が良好になる。
　また、調製してから長期間（例えば１か月）経過した硬化性組成物を用いた場合でも、式（１）で計算される値が、上述のような範囲内に収まる場合、作製される硬化膜の断面形状の矩形性が劣化しにくい。 When X, which is the optical density A in the formula (1), is large, the light irradiated in the exposure step is likely to be blocked at the surface layer portion of the curable composition layer, and the curing reaction in the lower layer portion hardly progresses.
When Y which is an oxygen concentration at the time of exposure is large, the curing reaction in the surface layer portion of the curable composition layer is easily suppressed by oxygen.
When Z, which is the irradiance (W / m 2 ), is large, the curing reaction is promoted in both the surface layer portion and the lower layer portion of the curable composition layer.
Curing if the value calculated by the equation (1) in which X, Y and Z are combined, which is closely related to the progress of curing of these curable composition layers, falls within the above-mentioned range The rectangularity of the film is good.
In addition, even when using a curable composition which has been prepared for a long time (for example, one month), it is produced when the value calculated by the formula (1) falls within the above range. The rectangularity of the cross-sectional shape of the cured film does not easily deteriorate.
　式（１）に基づく具体的な計算は、例えば以下のとおりである。
　光学濃度Ａが３．００である硬化性組成物層に対して、酸素濃度が３０質量％、放射照度が３００００Ｗ／ｍ２の条件で露光を行う場合、Ｘ＝３．００、Ｙ＝０．３０、Ｚ＝３００００となり、式（１）の計算値は３．００×１０－５である。 The specific calculation based on Formula (1) is as follows, for example.
In the case of performing exposure under the conditions of an oxygen concentration of 30% by mass and an irradiance of 30,000 W / m 2 to the curable composition layer having an optical density A of 3.00, X = 3.00, Y = 0. 30, Z = 30000, and the calculated value of equation (1) is 3.00 × 10 −5 .
〔現像工程〕
　現像工程は、露光後の上記硬化性組成物層を現像して硬化膜を形成する工程である。本工程により、露光工程における光未照射部分の硬化性組成物層が溶出し、光硬化した部分だけが残り、パターン状の硬化膜が得られる。
　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などにダメージを起さない、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秒である。より残渣を除去するため、近年では１２０～１８０秒実施する場合もある。更には、より残渣除去性を向上するため、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 curable composition layer after exposure to form a cured film. In this step, the curable composition layer in the non-light-irradiated portion in the exposure step is eluted, and only the light-cured portion remains, and a patterned cured film is obtained.
The type of developing solution used in the developing step is not particularly limited, but an alkaline developing solution which does not cause damage to the underlying imaging device and circuit is desirable.
The development temperature is, for example, 20 to 30.degree.
The developing time is, for example, 20 to 90 seconds. In order to remove more residue, it may be carried out for 120 to 180 seconds in recent years. Furthermore, in order to further improve the residue removability, the process of shaking off the developer every 60 seconds and further 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。 The alkaline developer is preferably an alkaline aqueous solution prepared by dissolving an alkaline compound in water so that the concentration is 0.001 to 10% by mass (preferably 0.01 to 5% by mass).
The alkaline compound is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium borate, sodium metaborate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl Ammonium hydroxide, tetrabutylammonium hydroxy, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo [5.4.0] -7-undecene etc. (of which the organic alkali is preferable.).
In addition, when using as an alkali developing solution, washing processing is generally performed by water after image development.
〔ポストベーク〕
　露光工程の後、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うことができる。 Post-bake
After the exposure step, heat treatment (post-baking) is preferably performed. Post-baking is a heat treatment after development to complete curing. 240 degrees C or less is preferable and, as for the heating temperature, 220 degrees C or less is more preferable. There is no particular lower limit, but in consideration of efficient and effective treatment, 50 ° C. or higher is preferable, and 100 ° C. or higher is more preferable.
Post-baking can be performed by a continuous system or a batch system using 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％以下であるのが好ましく、１５体積％以下であるのがより好ましく、１０体積％以下であるのが更に好ましく、７体積％以下であるのが特に好ましく、３体積％以下であるのが最も好ましい。下限は特にないが、１０体積ｐｐｍ以上が実際的である。 The above post-baking is preferably performed in an atmosphere of 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, 3 volumes Most preferably, it is at most%. 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全にしてもよい。
　この場合、上述した硬化性組成物は、更にＵＶ硬化剤を含有するのが好ましい。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、硬化性組成物層が波長３４０ｎｍ以下で硬化する材料であるのが好ましい。波長の下限値は特にないが、２２０ｎｍ以上であるのが一般的である。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、リソグラフィー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のが好ましい。 Also, instead of the post-baking by heating described above, UV (ultraviolet) irradiation may complete the curing.
In this case, the curable composition described above 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 by ordinary i-ray exposure. Examples of UV curing agents include Ciba Irgacure 2959 (trade name). When UV irradiation is performed, the curable composition layer is preferably a material that cures at a wavelength of 340 nm or less. Although the lower limit of the wavelength is not particularly limited, it is generally 220 nm or more. The exposure dose of UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, and still more preferably 800 to 3500 mJ. This UV curing step is preferably performed after the lithography step in order to perform low temperature curing more effectively. The exposure light source is preferably an ozoneless mercury lamp.
［硬化膜の物性、及び、硬化膜の用途］
〔硬化膜の物性〕
　本発明の製造方法で得られる硬化膜は、膜厚１．５μｍあたりの波長３６５ｎｍにおける光学濃度は、２．６０～１０．００が好ましく、２．８０～４．００がより好ましく、２．９０～３．５０が更に好ましい。
　本発明の製造方法で得られる硬化膜の、膜厚１．５μｍあたりの波長５５０ｎｍにおける光学濃度は、２．００～１０．００が好ましく、２．５０～７．００がより好ましく、２．８０～６．５０が更に好ましい。
　また、硬化膜は、後述する遮光膜とした場合の性能がより優れる点で、硬化膜の、４００～１２００ｎｍの波長領域における膜厚１．５μｍあたりの光学濃度は、２．００超が好ましく、３．００超がより好ましい。なお、上限値は特に制限されないが、１０以下が好ましい。このような硬化膜は、遮光膜として好ましく使用できる。
　なお、本明細書において、硬化膜の光学濃度の測定方法としては、まず、ガラス基板上硬化膜を形成して、透過濃度計（Ｘ－ｒｉｔｅ　３６１Ｔ（ｖｉｓｕａｌ）ｄｅｎｓｉｔｏｍｅｔｅｒ）を用いて測定し、測定箇所の膜厚も測定し、所定の膜厚あたりの光学濃度を算出する。
　また、本明細書において、４００～１２００ｎｍの波長領域における膜厚１．５μｍあたりの光学濃度が、２．００超とは、波長４００～１２００ｎｍの全域において、膜厚１．５μｍあたりの光学濃度が２．００超であることを意図する。 [Physical properties of cured film, and application of cured film]
[Physical properties of cured film]
The cured film obtained by the production method of the present invention preferably has an optical density at a wavelength of 365 nm per 1.5 μm of film thickness of 2.60 to 10.00, more preferably 2.80 to 4.00, 2.90 -3.50 is more preferable.
The optical density at a wavelength of 550 nm per 1.5 μm of film thickness of the cured film obtained by the production method of the present invention is preferably 2.00 to 10.00, more preferably 2.50 to 7.00, 2.80 To 6.50 is more preferable.
The cured film preferably has an optical density of more than 2.00 per 1.5 μm in the wavelength region of 400 to 1200 nm, since the cured film has better performance when used as a light shielding film described later. More than 3.00 is more preferable. Although the upper limit value is not particularly limited, it is preferably 10 or less. Such a cured film can be preferably used as a light shielding film.
In the present specification, as a method of measuring the optical density of a cured film, first, a cured film on a glass substrate is formed, and measurement is performed using a transmission densitometer (X-rite 361 T (visual) densitometer). The film thickness of the portion is also measured, and the optical density per predetermined film thickness is calculated.
In the present specification, an optical density of 1.5 μm or more in the wavelength range of 400 to 1200 nm means an optical density of 1.5 μm or more in the entire wavelength range of 400 to 1200 nm. Intended to be over 2.00.
　また、上記硬化膜は、表面凹凸構造を有するのも好ましい。そうすることで、硬化膜を遮光膜とした場合における、硬化膜の反射率を低減できる。硬化膜そのものの表面に凹凸構造を有しても、硬化膜上に別の層を設けて凹凸構造を付与してもよい。表面凹凸構造の形状は特に限定されないが、表面粗さが０．５５μｍ以上１．５μｍ以下の範囲であるのが好ましい。
　硬化膜の反射率は、５％以下が好ましく、３％以下がより好ましく、２％以下が更に好ましい。
　表面凹凸構造を作製する方法は特に限定されないが、硬化膜若しくはそれ以外の層に、有機フィラー及び／又は無機フィラーを含む方法、露光現像を利用したリソグラフィー法、又は、エッチング法、スパッタ法及びナノインプリント法などで硬化膜若しくはそれ以外の層の表面を粗面化する方法であってもよい。
　また、上記硬化膜の反射率をさげる方法としては、上記以外に、硬化膜上に低屈折率層を設ける方法、更に屈折率の異なる層（例えば、高屈折率層）を複数設ける方法、及び、特開２０１５－１６５４号公報に記載の、低光学濃度層と高光学濃度層とを形成する方法等が挙げられる。 Moreover, it is also preferable that the said cured film has a surface asperity structure. By doing so, the reflectance of the cured film can be reduced when the cured film is a light shielding film. Even if it has a concavo-convex structure on the surface of a cured film itself, another layer may be provided on a cured film and a concavo-convex structure may be given. The shape of the surface asperity structure is not particularly limited, but the surface roughness is preferably in the range of 0.55 μm to 1.5 μm.
5% or less is preferable, as for the reflectance of a cured film, 3% or less is more preferable, and 2% or less is still more preferable.
Although the method for producing the surface concavo-convex structure is not particularly limited, a method including an organic filler and / or an inorganic filler in a cured film or other layers, a lithography method using exposure and development, or an etching method, a sputtering method and nanoimprinting The surface of the cured film or other layers may be roughened by a method or the like.
In addition to the above methods, a method of providing a low refractive index layer on the cured film, a method of providing a plurality of layers having different refractive indexes (for example, high refractive index layers), and a method of reducing the reflectance of the cured film And a method of forming a low optical density layer and a high optical density layer, as described in JP-A-2015-1654.
　また、上記硬化膜は、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、バイオセンサー、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。 The cured film is a portable computer such as a personal computer, a tablet, a cellular phone, a smart phone, and a digital camera; a printer complex machine, an OA (Office Automation) equipment such as a scanner; a surveillance camera, a barcode reader, cash Industrial equipment such as an automated teller machine (ATM), a high speed camera, and a device having an identity authentication function using face image authentication; automotive camera devices; endoscopes, capsule endoscopes, And medical camera devices such as catheters; and bio-sensors, biosensors, cameras for military reconnaissance, cameras for stereoscopic maps, cameras for weather and ocean observation, land resource exploration cameras, astronomy for space and deep space targets Space equipment such as exploration cameras; etc. Light blocking member and the light-shielding film of the optical filter and the module is used, yet is suitable for anti-reflection member and the antireflection film.
　上記硬化膜は、マイクロＬＥＤ（Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）及びマイクロＯＬＥＤ（Ｏｒｇａｎｉｃ　Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）などの用途にも使用できる。上記硬化膜は、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号及び特表２０１４－５３３８９０に記載されたものが挙げられる。 The said cured film can be used also for uses, such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). The said cured film is suitable for the member which provides a light shielding function or an antireflection function other than the optical filter and optical film which are used for micro LED and micro OLED.
Examples of micro LEDs and micro OLEDs include those described in JP-A-2015-500562 and JP-A-2014-533890.
　上記硬化膜は、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号及び国際公開第２００８／１３１３１３号パンフレットに記載されたもの等が挙げられる。 The cured 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. Moreover, it is suitable as a member which provides a light shielding function and a reflection preventing function. Examples of the quantum dot sensor and the quantum dot solid-state imaging device include those described in U.S. Patent Application Publication 2012/37789 and WO 2008/131313.
〔遮光膜、並びに、固体撮像素子及び固体撮像装置〕
　本発明の製造方法で得られた硬化膜は、いわゆる遮光膜として使用するのも好ましい。このような遮光膜は、固体撮像素子に使用するのも好ましい。
　なお、遮光膜は、本発明の製造方法で得られる硬化膜における好ましい用途の１つであって、本発明の遮光膜の製造方法は、上述の硬化膜の製造方法として説明した方法で同様に行える。具体的には、基板に硬化性組成物を塗布して、硬化性組成物層を形成し、露光、及び、現像して遮光膜を製造できる。
　また、本発明の固体撮像素子の製造方法は、上述した本発明の製造方法を介して硬化膜（遮光膜）を製造する工程を含有する、上記硬化膜（遮光膜）を有する固体撮像素子を製造する方法である。
　上述の通り、本発明の製造方法に係る、固体撮像素子は、上記硬化膜（遮光膜）を含有する。固体撮像素子が硬化膜（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硬化膜を有するものが挙げられる。
　固体撮像装置は、上記固体撮像素子を含有する。 [Light-shielding film, solid-state imaging device and solid-state imaging device]
It is also preferable to use the cured film obtained by the manufacturing method of the present invention as a so-called light shielding film. It is also preferable to use such a light shielding film for a solid-state imaging device.
In addition, a light shielding film is one of the preferable uses in the cured film obtained by the manufacturing method of this invention, Comprising: The manufacturing method of the light shielding film of this invention is similarly the method demonstrated as the manufacturing method of the above-mentioned cured film. It can do. Specifically, the curable composition is applied to a substrate to form a curable composition layer, and the light shielding film can be produced by exposure and development.
Further, a method of manufacturing a solid-state imaging device according to the present invention includes a step of manufacturing a cured film (light shielding film) through the above-described manufacturing method of the present invention, the solid-state imaging device having the cured film (light shielding film) It is a method of manufacturing.
As described above, the solid-state imaging device according to the manufacturing method of the present invention contains the cured film (light shielding film). The form in which the solid-state imaging device contains a cured film (light-shielding film) is not particularly limited. For example, a plurality of photodiodes constituting the light receiving area of the solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) on a substrate And a light receiving element made of polysilicon or the like, and having a cured film on the light receiving element forming surface side of the support (for example, a portion other than the light receiving portion and / or a pixel for color adjustment) It can be mentioned.
The solid-state imaging device contains the above-described 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、相互の厚み及び／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。本発明の製造方法で得られる硬化膜は上記遮光膜１１４としても使用できる。 A configuration example of a solid-state imaging device and a solid-state imaging device will be described with reference to FIGS. In addition, in FIGS. 1 and 2, in order to clarify each part, the mutual thickness and / or the ratio of the width is neglected and is partially displayed in an exaggerated manner.
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 held above the solid-state imaging device 101 and sealing the solid-state imaging device 101. There is. Furthermore, on the cover glass 103, a lens layer 111 is provided so as to overlap via a spacer 104. The lens layer 111 is composed of 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 is incident on the peripheral region of the lens layer 111, light diffusion reduces the light condensing effect of the lens material 112, and the light reaching the imaging unit 102 is reduced. In addition, generation of noise due to stray light also occurs. Therefore, a light shielding film 114 is provided to shield the peripheral region of the lens layer 111 from light. The cured film obtained by the manufacturing method of the present invention can also 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 serving as the light receiving surface and outputs the image as an image signal. The solid-state imaging device 101 includes a laminated substrate 105 in which two substrates are laminated. The laminated substrate 105 is composed of a rectangular chip substrate 106 and a circuit substrate 107 of 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 known materials 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の周縁領域に迷光が入射すると、この周縁領域内の回路から暗電流（ノイズ）が発生するため、この周縁領域は、遮光膜１１５が設けられて遮光されている。本発明の製造方法で得られる硬化膜は遮光膜１１５として用いるのが好ましい。 An imaging unit 102 is provided at the center of the surface of the chip substrate 106. In addition, when stray light enters the peripheral region of the imaging unit 102, a dark current (noise) is generated from the circuit in the peripheral region, and the peripheral region is shielded by the light shielding film 115 provided. The cured film obtained by the production method of the present invention is preferably used 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 at 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) (which may be a bonding wire) 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。 On the back surface of the circuit board 107, external connection terminals 109 are provided substantially below the electrode pads 108, respectively. Each external connection terminal 109 is connected to the electrode pad 108 through the penetration electrode 110 which penetrates the lamination substrate 105 perpendicularly. Further, each external connection terminal 109 is connected to a control circuit that controls the 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, etc. It is done.
　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。本発明の製造方法で得られる硬化膜は、ブラックマトリクス２０５ｂｍとして用いることもできる。 As shown in FIG. 2, the imaging unit 102 includes components provided on the substrate 204 such as the light receiving element 201, the color filter 202, and the microlens 203. The color filter 202 includes a blue pixel 205b, a red pixel 205r, a green pixel 205g, and a black matrix 205bm. The cured film obtained by the production method of the present invention can also be used as a 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 a material of the substrate 204, the same material as 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 n-type layers and generate and accumulate signal charges by photoelectric conversion are arranged and formed in a square lattice shape.
　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。 A vertical transfer path 208 formed of an n-type layer is formed on one side of the light receiving element 201 via the readout gate portion 207 on the surface layer of the p well layer 206. Further, 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 formed of a p-type layer. The read gate unit 207 is a channel region for reading out the signal charge stored 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。 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 on the gate insulating film 210 so as to cover the vertical transfer path 208, the read gate portion 207, and the element isolation region 209 almost immediately. The vertical transfer electrode 211 functions as a drive electrode that drives the vertical transfer path 208 to perform charge transfer, and a read electrode that drives the read gate unit 207 to read a signal charge. The signal charges are sequentially transferred from the vertical transfer path 208 to a horizontal transfer path and an output unit (floating diffusion amplifier) not shown, 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。本発明の製造方法で得られる硬化膜は、遮光膜２１２として用いることもできる。
　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。 A light shielding film 212 is formed on the vertical transfer electrode 211 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 the other regions. The cured film obtained by the manufacturing method of the present invention can also be used as the light shielding film 212.
On the light shielding film 212, a transparent intermediate layer formed of an insulating film 213 made of borophospho silicate glass (BPSG), an insulating film (passivation film) 214 made of P-SiN, and a planarizing film 215 made of a transparent resin or the like is provided. ing. The color filter 202 is formed on the intermediate layer.
〔画像表示装置〕
　本発明の製造方法で製造される画像表示装置は、本発明の製造方法で得られる硬化膜を含有する。
　また、本発明の画像表示装置の製造方法は、上述した本発明の製造方法を介して硬化膜を製造する工程を含有する、上記硬化膜を有する画像表示装置を製造する方法である。
　画像表示装置が硬化膜を有する形態としては、例えば、硬化膜がブラックマトリクスに含有され、このようなブラックマトリクス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 manufactured by the manufacturing method of this invention contains the cured film obtained by the manufacturing method of this invention.
Further, a method of producing an image display device of the present invention is a method of producing an image display device having the above-mentioned cured film, including the step of producing a cured film through the above-mentioned production method of the present invention.
As a form in which an image display apparatus has a cured film, a form in which a cured film is contained in a black matrix, and the color filter containing such a black matrix is used for an image display apparatus is mentioned, for example.
Next, a black matrix and a color filter containing the black matrix will be described, and a liquid crystal display device containing such a color filter will be described as a specific example of the image display device.
＜ブラックマトリクス＞
　本発明の製造方法で得られる硬化膜は、ブラックマトリクスに含有されるのも好ましい。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、液晶表示装置など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）を有するのが好ましい。 <Black matrix>
It is also preferable that the cured film obtained by the production method of the present invention is contained in a black matrix. The black matrix may be contained 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 at the periphery of an image display device such as a liquid crystal display device; grids between red, blue and green pixels, and / or stripes Black portions; dot-like and / or linear black patterns for light shielding of TFT (thin film transistor); and the like. For the definition of the black matrix, see, for example, Taiho Ogino, "Glossary of Liquid Crystal Display Manufacturing Device Dictionary", Second Edition, Nikkan Kogyo Shimbun, 1996, p. 64.
The black matrix has a high light-shielding property (optical density OD) in order to improve the display contrast, and in the case of an active matrix drive liquid crystal display device using thin film transistors (TFTs), to prevent image quality deterioration due to light current leakage. It is preferable to have three 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、上記の硬化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、基板に硬化性組成物を塗布して、硬化性組成物層を形成し、露光、及び、現像してパターン状の硬化膜（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硬化膜の膜厚としては、０．１～４．０μｍが好ましい。 The method for producing the black matrix is not particularly limited, but it can be produced by the same method as the method for producing a cured film described above. Specifically, a curable composition can be applied to a substrate to form a curable composition layer, exposed, and developed to produce a patterned cured film (black matrix). The thickness of the cured film used as the black matrix is preferably 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のが好ましい。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などのプラスチック；等が挙げられ、耐薬品性、及び、耐熱性の観点から、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 to visible light (wavelength 400 to 800 nm). As such a material, specifically, for example, glass such as soda lime glass, non-alkali glass, quartz glass, and borosilicate glass; plastics such as polyester resin and polyolefin resin; From the viewpoint of chemical resistance and heat resistance, alkali-free glass, quartz glass and the like are preferable.
＜カラーフィルタ＞
　本発明の製造方法で得られる硬化膜は、カラーフィルタに含有されるのも好ましい。
　カラーフィルタが硬化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>
It is also preferable that the cured film obtained by the production method of the present invention is contained in a color filter.
Although it does not restrict | limit especially as a form in which a color filter contains a cured film, A color filter provided with a board | substrate and said black matrix is mentioned. That is, a color filter provided with red, green and blue colored pixels formed in the opening of the black matrix formed on the substrate can be exemplified.
　ブラックマトリクス（硬化膜）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樹脂組成物の塗膜（樹脂組成物層）を形成する。なお、各色用樹脂組成物としては特に制限されず、公知の樹脂組成物を使用できるが、本明細書で説明した硬化性組成物において、黒色顔料を、各画素に対応した着色剤に置き換えたものを使用するのが好ましい。
　次に、樹脂組成物層に対して、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、ベークすることで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樹脂組成物を用いて行うことにより、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。 The color filter containing the black matrix (cured film) can be produced, for example, by the following method.
First, a coating (resin composition layer) of a resin composition containing a pigment corresponding to each colored pixel of a color filter is formed in the opening of a pattern-like black matrix formed on a substrate. In addition, it does not restrict | limit especially as a resin composition for each color, Although a well-known resin composition can be used, In the curable composition demonstrated in this specification, the black pigment was substituted to the coloring agent corresponding to each pixel It is preferred to use one.
Next, the resin composition layer is exposed to light through a photomask having a pattern corresponding to the opening of the black matrix. Next, after removing the unexposed area by development processing, baking is performed to form colored pixels in the opening of the black matrix. A color filter having red, green and blue pixels can be produced by performing a series of operations using, for example, resin compositions for each color containing red, green and blue pigments.
＜液晶表示装置＞
　本発明の製造方法で得られる硬化膜は、液晶表示装置に含有されるのも好ましい。液晶表示装置が硬化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（硬化膜）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>
It is also preferable that the cured film obtained by the production method of the present invention is contained in a liquid crystal display device. The form in which the liquid crystal display device contains the cured film is not particularly limited, but the form containing the color filter containing the black matrix (cured film) described above can be mentioned.
　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。 As a liquid crystal display device concerning this embodiment, a form provided with a pair of substrates arranged facing, and a liquid crystal compound enclosed between those substrates is mentioned, for example. The substrate is as described above 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 the user side, polarizing plate / substrate / color filter / transparent electrode layer / alignment film / liquid crystal layer / alignment film / transparent electrode layer / TFT (Thin Film Transistor) A laminate including an element / substrate / polarizer / backlight unit in this order may be mentioned.
　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）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）平成元年発行）」など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）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, and, for example, “Electronic display device (authored by Akio Sasaki, published by Industry Research Association 1990)”, “Display device (authored by Ibuki Osamu, Industrial Books (stock) The liquid crystal display device described in the Heisei 1st year publication etc. is mentioned. In addition, for example, a liquid crystal display device described in “Next-Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, Inc., Industrial Research Association, Inc. 1994)” may be mentioned.
〔赤外線センサ〕
　本発明の製造方法で得られる硬化膜は、赤外線センサに含有されるのも好ましい。
　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に示す赤外線センサ３００において、図番３１０は、固体撮像素子である。
　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させることができる樹脂膜３１４（例えば、透明樹脂膜など）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、ビス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、本発明の製造方法で得られる硬化膜を使用できる。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の光を透過させるのが好ましい。
　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。本発明の製造方法で得られる硬化膜は、赤外線吸収フィルタ３１１の表面の端部及び／又は側面など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ることで、内部反射及び／又は受光部への意図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むことができるため、動きを検知する対象を認識したモーションセンシングなどが可能である。更には、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。 [Infrared sensor]
It is also preferable that the cured film obtained by the production method of the present invention is contained in an infrared sensor.
The infrared sensor according to the above embodiment will be described with reference to FIG. In the infrared sensor 300 shown in FIG. 3, reference numeral 310 denotes a solid-state imaging device.
The imaging region provided on the solid-state imaging device 310 is configured by combining the infrared absorption filter 311 and the color filter 312.
The infrared absorption filter 311 transmits light in the visible light range (for example, light with a wavelength of 400 to 700 nm) and light in the infrared range (for example, light with a wavelength of 800 to 1300 nm, preferably light with a wavelength of 900 to 1200 nm) Preferably, it is a film that shields light having a wavelength of 900 to 1000 nm, and a cured film containing an infrared ray absorbent (as described in the form of the infrared ray absorbent as described above) as a colorant 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, and for example, red (R), green (G), and blue (B) pixels are formed. The 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 of the wavelength transmitted through the infrared transmission filter 313 is disposed between the infrared transmission filter 313 and the solid-state imaging device 310.
The infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared light of a specific wavelength, and is a colorant (for example, a perylene compound and / or bisbenzo) that absorbs light in the visible light range. A cured film obtained by the production method of the present invention, which contains a furanone 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. For example, it is preferable that the infrared transmission filter 313 shields light having a wavelength of 400 to 830 nm and transmit light having a wavelength of 900 to 1300 nm.
A microlens 315 is disposed on the incident light hν side of the color filter 312 and the infrared transmission filter 313. A planarization film 316 is formed to cover the microlenses 315.
Although the resin film 314 is disposed in the embodiment shown in FIG. 3, the infrared transmission filter 313 may be formed instead of the resin film 314. That is, the infrared ray transmission filter 313 may be formed on the solid-state imaging device 310.
Moreover, in the form shown in FIG. 3, although the film thickness of the color filter 312 and the film thickness of the infrared rays permeable filter 313 are the same, the film thickness of both may be different.
Further, in the embodiment shown in FIG. 3, the color filter 312 is provided closer to the incident light hν than the infrared absorption filter 311, but the infrared absorption filter 311 and the color filter 312 are interchanged in order and the infrared absorption filter 311 may be provided closer to the incident light hν than the color filter 312.
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 cured film obtained by the manufacturing method of the present invention can be used as a light shielding film for the edge and / or the side of the surface of the infrared absorption filter 311, and by using for the inner wall of the infrared sensor, internal reflection and / or light reception. Unintended light can be prevented from entering the unit and sensitivity can be improved.
According to this infrared sensor, it is possible to simultaneously capture image information, so that it is possible to perform motion sensing in which an object whose motion is to be detected is recognized. Furthermore, since distance information can be acquired, it is also possible to capture an image including 3D information.
　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 in JP-A-2011-233983 can be referred to, and the contents thereof are incorporated in the present specification.
　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, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the following examples.
〔分散組成物の調製〕
　硬化性組成物の調製に用いられる分散組成物を調製した。
　以下の表１に各分散組成物における各成分の組成比（質量部比）を示す。なお、分散組成物１、１３、及び、１４は同一の配合である。 [Preparation of Dispersion Composition]
A dispersion composition was prepared which was used to prepare a curable composition.
Table 1 below shows the composition ratio (parts by mass) of each component in each dispersion composition. The dispersion compositions 1, 13 and 14 have the same composition.
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
　以下に、表１中の記載に対応する成分の詳細を示す。 Below, the detail of the component corresponding to the description in Table 1 is shown.
＜顔料＞
　以下に示す顔料を使用した。
　なお、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、及び、ＣＢ、無機黒色顔料（Ａ）、無機黒色顔料（Ｂ）、無機黒色顔料（Ｃ）が黒色顔料で、ＰＧ５８及びＰＹ１８５は黒色顔料以外の顔料である。 <Pigment>
The pigment shown below was used.
In addition, Ti, Zr, V, Nb, and CB, inorganic black pigment (A), inorganic black pigment (B), inorganic black pigment (C) are black pigments, and PG58 and PY185 are pigments other than black pigments. .
・Ｔｉ：以下に示す金属窒化物含有粒子の作製方法で作製した窒化チタン含有粒子。 Ti: titanium nitride-containing particles produced by the method for producing metal nitride-containing particles shown below.
　金属窒化物含有粒子（窒化チタン含有粒子）の作製には、特開２００５－３４３７８４号公報の００４２段落、及び、図１に記載された装置を用いた。具体的には、上記公報の図１における、放電容器１をステンレス製の真空チャンバ（福伸工業株式会社製）とした装置（以下、「ナノ粒子製造装置」という。）を用いて金属窒化物含有粒子（窒化チタン含有粒子）を作製した。まず、排気ポンプにより真空チャンバ内の空気を排気した。次に、真空チャンバに、ヘリウム（Ｈｅ）ガス（純度９９．９９％）、及び、アルゴンガスの混合ガス（標準状態での混合比５０／５０体積％）を６００Ｔｏｒｒ（７９．９９ｋＰａ）の圧力となるまで供給した。 For the production of metal nitride-containing particles (titanium nitride-containing particles), the apparatus described in paragraph 0042 of JP-A-2005-343784 and FIG. 1 was used. Specifically, metal nitride is used with an apparatus (hereinafter referred to as “nanoparticle manufacturing apparatus”) in which the discharge vessel 1 in FIG. 1 of the above publication is a stainless steel vacuum chamber (manufactured by Fukushin Kogyo Co., Ltd.). Containing particles (titanium nitride containing particles) were produced. First, the air in the vacuum chamber was exhausted by the exhaust pump. Next, in the vacuum chamber, a mixture gas of helium (He) gas (purity 99.99%) and argon gas (mixture ratio 50/50 volume% under standard conditions) at a pressure of 600 Torr (79.99 kPa) It supplied until it became.
　ナノ粒子製造装置の放電電極としては、タングステンを長さ５００ｍｍ、直径１２ｍｍ、及び、中空口径６ｍｍの中空構造の棒状に成形加工したものを使用した。放電電極の配置は、特開２００５－３４３７８４号公報の図１と同様にした。具体的には、１２個の放電電極を６個ずつ２段に配置した。なお、上段と下段との間の距離は約１６０ｍｍとした。
　中空構造の放電電極は、原材料供給装置と接続されており、放電電極の中空部分から原料ガスを真空チャンバ内へと供給できるようにした。 As a discharge electrode of the nano-particle production apparatus, a tungsten rod having a length of 500 mm, a diameter of 12 mm, and a rod shape of a hollow structure having a hollow diameter of 6 mm was used. The arrangement of the discharge electrodes was the same as that of FIG. 1 of JP-A-2005-343784. Specifically, 12 discharge electrodes were arranged in two stages of six each. The distance between the upper and lower portions was about 160 mm.
The hollow discharge electrode was connected to the raw material supply device so that the raw material gas could be supplied into the vacuum chamber from the hollow portion of the discharge electrode.
　放電は、各放電電極に位相差のある交流（電圧２０～４０Ｖ、電流７０～１００Ａ）を印加しながら、各放電電極の先端を接触させた状態で開始する。アーク放電が発生した後各放電電極の先端を離間させるように外方に向かって移動させ、隣接する放電電極の先端の間の距離が５～１０ｍｍとなる位置にセットしてアーク放電を続行した。 The discharge starts in a state where the tips of the discharge electrodes are in contact with each other while applying an alternating current (voltage: 20 to 40 V, current: 70 to 100 A) having a phase difference to each discharge electrode. After the arc discharge occurred, the tips of the discharge electrodes were moved outward so as to separate them, and the distance between the tips of the adjacent discharge electrodes was set to a position of 5 to 10 mm to continue the arc discharge .
　アーク放電を１５分行った後、原材料供給装置の供給タンクを加温して、原料ガスを真空チャンバ内へと導入した。まず、ＮＨ３ガス（液化アンモニウムＥＣＯＡＮ、昭和電工社製）を０．５気圧、Ｈ２ガス（水素ガス、昭和電工ガスプロダクツ）を０．１気圧、Ａｒガス（アルゴンガス、大陽日酸）を０．４気圧で導入した。続いて、供給タンクを２１０℃に加温し、ＴｉＣｌ４ガス（ＴＬＴ－１、東邦チタニウム社）製を、放電電極から６００気圧で導入した。ＴｉＣｌ４ガスの導入と同時に、粉末供給装置ＴＰ－９９０１０ＦＤＲ（日本電子製）を用いて硫黄微粉末（微粉硫黄３２５ｍｅｓｈ、鶴見化学工業製）を窒素ガスにより供給した。供給量は、得られる金属窒化物含有粒子（窒化チタン含有粒子）中における、Ｘ線光電子分光分析により検出される硫黄原子の質量基準の含有量をＴＥ（質量％）とし、蛍光Ｘ線分析により検出される硫黄原子の質量基準の含有量をＴＸ（質量％）とした両者の比（ＴＥ／ＴＸ）が１．１未満となるように調整した。真空チャンバ内にＴｉＣｌ４ガス、及び、硫黄微粉末を混合した窒素ガスの導入を１時間行った後、交流電源からの電圧印加を停止し、上記ガスの供給を停止した。次に、真空チャンバの内壁に付着した粒子を回収した。 After the arc discharge was performed for 15 minutes, the feed tank of the raw material feeder was heated to introduce the raw material gas into the vacuum chamber. First, NH 3 gas (liquefied ammonium ECOAN, manufactured by Showa Denko KK) at 0.5 atm, H 2 gas (hydrogen gas, Showa Denko gas products) at 0.1 atm, Ar gas (argon gas, Taiyo Nichi acid) Was introduced at 0.4 atm. Subsequently, the supply tank was heated to 210 ° C., and TiCl 4 gas (TLT-1, manufactured by Toho Titanium Co., Ltd.) was introduced from the discharge electrode at 600 atm. At the same time as the introduction of the TiCl 4 gas, sulfur fine powder (fine powder sulfur 325 mesh, manufactured by Tsurumi Chemical Industry Co., Ltd.) was supplied as nitrogen gas using a powder supply device TP-99010 FDR (manufactured by JEOL). The feed rate is determined by X-ray fluorescence analysis using the content by mass of sulfur atoms detected by X-ray photoelectron spectroscopy in the obtained metal nitride-containing particles (particles containing titanium nitride) as T E (mass%). The ratio (T E / T X ) of the two was set to be less than 1.1, where T X (mass%) was the content by mass of sulfur atoms detected by After introducing TiCl 4 gas and nitrogen gas mixed with sulfur fine powder into the vacuum chamber for 1 hour, voltage application from the AC power supply was stopped, and the supply of the gas was stopped. Next, particles attached to the inner wall of the vacuum chamber were recovered.
　次に、得られた粒子を、Ｏ２含有量、及び、水分含有量をそれぞれ１００ｐｐｍ以下に制御した窒素（Ｎ２）ガスを導入した密閉容器内に入れ、２４時間静置した。 Next, the obtained particles were placed in a closed vessel into which nitrogen (N 2 ) gas having an O 2 content and a water content controlled to 100 ppm or less, respectively, was introduced and allowed to stand for 24 hours.
　上記で得られた粒子を、減圧オーブンＶＡＣ－１０１Ｐ（エスペック製）を用いて２００℃で加熱して、金属窒化物含有粒子（窒化チタン含有粒子）を得た。なお、加熱中の減圧オーブンの内圧は１．０×１０３Ｐａとした。 The particles obtained above were heated at 200 ° C. using a vacuum oven VAC-101P (manufactured by ESPEC) to obtain metal nitride-containing particles (titanium nitride-containing particles). The internal pressure of the decompression oven during heating was 1.0 × 10 3 Pa.
・Ｚｒ：ＴｉＣｌ４ガスの導入に換えて、ジルコニウム粉末（和光純薬工業製ジルコニウム粉末）を粉末供給装置ＴＰ－９９０１０ＦＤＲ（日本電子製）で導入した以外は上述の窒化チタン含有粒子と同様の方法で作製した、窒化ジルコニウム含有粒子。 · The same method as described above for the titanium nitride-containing particles except that zirconium powder (zirconium powder manufactured by Wako Pure Chemical Industries, Ltd.) was introduced by the powder feeder TP-99010 FDR (manufactured by JEOL Ltd.) instead of Zr: TiCl 4 gas. Zirconium nitride-containing particles produced by
・Ｖ：ＴｉＣｌ４ガスの導入に換えて、バナジウム粉末（太陽鉱工製金属バナジウム粉末ＶＨＯ）を粉末供給装置ＴＰ－９９０１０ＦＤＲ（日本電子製）で導入した以外は上述の窒化チタン含有粒子と同様の方法で作製した、窒化バナジウム含有粒子。 V: Similar to the titanium nitride-containing particles described above, except that vanadium powder (Vanadium metal powder VHO manufactured by Taiyo Mining Co., Ltd.) was introduced by a powder supply device TP-99010FDR (manufactured by JEOL Ltd.) instead of the introduction of TiCl 4 gas. Vanadium nitride-containing particles produced by the method.
・Ｎｂ：ＴｉＣｌ４ガスの導入に換えて、ニオブ粉末（三津和化学薬品製ニオブ（粉末）＜１００－３２５ｍｅｓｈ＞）を粉末供給装置ＴＰ－９９０１０ＦＤＲ（日本電子製）で導入した以外は上述の窒化チタン含有粒子と同様の方法で作製した、窒化ニオブ含有粒子。 -Nb: Nitriding as described above except that niobium powder (Niobium (powder) <100-325 mesh> manufactured by Mitsuwa Chemical Co., Ltd.) was introduced by a powder feeder TP-99010 FDR (manufactured by JEOL Ltd.) instead of introducing TiCl 4 gas Niobium nitride-containing particles produced by the same method as titanium-containing particles.
　なお、上述した各金属窒化物含有粒子（窒化チタン含有粒子、窒化ジルコニウム含有粒子、窒化バナジウム含有粒子、及び、窒化ニオブ含有粒子）のＴＥ／ＴＸは以下の方法により測定した。
　各金属窒化物含有粒子を、プレス機を用いてペレット状に成形して試料とした。上記試料について、Ｘ線光電子分光分析装置、及び、蛍光Ｘ線分析装置を用いて、以下測定条件で、金属窒化物含有粒子のＴＥ／ＴＸを測定した。 In addition, T E / T X of each metal nitride containing particle (a titanium nitride containing particle, a zirconium nitride containing particle, a vanadium nitride containing particle, and a niobium nitride containing particle) mentioned above was measured by the following method.
Each metal nitride-containing particle was formed into a pellet by using a press to obtain a sample. About the said sample, T E / T X of metal nitride containing particle | grains was measured on the following measurement conditions using a X-ray-photoelectron-spectroscopic-analysis apparatus and a fluorescent-X-ray-analysis apparatus.
　Ｘ線光電子分光分析装置（ＴＥの測定）
　　装置：ＰＨＩ社製Ｑｕａｎｔｅｒａ－ＳＸＭ（商品名）装置
　　Ｘ線源：単色化Ａｌ　Ｋα線（１４８６．６ｅｖ、２５Ｗ、１５ｋＶ、ビーム径２００μｍφ）
　　測定領域：２００μｍφ
　　測定条件：Ｐａｓｓ　Ｅｎｅｒｇｙ＝１４０ｅＶ、ｓｔｅｐ＝０．１ｅＶ、積算回数４～８回
　　測定方法：試料を装置にセットし、光電子取り出し角を１０度として測定した。 X-ray photoelectron spectrometer (Measurement of T E)
Device: Quantera-SXM (trade name) device manufactured by PHI X-ray source: monochromatized Al K α ray (1486.6 ev, 25 W, 15 kV, beam diameter 200 μmφ)
Measurement area: 200 μmφ
Measurement conditions: Pass Energy = 140 eV, step = 0.1 eV, integration number 4 to 8 times Measurement method: The sample was set in the apparatus, and the photoelectron extraction angle was measured at 10 degrees.
　蛍光Ｘ線分析装置（ＴＸの測定）
　　装置　Ｒｉｇａｋｕ製ＺＳＭ　ＰｒｉｍｕｓＩＩ型ＸＲＦ
　　Ｘ線　Ｒｈ　３０－５０　ｋＶ，　４８－８０　ｍＡ
　　測定領域　１０μｍφ
　　測定時間　１０－２４０　ｄｅｇ／ｍｉｎ X-ray fluorescence analyzer (measurement of T X )
Equipment Rigaku ZSM Primus II XRF
X-ray Rh 30-50 kV, 48-80 mA
Measurement area 10 μmφ
Measurement time 10-240 deg / min
　また、各金属窒化物含有粒子（窒化チタン含有粒子、窒化ジルコニウム含有粒子、窒化バナジウム含有粒子、及び、窒化ニオブ含有粒子）における、窒化物が含有する遷移金属原子（チタン、ジルコニウム、バナジウム、又は、ニオブ）の含有量に対する窒素原子の含有量の含有原子数比Ｘ、窒化物が含有する遷移金属原子の含有量に対する酸素原子の含有量の含有原子数比Ｙ、及び、窒化物が含有する遷移金属原子の含有量に対する硫黄原子の含有原子数比Ｚは、それぞれ、Ｘ＝０．８、Ｙ＝０．１、Ｚ＝０．１となるようにした。
　なお、得られた各金属窒化物含有粒子中の各原子の含有量は、蛍光Ｘ線分析装置を用いて測定した。具体的には、試料として各金属窒化物含有粒子を、プレス機を用いてペレット状に成形したものを準備し、上記試料について、蛍光Ｘ線分析装置を用いて、以下の条件で測定した。
　　装置　Ｒｉｇａｋｕ製ＺＳＭ　ＰｒｉｍｕｓＩＩ型ＸＲＦ
　　Ｘ線　Ｒｈ　３０－５０　ｋＶ，　４８－８０　ｍＡ
　　測定領域　１０μｍφ
　　測定時間　１０－２４０　ｄｅｇ／ｍｉｎ Also, transition metal atoms (titanium, zirconium, vanadium, or nitride) contained in each metal nitride-containing particle (titanium nitride-containing particle, zirconium nitride-containing particle, vanadium nitride-containing particle, and niobium nitride-containing particle) Containing atom number ratio X of content of nitrogen atom to content of niobium), contained atom number ratio Y of content of oxygen atom to content of transition metal atom contained in nitride, and transition contained in nitride The atomic number ratio Z of the sulfur atom to the content of the metal atom was such that X = 0.8, Y = 0.1, and Z = 0.1.
The content of each atom in each of the obtained metal nitride-containing particles was measured using a fluorescent X-ray analyzer. Specifically, each metal nitride-containing particle as a sample was formed into a pellet by using a press, and the sample was measured using the fluorescent X-ray analyzer under the following conditions.
Equipment Rigaku ZSM Primus II XRF
X-ray Rh 30-50 kV, 48-80 mA
Measurement area 10 μmφ
Measurement time 10-240 deg / min
　また、各金属窒化物含有粒子（窒化チタン含有粒子、窒化ジルコニウム含有粒子、窒化バナジウム含有粒子、及び、窒化ニオブ含有粒子）の平均一次粒子径は、いずれも８０ｎｍ未満であった。 The average primary particle diameter of each of the metal nitride-containing particles (titanium nitride-containing particles, zirconium nitride-containing particles, vanadium nitride-containing particles, and niobium nitride-containing particles) was less than 80 nm.
・ＣＢ：カーボンブラック（商品名「カラーブラック　Ｓ１７０」、デグサ社製、平均一次粒子径１７ｎｍ、ＢＥＴ比表面積２００ｍ２／ｇ）
・ＰＧ５８：ピグメントグリーン５８
・ＰＹ１８５：ピグメントイエロー１８５
・無機黒色顔料（Ａ）：商品名「ＮＩＴＲＢＬＡＣＫ（ナイトブラック）ＵＢ－１」、三菱マテリアル社製
・無機黒色顔料（Ｂ）：特開２０１７－２２２５５９号公報の実施例１に記載の窒化ジルコニウム粉末
・無機黒色顔料（Ｃ）：特許第４９３１０１１号公報の実施例１に記載の微粒子低次酸化ジルコニウム・窒化ジルコニウム複合体。 -CB: carbon black (trade name "color black S170", manufactured by Degussa, average primary particle diameter 17 nm, BET specific surface area 200 m 2 / g)
・ PG 58: pigment green 58
・ PY 185: pigment yellow 185
Inorganic black pigment (A): trade name “NITRBLACK (night black) UB-1”, manufactured by Mitsubishi Materials Corporation Inorganic black pigment (B): zirconium nitride powder described in Example 1 of JP-A-2017-222559 Inorganic black pigment (C): The particulate low-order zirconium oxide-zirconium nitride composite described in Example 1 of Japanese Patent No. 4931011.
　なお、分散組成物１１においてはＰＧ５８とＰＹ１８５とを併用して、全体として緑色としている。 In addition, in the dispersion composition 11, PG58 and PY185 are used together to make it green as a whole.
＜分散剤＞
・分散剤Ａ（エチレン性不飽和基を有さない樹脂）：以下に示す方法で合成した。 <Dispersing agent>
Dispersant A (resin having no ethylenically unsaturated group): Synthesized by the method shown below.
（合成例Ａ１：マクロモノマーＡ－１の合成）
　容量３０００ｍＬの三口フラスコに、ε－カプロラクトン（１０４４．２ｇ）、δ－バレロラクトン（１８４．３ｇ）、及び、２－エチル－１－ヘキサノール（７１．６ｇ）を導入し、混合物を得た。次に、窒素を吹き込みながら、上記混合物を撹拌した。次に、混合物にＤｉｓｐｅｒｂｙｋ１１１（１２．５ｇ、ビックケミー社製、リン酸樹脂）を加え、得られた混合物を９０℃に加熱した。６時間後、１Ｈ－ＮＭＲ（ｎｕｃｌｅａｒ　ｍａｇｎｅｔｉｃ　ｒｅｓｏｎａｎｃｅ）を用いて、混合物中における２－エチル－１－ヘキサノールに由来するシグナルが消失したのを確認後、混合物を１１０℃に加熱した。窒素下にて１１０℃で１２時間重合反応を続けた後、１Ｈ－ＮＭＲでε－カプロラクトン及びδ－バレロラクトンに由来するシグナルの消失を確認し、得られた化合物について、ＧＰＣ法により分子量測定を行った。化合物の分子量が所望の値に到達したことを確認した後、上記化合物を含有する混合物に２，６－ジｔ－ブチル－４－メチルフェノール（０．３５ｇ）を添加した後、更に、得られた混合物に対して、２－メタクリロイロキシエチルイソシアネート（８７．０ｇ）を３０分かけて滴下した。滴下終了から６時間後、１Ｈ－ＮＭＲにて２－メタクリロイロキシエチルイソシアネート（ＭＯＩ）に由来するシグナルが消失したのを確認後、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）（１３８７．０ｇ）を混合物に添加し、濃度が５０質量％のマクロモノマーＡ－１溶液（２７７０ｇ）を得た。得られたマクロモノマーＡ－１の重量平均分子量は６，０００であった。 Synthesis Example A1: Synthesis of Macromonomer A-1
In a three-necked flask with a volume of 3000 mL, ε-caprolactone (1044.2 g), δ-valerolactone (184.3 g), and 2-ethyl-1-hexanol (71.6 g) were introduced to obtain a mixture. The mixture was then stirred while blowing with nitrogen. Next, Disperbyk 111 (12.5 g, manufactured by Bick Chemie, phosphoric acid resin) was added to the mixture, and the resulting mixture was heated to 90 ° C. After 6 hours, the mixture was heated to 110 ° C. after confirming that the signal derived from 2-ethyl-1-hexanol in the mixture had disappeared using 1 H-NMR (nuclear magnetic resonance). After continuing the polymerization reaction at 110 ° C. under nitrogen for 12 hours, the disappearance of the signal derived from ε-caprolactone and δ-valerolactone is confirmed by 1 H-NMR, and the molecular weight of the obtained compound is measured by GPC. Did. After confirming that the molecular weight of the compound has reached the desired value, 2,6-di-t-butyl-4-methylphenol (0.35 g) is added to the mixture containing the above-mentioned compound, and further obtained To the resulting mixture, 2-methacryloyloxyethyl isocyanate (87.Og) was added dropwise over 30 minutes. After confirming that the signal derived from 2-methacryloyloxyethyl isocyanate (MOI) disappeared by 1 H-NMR six hours after the completion of the dropwise addition, a mixture of propylene glycol monomethyl ether acetate (PGMEA) (1387.0 g) was used. To give a 50% by weight solution of macromonomer A-1 (2770 g). The weight average molecular weight of the obtained macromonomer A-1 was 6,000.
（分散剤Ａの合成）
　容量１０００ｍＬの三口フラスコに、上記マクロモノマーＡ－１溶液（２００．０ｇ）、メタクリル酸（以下「ＭＡＡ」ともいう、６０．０ｇ）、ベンジルメタクリレート（以下「ＢｚＭＡ」ともいう、４０．０ｇ）、ＰＧＭＥＡ（プロピレングリコール１－モノメチルエーテル２－アセタート、３６６．７ｇ）を導入し、混合物を得た。窒素を吹き込みながら、上記混合物を撹拌した。次に、窒素をフラスコ内に流しながら、混合物を７５℃まで昇温した。次に、混合物に、ドデシルメルカプタン（５．８５ｇ）、次いで、２，２’－アゾビス（２－メチルプロピオン酸メチル）（１．４８ｇ、以下「Ｖ－６０１」ともいう。）を添加し、重合反応を開始した。混合物を７５℃で２時間加熱した後、更にＶ－６０１（１．４８ｇ）を混合物に追加した。２時間後、更にＶ－６０１（１．４８ｇ）を混合物に追加した。更に２時間反応後、混合物を９０℃に昇温し、３時間撹拌した。上記操作により、重合反応は終了し、その後、固形分を精製して分散剤Ａを得た。
　その後、分散剤Ａを３０質量％溶液（溶媒：ＰＧＭＥＡ）として分散組成物の調製に使用した。 (Synthesis of Dispersant A)
The above macromonomer A-1 solution (200.0 g), methacrylic acid (hereinafter also referred to as “MAA”, 60.0 g), benzyl methacrylate (hereinafter also referred to as “BzMA”, 40.0 g) in a 1000 mL three-necked flask PGMEA (propylene glycol 1-monomethyl ether 2-acetate, 366.7 g) was introduced to give a mixture. The mixture was stirred while blowing with nitrogen. The mixture was then warmed to 75 ° C. while flowing nitrogen into the flask. Next, to the mixture, dodecyl mercaptan (5.85 g) and then 2,2'-azobis (methyl 2-methylpropionate) (1.48 g, hereinafter also referred to as "V-601") are added, and polymerization is performed. The reaction has started. After heating the mixture at 75 ° C. for 2 hours, more V-601 (1.48 g) was added to the mixture. After 2 hours, more V-601 (1.48 g) was added to the mixture. After further reacting for 2 hours, the mixture was heated to 90 ° C. and stirred for 3 hours. By the above operation, the polymerization reaction was completed, and then the solid content was purified to obtain dispersant A.
Thereafter, Dispersant A was used as a 30% by mass solution (solvent: PGMEA) for the preparation of the dispersion composition.
・分散剤Ｂ（エチレン性不飽和基を有する樹脂）：以下に示す方法で合成した。 Dispersant B (resin having an ethylenically unsaturated group): Synthesized by the method shown below.
（分散剤Ｂの合成）
　容量１０００ｍＬの三口フラスコに、上記マクロモノマーＡ－１溶液（２００．０ｇ）、ＭＡＡ（６０．０ｇ）、ＢｚＭＡ（４０．０ｇ）、ＰＧＭＥＡ（３６６．７ｇ）を導入し、混合物を得た。窒素を吹き込みながら、上記混合物を撹拌した。次に、窒素をフラスコ内に流しながら、混合物を７５℃まで昇温した。次に、混合物に、ドデシルメルカプタン（５．８５ｇ）、次いで、Ｖ－６０１（１．４８ｇ）を添加し、重合反応を開始した。混合物を７５℃で２時間加熱した後、更にＶ－６０１（１．４８ｇ）を混合物に追加した。２時間後、更にＶ－６０１（１．４８ｇ）を混合物に追加した。更に２時間反応後、混合物を９０℃に昇温し、３時間撹拌した。上記操作により、重合反応は終了した。
　反応終了後、空気下でテトラブチルアンモニウムブロミド（ＴＢＡＢ、７．５ｇ）とｐ－メトキシフェノール（ＭＥＨＱ，０．１３ｇ）を加えた後、メタクリル酸グリシジル（以下、「ＧＭＡ」ともいう、６６．１ｇ）を滴下した。滴下終了後、空気下で、７時間反応を続けた後、酸価測定により反応終了を確認した。得られた混合物にＰＧＭＥＡ（６４３．６ｇ）を追加することで分散剤Ｂの２０質量％溶液を得た。得られた分散剤Ｂの重量平均分子量は３５０００、酸価は５０ｍｇＫＯＨ／ｍｇであった。 (Synthesis of Dispersant B)
The above macromonomer A-1 solution (200.0 g), MAA (60.0 g), BzMA (40.0 g), and PGMEA (366.7 g) were introduced into a 1000 mL three-necked flask to obtain a mixture. The mixture was stirred while blowing with nitrogen. The mixture was then warmed to 75 ° C. while flowing nitrogen into the flask. Next, to the mixture, dodecyl mercaptan (5.85 g) and then V-601 (1.48 g) were added to initiate the polymerization reaction. After heating the mixture at 75 ° C. for 2 hours, more V-601 (1.48 g) was added to the mixture. After 2 hours, more V-601 (1.48 g) was added to the mixture. After further reacting for 2 hours, the mixture was heated to 90 ° C. and stirred for 3 hours. The polymerization reaction was completed by the above operation.
After completion of the reaction, tetrabutylammonium bromide (TBAB, 7.5 g) and p-methoxyphenol (MEHQ, 0.13 g) were added under air, and then glycidyl methacrylate (hereinafter also referred to as "GMA", 66.1 g) ) Was added dropwise. After completion of the dropwise addition, the reaction was continued under air for 7 hours, and the completion of the reaction was confirmed by acid value measurement. A 20% by mass solution of Dispersant B was obtained by adding PGMEA (643.6 g) to the obtained mixture. The weight average molecular weight of the resulting dispersant B was 35,000, and the acid value was 50 mg KOH / mg.
・分散剤Ｃ（エチレン性不飽和基を有する樹脂）：以下に示す方法で合成した。 Dispersant C (resin having an ethylenically unsaturated group): Synthesized by the method shown below.
（分散剤Ｃの合成）
　容量１０００ｍＬの三口フラスコに、上記マクロモノマーＡ－１溶液（1００．０ｇ）、ＭＡＡ（２００．０ｇ）、ＰＧＭＥＡ（３６６．７ｇ）を導入し、混合物を得た。これ以降は、分散剤Ｂの合成と同様の方法で、分散剤Ｃの２０質量％溶液を作製した。得られた分散剤Ｃの重量平均分子量は２８０００、酸価は５５ｍｇＫＯＨ／ｍｇであった。 (Synthesis of Dispersant C)
The above macromonomer A-1 solution (100.0 g), MAA (200.0 g), and PGMEA (366.7 g) were introduced into a 1000 mL three-necked flask to obtain a mixture. Thereafter, in the same manner as in the synthesis of Dispersant B, a 20 mass% solution of Dispersant C was prepared. The weight average molecular weight of the obtained dispersant C was 28,000, and the acid value was 55 mg KOH / mg.
＜溶剤＞
・ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート <Solvent>
PGMEA: Propylene glycol monomethyl ether acetate
＜分散組成物の調製方法＞
　各成分を表１に示す組成比（質量部比）になるように混合して、得られた混合物を、（株）シンマルエンタープライゼス製のＮＰＭ－Ｐｉｌｏｔを使用して下記条件にて分散させ、分散組成物を得た。 <Method of Preparing Dispersion Composition>
Each component is mixed to have a composition ratio (part by mass ratio) shown in Table 1, and the obtained mixture is dispersed under the following conditions using NPM-Pilot manufactured by Shinmaru Enterprises Co., Ltd. , A dispersion composition was obtained.
（分散条件）
・ビーズ径：φ０．０５ｍｍ、（ニッカトー製ジルコニアビーズ、ＹＴＺ）
・ビーズ充填率：６５体積％
・ミル周速：１０又は１２ｍ／ｓｅｃ
・セパレータ周速：１３ｍ／ｓ
・分散処理する混合液量：１５ｋｇ
・循環流量（ポンプ供給量）：９０ｋｇ／ｈｏｕｒ
・処理液温度：１９～２１℃
・冷却水：水
・処理時間：２２時間 (Distribution condition)
· Bead diameter: φ 0.05 mm, (Nikkato zirconia beads, YTZ)
・ Bead packing rate: 65% by volume
· Mill circumferential speed: 10 or 12 m / sec
・ Separator circumferential speed: 13 m / s
・ The amount of mixed liquid to be dispersed: 15 kg
Circulating flow rate (pump supply rate): 90 kg / hour
· Processing solution temperature: 19 to 21 ° C
Cooling water: Water Treatment time: 22 hours
〔硬化性組成物の調製〕
　上述した分散組成物と、以下に示す他の成分を混合して、実施例及び比較例で用いる各硬化性組成物を得た。
　以下の表２に各硬化性組成物における各成分の組成比（質量部比）を示す。
　なお、「含有する顔料の種類」の欄の「緑色」の記載は、ＰＧ５８とＰＹ１８５とが併用されており、全体として緑色の硬化膜を形成するため硬化性組成物となっていることを意味する。
　「顔料（Ａ）」、「顔料（Ｂ）」、「顔料（Ｃ）」の記載は、それぞれ「無機黒色顔料（Ａ）」、「無機黒色顔料（Ｂ）」、「無機黒色顔料（Ｃ）」を意味する。
　「樹脂のＣ＝Ｃ価」の欄は、各硬化性組成物中に含有される樹脂全質量に対する、エチレン性不飽和基含有量（Ｃ＝Ｃ価）（ｍｍｏｌ／ｇ）を意味する。
　なお、Ｃ＝Ｃ価は、以下の方法で求めた。まず、各樹脂の樹脂溶液（分散剤Ｂの２０質量％溶液等）を用いて、ＨＰＬＣ法（絶対検量線法）で各樹脂のＣ＝Ｃ価を求め、その上で、各硬化性組成物に配合した各樹脂の配合比から、各硬化性組成物中に含有される樹脂全体のＣ＝Ｃ価を計算して求めた。 [Preparation of Curable Composition]
The dispersion composition described above and other components shown below were mixed to obtain each curable composition used in Examples and Comparative Examples.
Table 2 below shows the composition ratio (parts by mass) of each component in each curable composition.
In addition, description of "green" of the column of "the kind of pigment to contain" means that PG58 and PY185 are used together and it becomes a curable composition in order to form a green cured film as a whole. Do.
The descriptions for "pigment (A)", "pigment (B)" and "pigment (C)" are "inorganic black pigment (A)", "inorganic black pigment (B)" and "inorganic black pigment (C), respectively. Means ".
The column "C = C value of resin" means an ethylenically unsaturated group content (C = C value) (mmol / g) based on the total mass of the resin contained in each curable composition.
In addition, C = C number was calculated | required by the following method. First, using a resin solution of each resin (20 mass% solution of Dispersant B, etc.), the C = C value of each resin is determined by HPLC method (absolute calibration method), and then each curable composition is determined. The C = C value of the entire resin contained in each curable composition was calculated from the compounding ratio of each resin compounded in the above.
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
　以下に、表２中の記載に対応する成分の詳細を示す。 Below, the detail of the component corresponding to description of Table 2 is shown.
＜分散組成物＞
　上述の方法で調製した分散組成物を使用した。
　それぞれの番号の硬化性組成物で、対応する番号の分散組成物を使用した。 <Dispersion composition>
The dispersion composition prepared by the method described above was used.
For each numbered curable composition, the corresponding numbered dispersion composition was used.
＜アルカリ可溶性樹脂＞ <Alkali-soluble resin>
・Ａ－１（エチレン性不飽和基を含有する樹脂）：アクリキュアＲＤ－Ｆ８、日本触媒社製、固形分４０％、（溶剤：プロピレングリコールモノメチルエーテル） · A-1 (resin containing an ethylenically unsaturated group): Acrycure RD-F8, manufactured by Nippon Shokuhin Co., Ltd., solid content 40%, (solvent: propylene glycol monomethyl ether)
　なお、アルカリ可溶性樹脂Ａ－１は樹脂を含有する溶液（樹脂溶液）として使用した。 The alkali-soluble resin A-1 was used as a resin-containing solution (resin solution).
＜重合開始剤＞
・Ｉ－１：下記の、式（Ｉ－１）で表される化合物 <Polymerization initiator>
I-1: a compound represented by the following formula (I-1)
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
＜重合性化合物＞
・Ｍ１：ＫＡＹＡＲＡＤ　ＤＰＨＡ、日本化薬社製、６官能重合性化合物（エチレン性不飽和基の量：１０．４ｍｍｏｌ／ｇ）、及び、５官能重合性化合物（エチレン性不飽和基の量：９．５ｍｍｏｌ／ｇ）の混合物）
・Ｍ２：Ａ－ＤＰＨ－１２Ｅ、新中村化学社製、６官能重合性化合物（エチレン性不飽和基の量：５．４１ｍｍｏｌ／ｇ）
・Ｍ３：Ａ－９３００、新中村化学社製、３官能重合性化合物（エチレン性不飽和基の量：７．０９ｍｍｏｌ／ｇ） <Polymerizable compound>
M1: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., hexafunctional polymerizable compound (amount of ethylenically unsaturated group: 10.4 mmol / g), and pentafunctional polymerizable compound (amount of ethylenically unsaturated group: 9 .5 mmol / g))
M2: A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., 6-functional polymerizable compound (amount of ethylenically unsaturated group: 5.41 mmol / g)
M3: A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd., trifunctional polymerizable compound (amount of ethylenically unsaturated group: 7.09 mmol / g)
＜重合禁止剤＞
・ＰＩ－１：ｐ－メトキシフェノール <Polymerization inhibitor>
PI-1: p-methoxyphenol
＜界面活性剤＞
・１：下記式により表される界面活性剤（重量平均分子量（Ｍｗ）＝１５３１１）
　ただし、下記式において、式中（Ａ）及び（Ｂ）で表される構造単位はそれぞれ６２モル％、３８モル％である。式（Ｂ）で表される構造単位中、ａは、ｂ、ｃは、それぞれ、ａ＋ｃ＝１４、ｂ＝１７の関係を満たす。 <Surfactant>
· 1: Surfactant represented by the following formula (weight-average molecular weight (Mw) = 15311)
However, in the following formulas, structural units represented by (A) and (B) in the formula are 62 mol% and 38 mol%, respectively. In the structural unit represented by Formula (B), a and b and c satisfy the relationship of a + c = 14 and b = 17, respectively.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
＜溶剤＞ <Solvent>
・ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート PGMEA: Propylene glycol monomethyl ether acetate
［評価］
〔各硬化性組成物層の光学濃度〕
　厚み０．７ｍｍ、大きさ１０ｃｍ角のガラス基板（ＥａｇｌｅＸＧ、Ｃｏｒｎｉｎｇ社製）上に、各硬化性組成物をスピンコート法で塗布して、硬化性組成物層を得た。なお、このとき、９０℃のホットプレートを用いて１５０秒間加熱処理（プリベーク）を行なって、乾燥させた後の硬化性組成物層の膜厚が１．５μｍとなるように、スピンコーターの回転数を調整した。
　得られた乾燥後の硬化性組成物層について、透過濃度計（Ｘ－ｒｉｔｅ　３６１Ｔ（ｖｉｓｕａｌ）ｄｅｎｓｉｔｏｍｅｔｅｒ）を用いて、波長３６５ｎｍ及び波長５５０ｎｍにおける光学濃度を測定した。
　結果を表３に示す。 [Evaluation]
[Optical density of each curable composition layer]
Each curable composition was applied by spin coating on a glass substrate (EagleXG, manufactured by Corning) having a thickness of 0.7 mm and a size of 10 cm square to obtain a curable composition layer. At this time, heat treatment (pre-baking) is performed for 150 seconds using a hot plate at 90 ° C., and rotation of the spin coater is performed so that the film thickness of the curable composition layer after drying becomes 1.5 μm. Adjusted the number.
The optical density at a wavelength of 365 nm and a wavelength of 550 nm was measured for the resulting curable composition layer after drying using a transmission densitometer (X-rite 361 T (visual) densitometer).
The results are shown in Table 3.
〔矩形性評価（初期）〕
　あらかじめヘキサメチルジシラザンを噴霧した２００ｍｍ（８インチ）シリコンウエハ（基板）に、調製直後の各硬化膜形成用組成物をスピンコート法で塗布し、硬化性組成物層を形成した。なお、このとき、９０℃のホットプレートを用いて１５０秒間加熱処理（プリベーク）を行なって、乾燥させた後の硬化性組成物層の膜厚が１．５μｍとなるように、スピンコーターの回転数を調整した。
　乾燥させた膜厚１．５μｍの硬化性組成物層に対して、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（Ｃａｎｏｎ（株）製）を使用して、３６５ｎｍの波長で、パターンが３．０μｍ四方のＩｓｌａｎｄパターンマスクを通して露光した。
　各実施例及び比較例において、露光時の酸素濃度は２５～５５体積％の範囲、放射照度は１５０００～５５０００Ｗ／ｍ２の範囲とし、最適露光量で露光した。
　なお、露光は、プリベークをしてから１０分以内に行った。 [Rectangularity evaluation (initial)]
The composition for cured film formation immediately after preparation was applied by spin coating to a 200 mm (8 inch) silicon wafer (substrate) previously sprayed with hexamethyldisilazane, to form a curable composition layer. At this time, heat treatment (pre-baking) is performed for 150 seconds using a hot plate at 90 ° C., and rotation of the spin coater is performed so that the film thickness of the curable composition layer after drying becomes 1.5 μm. Adjusted the number.
An i-line stepper exposure apparatus FPA-3000i5 + (Canon Co., Ltd.) is used for the dried curable composition layer with a film thickness of 1.5 μm to form a 3.0 μm-square pattern at a wavelength of 365 nm. It exposed through an Island pattern mask.
In each of the examples and the comparative examples, the exposure was performed at the optimum exposure dose with the oxygen concentration at the time of exposure set in the range of 25 to 55% by volume and the irradiance set in the range of 15,000 to 55,000 W / m 2 .
The exposure was performed within 10 minutes after prebaking.
　その後、露光された硬化性組成物層が形成されているシリコンウエハをスピン・シャワー現像機（ＤＷ－３０型、ケミトロニクス社製）の水平回転テーブル上に載置し、ＣＤ－２０００（有機アルカリ現像液、富士フイルムエレクトロニクスマテリアルズ社製）を用いて２３℃で６０秒間パドル現像した。
　このようにして、下塗り層付シリコンウエハに、パターン（３．０μｍ角の正方形ピクセルパターン状の硬化膜）を形成した。パターンが形成されたシリコンウエハを、真空チャック方式で水平回転テーブルに固定し、このシリコンウエハを回転装置によって回転数５０ｒｐｍで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理した。その後、このシリコンウエハを乾燥した。得られたシリコンウエハを、更に、２００℃で３００秒間過熱（ポストベーク）して、パターン状硬化膜付シリコンウエハを得た。 After that, the silicon wafer on which the curable composition layer that has been exposed is formed is placed on the horizontal rotation table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (organic alkali) Paddle development was carried out at 23 ° C. for 60 seconds using a developer, manufactured by Fujifilm Electronics Materials.
In this way, a pattern (a cured film in the form of a square pixel pattern of 3.0 μm square) was formed on the undercoating silicon wafer. A silicon wafer on which a pattern is formed is fixed to a horizontal rotation table by a vacuum chuck method, and while rotating this silicon wafer at a rotation speed of 50 rpm by a rotation device, pure water is showered from above the rotation center from a spray nozzle It was supplied and rinsed. Thereafter, the silicon wafer was dried. The obtained silicon wafer was further heated (post-baked) at 200 ° C. for 300 seconds to obtain a silicon wafer with a patterned cured film.
　得られたシリコンウエハの断面を走査型電子顕微鏡で観察し、３．０μｍ角の正方形ピクセルパターン側壁（正方形の硬化膜の側壁）の、シリコンウエハ表面に対する角度を測定し、以下の評価基準でパターンの矩形性を評価した。
　結果を表３に示す。 The cross section of the obtained silicon wafer is observed with a scanning electron microscope, and the angle of the 3.0 μm square pixel pixel side wall (side wall of the square cured film) with respect to the silicon wafer surface is measured. Of the rectangularity of
The results are shown in Table 3.
　「ＡＡ」：側壁の角度が８０°以上１００°未満
　「Ａ」：側壁の角度が７５°以上８０°未満、又は、１００°以上１０５°未満
　「Ｂ」：側壁の角度が７０°以上７５°未満、又は、１０５°以上１１０°未満
　「Ｃ」：側壁の角度が６０°以上７０°未満、又は、１１０°以上１２０°未満
　「Ｄ」：側壁の角度が５０°以上６０°未満、又は、１２０°以上１３０°未満
　「Ｅ」：側壁の角度が５０°未満、又は、１３０°以上 “AA”: angle of side wall 80 ° to 100 ° “A”: angle of side wall 75 ° to less than 80 °, or 100 ° to less than 105 ° “B”: angle of side wall 70 ° to 75 ° Less than 105 ° or more and less than 110 ° “C”: angle of sidewall 60 ° or more and less than 70 °, or 110 ° or more but less than 120 ° “D”: angle of sidewall 50 ° or more and less than 60 ° or 120 ° or more and less than 130 ° "E": Sidewall angle is less than 50 ° or 130 ° or more
〔パターンの矩形性評価（プリベークをしてから１週間後）〕
　露光を、プリベークをしたあと１週間引き置きしてから行った以外は、上述したのと同様に矩形性評価を実施し、同様の基準で評価した。
　結果を表３に示す。 [Evaluation of pattern rectangularity (one week after prebaking)]
The rectangularity evaluation was carried out in the same manner as described above except that exposure was carried out for 1 week after prebaking and then carried out, and evaluation was made based on the same criteria.
The results are shown in Table 3.
〔パターンの矩形性評価（液経時１ヶ月後）〕
　調製してから室温（２３℃、相対湿度５０％）で１ヶ月保管した後の硬化性組成物を使用して硬化性組成物層を形成した以外は、上述したのと同様に〔矩形性評価（初期）〕を実施し、同様の基準で評価した。
　結果を表３に示す。 [Rectangularity evaluation of pattern (after one month of liquid aging)]
[Square property evaluation is the same as that described above except that a curable composition layer is formed using the curable composition after being prepared and stored for 1 month at room temperature (23.degree. C., relative humidity 50%). (Early)] was carried out and evaluated on the same basis.
The results are shown in Table 3.
［結果］
　以下の表３に、試験結果を示す。
　なお、表３中、「顔料」の欄は、使用した硬化性組成物が含有する黒色顔料の種類を示す。この欄に記載の略号は、〔分散組成物の調製〕で説明したのと同様である。なお、「緑色」の記載は、ＰＧ５８とＰＹ１８５とを併用して、全体として緑色の硬化膜としたことを意味する。「顔料（Ａ）」、「顔料（Ｂ）」、「顔料（Ｃ）」の記載は、それぞれ「無機黒色顔料（Ａ）」、「無機黒色顔料（Ｂ）」、「無機黒色顔料（Ｃ）」を意味する。
　「樹脂のＣ＝Ｃ価」の欄は、使用した硬化性組成物中に含有される樹脂全体のエチレン性不飽和基含有量（ｍｍｏｌ／ｇ）を意味する。
　「分散機ミル周速」の欄は、硬化性組成物の作製に使用した分散組成物を調製する際のミル周速を意味する。
　「式（１）値」の欄は、各試験条件を上述の式（１）（Ｘ×Ｙ÷Ｚ）に当てはめて計算して得られた値である。計算方法は上述の通りである。
　「矩形性」の欄における、「初期」「１週間」「１ヶ月」の欄には、それぞれ、〔矩形性評価（初期）〕〔パターンの矩形性評価（プリベークをしてから１週間後）〕〔パターンの矩形性評価（液経時１ヶ月後）〕の試験の評価結果を記載する。 [result]
The test results are shown in Table 3 below.
In Table 3, the column "pigment" indicates the type of black pigment contained in the curable composition used. The abbreviations described in this column are the same as those described in [Preparation of Dispersion Composition]. In addition, description of "green" means that PG58 and PY185 are used together and it was set as the green cured film as a whole. The descriptions for "pigment (A)", "pigment (B)" and "pigment (C)" are "inorganic black pigment (A)", "inorganic black pigment (B)" and "inorganic black pigment (C), respectively. Means ".
The column "C = C value of resin" means the ethylenic unsaturated group content (mmol / g) of the entire resin contained in the curable composition used.
The column "Disperser Mill Peripheral Speed" means the mill peripheral speed when preparing the dispersion composition used to make the curable composition.
The column of “Expression (1) value” is a value obtained by applying each test condition to the above-mentioned Expression (1) (X × Y ÷ Z). The calculation method is as described above.
[Rectangularity evaluation (initial)] [rectangularity evaluation of pattern (one week after prebaking) in the columns of “initial”, “one week” and “one month” in the “rectangularity” column Evaluation results of the test of [squareness evaluation of pattern (after 1 month liquid aging)] are described.
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
　表３に示すように、本発明の製造方法によれば、断面形状の矩形性が優れる硬化膜（パターン状の硬化膜）を製造でき、引き置きされた硬化性組成物層を用いた場合でも優れた矩形性を維持できる（矩形性の評価がＣ以上である）傾向が確認された。
　黒色顔料として、チタンの窒化物若しくは酸窒化物、ジルコニウムの窒化物若しくは酸窒化物、バナジウムの窒化物若しくは酸窒化物、又は、ニオブの窒化物若しくは酸窒化物を使用する場合、引置き期間をおいても、得られるパターンの矩形性が劣化しにくい傾向が確認された（実施例１０とその他の実施例との比較）。
　黒色顔料として、チタンの窒化物若しくは酸窒化物、又は、ジルコニウムの窒化物若しくは酸窒化物を使用する場合、より矩形性が優れる硬化膜を得られる傾向が確認された（実施例１、３、及び、７の結果）。
　硬化性組成物に含有される樹脂全体に対するエチレン性不飽和基の含有量が０．１０～３．００ｍｍｏｌ／ｇである場合、より矩形性が優れる硬化膜を得られる傾向が確認された（実施例１、１３、及び、１４の比較）。
　硬化性組成物を用いて形成された硬化性組成物層の光学濃度Ａが２．８０～４．００となり、かつ、光学濃度Ｂが２．５０～７．００である場合、より矩形性が優れる硬化膜を得られる傾向が確認された（実施例１、２、及び、６の結果）。
　露光時の放射照度が２００００～５００００Ｗ／ｍ２である場合、より矩形性が優れる硬化膜を得られ、露光時の放射照度が２５０００～４００００Ｗ／ｍ２である場合、更に矩形性が優れる硬化膜を得られる傾向が確認された（実施例１、４、５、１１、１２の結果）。
　黒色顔料として、無機黒色顔料（Ａ）、（Ｂ）、（Ｃ）を使用する場合、実施例１と同様に、より矩形性が優れる硬化膜を得られる傾向が確認された（実施例１、１８、１９、及び、２０の結果）。
　また、式（１）で算出した値が、２．８０×１０－５～５．２０×１０－５の範囲内である場合、室温（２３℃、相対湿度５０％）１ヶ月保管処理をした後の硬化性組成物を用いた場合においても、保管処理を経ていない硬化性組成物を用いて評価した場合とくらべて、作製される硬化膜の断面形状の矩形性の劣化が抑制されていた（実施例１～４、７～９、及び、１３～１７の結果）。 As shown in Table 3, according to the production method of the present invention, a cured film (patterned cured film) excellent in rectangularity of the cross-sectional shape can be produced, and even in the case where the drawn curable composition layer is used. The tendency to maintain excellent rectangularity (the evaluation of rectangularity is C or higher) was confirmed.
When using a nitride or oxynitride of titanium, a nitride or oxynitride of zirconium, a nitride or oxynitride of vanadium, or a nitride or oxynitride of niobium as the black pigment, the drawing period should be Also in this case, it was confirmed that the rectangularity of the obtained pattern did not easily deteriorate (comparison of Example 10 with other Examples).
When a nitride or oxynitride of titanium, or a nitride or oxynitride of zirconium is used as the black pigment, a tendency to obtain a cured film with more rectangularity was confirmed (Examples 1, 3, And 7).
When the content of the ethylenically unsaturated group with respect to the entire resin contained in the curable composition is 0.10 to 3.00 mmol / g, a tendency to obtain a cured film having more excellent rectangularity was confirmed (implementation Comparison of Examples 1, 13 and 14).
When the optical density A of the curable composition layer formed using the curable composition is 2.80 to 4.00 and the optical density B is 2.50 to 7.00, more rectangularity is obtained. The tendency which can acquire the outstanding cured film was confirmed (result of Example 1, 2 and 6).
When the irradiance at the time of exposure is from 20000 to 50000 W / m 2 , a cured film having more rectangularity is obtained, and when the irradiance at the exposure is from 25000 to 40000 W / m 2 , the cured film is more excellent in rectangularity. Tend to be obtained (Results of Examples 1, 4, 5, 11 and 12).
When inorganic black pigments (A), (B) and (C) were used as the black pigment, it was confirmed that a cured film having more excellent rectangularity could be obtained as in Example 1 (Example 1, 18, 19 and 20 results).
Moreover, when the value calculated by Formula (1) is in the range of 2.80 × 10 −5 to 5.20 × 10 −5 , storage treatment was performed for 1 month at room temperature (23 ° C., relative humidity 50%) Even in the case of using the later curable composition, deterioration of the rectangularity of the cross-sectional shape of the cured film to be produced was suppressed as compared with the case of evaluation using the curable composition which did not go through storage processing (Results of Examples 1 to 4, 7 to 9, and 13 to 17).
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・・・硬化膜
２０１・・・受光素子
２０２・・・カラーフィルタ
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・・・硬化膜
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
  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 substrate 108 ... electrode pad 109 ... external connection terminal 110 ... penetrating electrode 111 ... lens layer 112 ... lens material 113 ... support 114, 115 ... cured film 201 ... light receiving element 202: color filter 201: light receiving element 202: color filter 203: microlens 204: substrate 205b: blue pixel 205r: red pixel 205g: green pixel 205bm,. Black matrix 206 p well layer 207 read gate portion 208 vertical transfer path 209 element isolation region 210 Insulating film 211 ... vertical transfer electrode 212 ... cured film 213, 214 ... insulating film 215 ... flattening film 300 ... infrared sensor 310 ... solid imaging element 311 ... infrared Absorption filter 312 ... color filter 313 ... infrared transmission filter 314 ... resin film 315 ... micro lens 316 ... flattening film

Claims (16)

  1. 　黒色顔料及び重合性化合物を含有する硬化性組成物を用いて、膜厚１．５μｍあたりの波長３６５ｎｍにおける光学濃度Ａが２．６０～１０．００であり、かつ、膜厚１．５μｍあたりの波長５５０ｎｍにおける光学濃度Ｂが２．００～１０．００である硬化性組成物層を形成する工程と、
    　前記硬化性組成物層を、酸素濃度が３０～５０体積％の条件下で露光する工程と、
    　前記露光後の前記硬化性組成物層を現像して硬化膜を形成する工程と、を含有する、
    　硬化膜の製造方法。     When using a curable composition containing a black pigment and a polymerizable compound, the optical density A at a wavelength of 365 nm per 1.5 μm of film thickness is 2.60 to 10.00, and per 1.5 μm of film thickness Forming a curable composition layer having an optical density B at a wavelength of 550 nm of 2.00 to 10.00,
    Exposing the curable composition layer under conditions of an oxygen concentration of 30 to 50% by volume;
    Developing the curable composition layer after the exposure to form a cured film,
    Method of producing a cured film.
  2. 　前記黒色顔料が、第４族の金属元素の窒化物若しくは酸窒化物、第５族の金属元素の窒化物若しくは酸窒化物、又は、カーボンブラックである、請求項１に記載の硬化膜の製造方法。 The production of a cured film according to claim 1, wherein the black pigment is a nitride or oxynitride of a group 4 metal element, a nitride or oxynitride of a group 5 metal element, or carbon black. Method.
  3. 　前記黒色顔料が、チタンの窒化物若しくは酸窒化物、ジルコニウムの窒化物若しくは酸窒化物、バナジウムの窒化物若しくは酸窒化物、ニオブの窒化物若しくは酸窒化物、又は、カーボンブラックである、請求項１又は２に記載の硬化膜の製造方法。 The black pigment is a nitride or oxynitride of titanium, a nitride or oxynitride of zirconium, a nitride or oxynitride of vanadium, a nitride or oxynitride of niobium, or carbon black. The manufacturing method of the cured film as described in 1 or 2.
  4. 　前記黒色顔料が、チタンの窒化物若しくは酸窒化物、ジルコニウムの窒化物若しくは酸窒化物、バナジウムの窒化物若しくは酸窒化物、又は、ニオブの窒化物又は酸窒化物である、請求項１～３のいずれか１項に記載の硬化膜の製造方法。 4. The black pigment according to claim 1, wherein the black pigment is a nitride or oxynitride of titanium, a nitride or oxynitride of zirconium, a nitride or oxynitride of vanadium, or a nitride or oxynitride of niobium. The manufacturing method of the cured film of any one of these.
  5. 　前記黒色顔料が、チタンの窒化物若しくは酸窒化物、又は、ジルコニウムの窒化物若しくは酸窒化物である、請求項１～４のいずれか１項に記載の硬化膜の製造方法。 The method for producing a cured film according to any one of claims 1 to 4, wherein the black pigment is a nitride or oxynitride of titanium, or a nitride or oxynitride of zirconium.
  6. 　前記露光における、放射照度が２００００～５００００Ｗ／ｍ２である、請求項１～５のいずれか１項に記載の硬化膜の製造方法。 In the exposure, irradiance is 20000 ~ 50000W / m 2, process for preparing a cured film according to any one of claims 1 to 5.
  7. 　前記露光における、放射照度が２５０００～４００００Ｗ／ｍ２である、請求項１～６のいずれか１項に記載の硬化膜の製造方法。 In the exposure, irradiance is 25000 ~ 40000W / m 2, process for preparing a cured film according to any one of claims 1-6.
  8. 　前記光学濃度Ａが２．８０～４．００であり、かつ、前記光学濃度Ｂが２．５０～７．００である、請求項１～７のいずれか１項に記載の硬化膜の製造方法。 The method for producing a cured film according to any one of claims 1 to 7, wherein the optical density A is 2.80 to 4.00, and the optical density B is 2.50 to 7.00. .
  9. 　前記光学濃度Ａに対する前記光学濃度Ｂの比が０．５～２．０である、請求項１～８のいずれか１項に記載の硬化膜の製造方法。 The method for producing a cured film according to any one of claims 1 to 8, wherein a ratio of the optical density B to the optical density A is 0.5 to 2.0.
  10. 　前記硬化性組成物が、更に、樹脂を含有し、
    　前記樹脂が、エチレン性不飽和基を含有する樹脂を含有し、
    　前記樹脂の合計質量に対する、前記エチレン性不飽和基の含有量が、０．１０～３．００ｍｍｏｌ／ｇである、請求項１～９のいずれか１項に記載の硬化膜の製造方法。     The curable composition further contains a resin,
    The resin contains a resin containing an ethylenically unsaturated group,
    The method for producing a cured film according to any one of claims 1 to 9, wherein the content of the ethylenically unsaturated group is 0.10 to 3.00 mmol / g based on the total mass of the resin.
  11. 　前記硬化性組成物が、更に、重合開始剤を含有する、請求項１～１０のいずれか１項に記載の硬化膜の製造方法。 The method for producing a cured film according to any one of claims 1 to 10, wherein the curable composition further contains a polymerization initiator.
  12. 　前記硬化性組成物が、更に、重合禁止剤を含有する、請求項１～１１のいずれか１項に記載の硬化膜の製造方法。 The method for producing a cured film according to any one of claims 1 to 11, wherein the curable composition further contains a polymerization inhibitor.
  13. 　前記光学濃度ＡをＸ、前記露光時の酸素濃度をＹ、前記放射照度をＺとした場合に、下記式（１）で計算される値が２．８０×１０－５～５．２０×１０－５となる、請求項１～１２のいずれか１項に記載の硬化膜の製造方法。
    式（１）　Ｘ×Ｙ÷Ｚ     Assuming that the optical density A is X, the oxygen concentration at the exposure is Y, and the irradiance is Z, the value calculated by the following equation (1) is 2.80 × 10 −5 to 5.20 × 10 The method for producing a cured film according to any one of claims 1 to 12, which is -5 .
    Formula (1) X × Y ÷ Z
  14. 　前記硬化膜が遮光膜である、請求項１～１３のいずれか１項に記載の硬化膜の製造方法。 The method for producing a cured film according to any one of claims 1 to 13, wherein the cured film is a light shielding film.
  15. 　請求項１～１４のいずれか１項に記載の製造方法を介して、硬化膜を有する固体撮像素子の製造を行う、固体撮像素子の製造方法。 A method of manufacturing a solid-state imaging device, wherein a solid-state imaging device having a cured film is manufactured through the manufacturing method according to any one of claims 1 to 14.
  16. 　請求項１～１３のいずれか１項に記載の製造方法を介して、硬化膜を有する画像表示装置の製造を行う、画像表示装置の製造方法。
     
    　　　　　　　　　　　　　　　　　      A method of manufacturing an image display device, wherein the image display device having a cured film is manufactured through the method of manufacturing according to any one of claims 1 to 13.

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