WO2019171902A1 - Curable composition, cured film, optical element, solid-state imaging element and color filter - Google Patents

Curable composition, cured film, optical element, solid-state imaging element and color filter Download PDF

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Publication number
WO2019171902A1
WO2019171902A1 PCT/JP2019/005476 JP2019005476W WO2019171902A1 WO 2019171902 A1 WO2019171902 A1 WO 2019171902A1 JP 2019005476 W JP2019005476 W JP 2019005476W WO 2019171902 A1 WO2019171902 A1 WO 2019171902A1
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group
curable composition
resin
cured film
compound
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PCT/JP2019/005476
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French (fr)
Japanese (ja)
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貴洋 大谷
浜田　大輔
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富士フイルム株式会社
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Priority to JP2020504884A priority Critical patent/JP7083887B2/en
Publication of WO2019171902A1 publication Critical patent/WO2019171902A1/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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F290/08—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 side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—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

Definitions

  • the present invention relates to a curable composition, a cured film, an optical element, a solid-state imaging element, and a color filter.
  • a method for producing a cured film used in a solid-state imaging device or the like is generally a method in which a curable composition layer is formed on a substrate and then cured. Typically, the curable composition layer is irradiated with light through a predetermined mask pattern, and then development processing is performed.
  • Patent Document 1 discloses a photopolymerizable resin laminate in which a photopolymerizable resin layer and the like are laminated, and the photopolymerizable resin layer has an alkali-soluble polymer and an ethylenically unsaturated bond.
  • a photopolymerizable resin laminate comprising a photopolymerizable resin composition containing a compound, a photopolymerizable initiator, and a black pigment is disclosed.
  • [1] Contains black color material, polymerizable compound, resin A, photopolymerization initiator, and polymerization inhibitor, A curable composition, wherein the resin A satisfies any one of an acid value of 120 to 350 mgKOH / g and a weight average molecular weight of 3000 to 7500.
  • [3] [1] or [2] further containing a resin B which is a resin different from the resin A and has one or more groups selected from the group consisting of an oxyalkylene group and an oxyalkylenecarbonyl group.
  • a curable composition capable of producing a cured film having excellent line width stability
  • the present invention can provide a cured film formed using such a curable composition, and a color filter, an optical element, and a solid-state imaging device having the cured film.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the notation in which neither substitution nor substitution is described includes a group containing a substituent as well as a group not containing a substituent.
  • the “alkyl group” includes not only an alkyl group not containing a 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, deep ultraviolet, extreme ultraviolet (EUV), X-ray, and electron beam.
  • light means actinic rays and radiation.
  • Exposure in this specification includes not only exposure with far ultraviolet rays, X-rays, EUV light, etc., but also drawing with particle beams such as electron beams and ion beams, unless otherwise specified.
  • (meth) acrylate represents acrylate and methacrylate.
  • (meth) acryl represents acryl and methacryl.
  • (meth) acryloyl represents acryloyl and methacryloyl.
  • (meth) acrylamide represents acrylamide and methacrylamide.
  • “monomer” and “monomer” are synonymous.
  • ppm means “parts-per-million (10 ⁇ 6 )”
  • ppb means “parts-per-bilion (10 ⁇ 9 )”
  • ppt Means “parts-per-trilition (10 ⁇ 12 )”.
  • the weight average molecular weight (Mw) is a polystyrene equivalent value determined by a GPC (Gel Permeation Chromatography) method.
  • the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (4.6 mm ID ⁇ 15 cm, Tosoh Corporation) as columns and THF (tetrahydrofuran) as an eluent. ).
  • the curable composition of the present invention contains a black color material, a polymerizable compound, a resin A, a photopolymerization initiator, and a polymerization inhibitor.
  • the resin A has an acid value of 120 to 350 mg KOH / g (hereinafter also referred to as “requirement 1”) and a weight average molecular weight of 3000 to 7500 (hereinafter also referred to as “requirement 2”). It is a resin that satisfies one of the requirements.
  • a curable composition layer formed using a curable composition is usually cured through exposure and further developed. During the exposure, the irradiated light is diffracted and / or scattered, so that a slight amount of light leaks around the original exposure region, and the curable composition layer may be partially cured. As described above, the portion where the curable composition layer is partially cured around the original exposure region causes unintended enlargement of the cured film, and adversely affects the line width stability of the cured film.
  • the curable composition of the present invention contains a polymerization inhibitor, it is possible to reduce the occurrence of partial curing due to slight light leaking from the exposed area. Moreover, since the curable composition of this invention contains resin A which satisfy
  • the curable composition contains a black color material.
  • the black color material include one or more selected from the group consisting of black pigments and black dyes.
  • a black color material may be used individually by 1 type, and may use 2 or more types.
  • the content of the black color material in the curable composition is not particularly limited, but is preferably 1 to 99% by mass and more preferably 5 to 55% by mass with respect to the total solid content of the curable composition.
  • the total solid content of the curable composition intends a component that forms a cured film, and does not include a solvent. Moreover, if it is a component which forms a cured film, even if the property is a liquid state, it will be considered as solid content.
  • a plurality of colorants that cannot be used alone as a black color material may be combined and adjusted so as to be black as a whole to obtain a black color material.
  • a black pigment alone as a black pigment a plurality of pigments having colors other than black alone may be used in combination as a black pigment.
  • a black dye alone as a black dye a single dye having a color other than black may be used in combination as a black dye.
  • the black color material means a color material that has absorption over the entire wavelength range of 400 to 700 nm. More specifically, for example, a black color material that meets the evaluation standard Z described below is preferable.
  • a composition containing a coloring material, a transparent resin matrix (such as an acrylic resin) and a solvent and having a coloring material content of 60% by mass relative to the total solid content is prepared.
  • the obtained composition is applied onto a glass substrate so that the thickness of the dried coating film is 1 ⁇ m, thereby forming a coating film.
  • the light-shielding property of the coating film after drying is evaluated using a spectrophotometer (such as UV-3600 manufactured by Hitachi, Ltd.). If the maximum value of the transmittance at a wavelength of 400 to 700 nm of the coating film after drying is less than 10%, it can be determined that the color material is a black color material that meets the evaluation standard Z.
  • the black color material is preferably a black pigment from the viewpoint of obtaining a cured film having a reduced reflectance.
  • Various known black pigments can be used as the black pigment.
  • the black pigment may be an inorganic pigment or an organic pigment.
  • the black pigment a pigment that expresses black alone is preferable.
  • the black pigment is preferably a pigment that absorbs infrared rays, for example.
  • the black pigment that absorbs infrared rays has absorption in the wavelength region of the infrared region (preferably, wavelength 650 to 1300 nm), for example. It is also preferable to have a maximum absorption wavelength in the wavelength region of 675 to 900 nm.
  • Examples of inorganic pigments that absorb infrared rays and develop black alone include Group 4 metal elements such as titanium (Ti) and zirconium (Zr), and Group 5 such as vanadium (V) and niobium (Nb).
  • Metallic elements cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and silver (Ag)
  • Examples thereof include metal oxides, metal nitrides, and metal oxynitrides containing one or more metal elements selected from the group consisting of:
  • the inorganic pigment may be subjected to a surface modification treatment.
  • inorganic particles that have been surface-modified with a surface treatment agent having both a silicone group and an alkyl group can be mentioned, such as “KTP-09” series (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the metal oxide, the metal nitride, and the metal oxynitride may be used as particles in which other atoms are mixed.
  • it may be used as a metal nitride-containing particle that further contains an atom (preferably an oxygen atom and / or a sulfur atom) selected from Group 13 to 17 elements of the periodic table.
  • Carbon black is also mentioned as a pigment that absorbs infrared rays and develops black alone.
  • carbon black are commercially available C.I. I.
  • Organic pigments such as CI Pigment Black 1 and C.I. I.
  • inorganic pigments such as CI Pigment Black 7.
  • Carbon black whose surface is coated with a resin may be used as carbon black.
  • the nitride or oxide of a Group 4 metal element, or the nitride of a Group 5 metal element or Oxynitrides are preferred, titanium nitride or oxynitride, zirconium nitride or oxynitride, vanadium nitride or oxynitride, or niobium nitride or oxynitride, more preferably titanium nitride Or oxynitrides are more preferred.
  • the titanium nitride is titanium nitride, the zirconium nitride is zirconium nitride, the vanadium nitride is vanadium nitride, and the niobium nitride 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 Niobium.
  • titanium nitride is intended for TiN, and may contain oxygen atoms that are unavoidable in production (for example, the surface of TiN particles are unintentionally oxidized).
  • titanium nitride means a compound having a diffraction angle 2 ⁇ of a peak derived from the (200) plane when CuK ⁇ rays are used as an X-ray source is 42.5 ° to 42.8 °.
  • titanium oxynitride is intended to be a compound having a diffraction angle 2 ⁇ of a peak derived from the (200) plane when CuK ⁇ rays are used as an X-ray source and exceeding 42.8 °.
  • the upper limit of the diffraction angle 2 ⁇ of titanium oxynitride is not particularly limited, but is preferably 43.5 ° or less.
  • titanium oxynitride include titanium black. More specifically, for example, low-order titanium oxide represented by TiO 2 , Ti n O 2n-1 (1 ⁇ n ⁇ 20), and / or or include forms containing TiN x O y titanium oxynitride represented by (0 ⁇ x ⁇ 2.0,0.1 ⁇ y ⁇ 2.0).
  • 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 mixed.
  • titanium nitride may be used as titanium nitride-containing particles that further contain atoms (preferably silicon atoms or sulfur atoms) selected from Group 13-17 elements of the periodic table.
  • the metal nitride which is a combination of metal nitride and metal oxynitride may be used as particles in which other atoms are further mixed.
  • the metal nitride may be used as a metal nitride-containing particle that further contains an atom (preferably a silicon atom or a sulfur atom) selected from Group 13 to 17 elements of the periodic table.
  • titanium nitride contains titanium oxide TiO 2
  • TiO 2 is white and causes a reduction in the light-shielding property of the light-shielding film obtained by curing the curable composition, it is preferably reduced to such an extent that it is not observed as a peak.
  • the crystallite size constituting the titanium nitride can be determined from the half width of the peak obtained by measuring the X-ray diffraction spectrum.
  • the crystallite size can be calculated using Scherrer's equation.
  • the crystallite size constituting the titanium nitride is preferably 50 nm or less, and more preferably 20 nm or more.
  • the cured film formed using the curable composition tends to have higher ultraviolet (especially i-line (wavelength 365 nm)) transmittance and is more curable. 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.
  • the production method of the black pigment is not particularly limited, and a known production method can be used, and examples thereof include a gas phase reaction method.
  • the gas phase reaction method include an electric furnace method, a thermal plasma method, and the like.
  • the thermal plasma method is preferable in that impurities are less mixed, the particle diameter is easily uniformed, and productivity is high.
  • a method for generating thermal plasma is not particularly limited, and includes direct current arc discharge, multilayer arc discharge, radio frequency (RF) plasma, hybrid plasma, and the like, and there is little mixing of impurities from the electrodes. High frequency plasma is more preferred.
  • the specific method for producing the black pigment by the thermal plasma method is not particularly limited.
  • a method for producing titanium nitride a method of reacting titanium tetrachloride with ammonia gas in a plasma flame (JP-A-2-22110). No.), a method in which titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced as a carrier gas, and is nitrided and synthesized in the cooling process (Japanese Patent Laid-Open No. 61-11140), and ammonia gas is added to the periphery of the plasma. And a blowing method (Japanese Patent Laid-Open No. 63-85007).
  • the production method of the 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.
  • a metal pigment (oxy) nitride as described above may be coated with a silicon-containing compound to form a black pigment.
  • the method for coating the (oxy) nitride of the metal atom is not particularly limited, and a known method can be used. For example, it is described in JP-A No. 53-33228, page 2, lower right to page 4, upper right. Method (using (acid) nitride of metal atom instead of titanium oxide), method described in paragraphs 0015 to 0043 of JP-A-2008-69193 ((acid) of metal atom instead of fine particle titanium dioxide) And the method described in paragraphs 0020 and 0124 to 0138 of JP-A No. 2016-74870 (using (acid) nitride of metal atom instead of metal oxide fine particles). And the above content is incorporated herein.
  • a curable composition contains titanium black
  • titanium black is contained as a dispersion in the composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more in terms of mass. Is preferable, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is still more preferable.
  • the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).
  • titanium oxide and silica particles are dispersed using a disperser to obtain a dispersion, and this dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.) to thereby obtain titanium black particles mainly.
  • a dispersed material containing Si and Ti as components can be obtained.
  • the reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia.
  • titanium oxide include TTO-51N (trade name, manufactured by Ishihara Sangyo).
  • silica particles examples include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name, manufactured by Evonik).
  • a dispersing agent may be used for the dispersion of titanium oxide and silica particles. Examples of the dispersant include those described as the dispersant described later.
  • the dispersion may be performed in a solvent. Examples of the solvent include water and organic solvents. What is demonstrated in the column of the organic solvent mentioned later is mentioned. Titanium black in which Si / Ti is adjusted to, for example, 0.05 or more can be produced, for example, by the method described in paragraphs 0005 and 0016 to 0021 of JP-A-2008-266045.
  • the composition containing this dispersion by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to a suitable range (for example, 0.05 or more).
  • a suitable range for example, 0.05 or more.
  • a residue contains the component derived from compositions, such as a titanium black particle and a resin component. The reason why the residue is reduced is not yet clear, but the above-mentioned dispersed material tends to have a small particle size (for example, a particle size of 30 nm or less).
  • titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet light to infrared light, and thus the above-described dispersion to be dispersed containing titanium black and Si atoms (preferably Si / Ti is in terms of mass).
  • a light-shielding film formed using a material having a thickness of 0.05 or more exhibits excellent light-shielding properties.
  • the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A ). Whether or not the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more with respect to the dispersion to be contained in the cured film obtained by curing the composition Is determined using the method (2) described in paragraph 0035 of JP2013-249417A.
  • the above-described titanium black can be used.
  • materials used for introducing Si atoms into the dispersion will be described.
  • a Si-containing material such as silica may be used.
  • silica examples include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These can be selected and used as appropriate.
  • fine particle type silica examples include silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.
  • a plurality of pigments having a color other than black alone may be combined and used as a black pigment.
  • the pigment having a color other than black alone may be an inorganic pigment or an organic pigment.
  • chromatic pigments chromatic pigments
  • R (red), G (green), and B (blue) can also be used.
  • the inorganic pigment having a color other than black alone is not particularly limited, and a known inorganic pigment can be used.
  • the inorganic pigment include titanium oxide, chromium oxide, iron oxide, red lead, iron oxide red, yellow lead, zinc yellow (zinc yellow 1 type, zinc yellow 2 type), ultramarine blue, prussian blue (ferrocyanian).
  • the inorganic pigment may be subjected to a surface modification treatment. 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 “KTP-09” series (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the organic pigment having a color other than black alone is selected from, for example, the following organic pigments.
  • the pigment may be used in combination with a dye described later.
  • a dye described later.
  • a pigment that expresses black alone and / or a pigment that has a color other than black alone red, green
  • chromatic pigments such as yellow, orange, purple, and blue
  • a tungsten compound, a metal boride, or the like can be used as a pigment having a color other than black by itself and absorbing infrared rays.
  • a tungsten compound is preferable from the viewpoint of excellent light blocking properties at wavelengths in the infrared region.
  • the tungsten compound is excellent in the light absorption wavelength region of the oxime polymerization initiator related to the curing efficiency by exposure and the translucency in the visible light region.
  • the average primary particle size of the black pigment is preferably 0.01 to 0.1 ⁇ m, more preferably 0.01 to 0.05 ⁇ m.
  • the black pigment is composed of a combination of plural kinds of pigments, it is preferable that one or more of the pigments constituting the black pigment are within the above range, and that all the pigments constituting the black pigment are within the above range. More preferred.
  • the average primary particle diameter of a pigment can be measured using a transmission electron microscope (Transmission Electron Microscope, TEM).
  • TEM Transmission Electron Microscope
  • a transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
  • Maximum length of a particle image obtained using a transmission electron microscope (Dmax: maximum length at two points on the contour of the particle image), and maximum vertical length (DV-max: two straight lines parallel to the maximum length)
  • Dmax maximum length at two points on the contour of the particle image
  • DV-max maximum vertical length
  • the geometric mean value (Dmax ⁇ DV ⁇ max) 1 ⁇ 2 is taken as the particle diameter.
  • the particle diameter of 100 particles is measured by this method, and the arithmetic average value thereof is taken as the average particle diameter to obtain the average primary particle diameter of the pigment.
  • Black dye As the black dye, a dye that expresses black alone can be used. Furthermore, as described above, a single dye having a color other than black may be used in combination as a black dye. Examples of such coloring dyes include chromatic dyes (chromatic dyes) such as R (red), G (green), and B (blue), and paragraphs 0027 to 375 of JP-A-2014-42375. Colorants described in 0200 can also be used.
  • Examples of the dye include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Tokuho 2592207, US Pat. No. 4,808,501. No. 5, U.S. Pat. No. 5,667,920, U.S. Pat. No. 505950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, and JP-A-6-194828.
  • dye currently disclosed by the gazette etc. can be used.
  • a compound etc. can be used.
  • a dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A. Moreover, you may use the polymerizable dye which has polymerizability in a molecule
  • the black color material may further contain an infrared absorber as a color material having a color other than black by itself.
  • the infrared absorber means a compound having absorption in the wavelength region of the infrared region (preferably, wavelength 650 to 1300 nm).
  • a compound having a maximum absorption wavelength in a wavelength region of 675 to 900 nm is preferable.
  • colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterylenes.
  • Examples include compounds, dithiol metal complex compounds, and croconium compounds.
  • the phthalocyanine compound naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP 2010-1111750 A may be used. Embedded in the book.
  • the cyanine compound for example, “functional pigment, Shin Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein.
  • the compound having the maximum absorption wavelength in the wavelength region of 675 to 900 nm is preferably at least one selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound.
  • the infrared absorber is preferably a compound that dissolves 1% by mass or more in 25 ° C. water, and more preferably a compound that dissolves 10% by mass or more in 25 ° C. water. By using such a compound, the solvent resistance is improved.
  • paragraphs 0049 to 0062 of JP 2010-222557 A can be referred to, the contents of which are incorporated herein.
  • the cyanine compounds and squarylium compounds are disclosed in paragraphs 0022 to 0063 of International Publication No. 2014/088063, paragraphs 0053 to 0118 of International Publication No. 2014/030628, paragraphs 0028 to 0074 of JP 2014-59550 A, and International Publication No. 2012/0074.
  • paragraphs 0029 to 0085 of JP-A-2015-40895 paragraphs 0022 to 0036 of JP-A-2014-126642, paragraphs 0011 to 0017 of JP-A-2014-148567, and JP-A-2015-157893.
  • Paragraphs 0010 to 0025, paragraphs 0013 to 0026 of JP 2014-095007 A, paragraphs 0013 to 0047 of JP 2014-80487 A, paragraphs 0007 to 0028 of JP 2013-227403 A, and the like can be referred to. This content is incorporated herein.
  • the curable composition contains a polymerizable compound.
  • the polymerizable compound means a compound that polymerizes under the action of a photopolymerization initiator described later.
  • the content of the polymerizable compound in the curable composition is not particularly limited, but is preferably 5 to 30% by mass, more preferably 10 to 25% by mass with respect to the total solid content of the curable composition, 15 to 23 mass% is further more preferable.
  • a polymeric compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of polymeric compounds together, it is preferable that total content is in the said range.
  • the molecular weight of the polymerizable compound is preferably 2000 or less.
  • the polymerizable compound is a group containing an ethylenically unsaturated bond (hereinafter, also simply referred to as “ethylenically unsaturated group”) from the viewpoint of obtaining a cured film having a moderately roughened surface and reduced reflectance.
  • ethylenically unsaturated group an ethylenically unsaturated bond
  • ethylenically unsaturated group is a group containing an ethylenically unsaturated bond from the viewpoint of obtaining a cured film having a moderately roughened surface and reduced reflectance.
  • ethylenically unsaturated group are preferably 1 to 15 compounds, more preferably 3 to 6 compounds, further preferably 4 to 5 compounds, and particularly preferably 4 compounds.
  • the content of the polymerizable compound which is a compound containing 4 to 5 (preferably 4) ethylenically unsaturated groups is determined based on the total polymerizable content in the curable composition.
  • the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • polymerizable compound for example, compounds described in paragraph 0050 of JP2008-260927A and paragraph 0040 of JP2015-68893A can be used, and the above contents are incorporated in the present specification. It is.
  • the polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof.
  • the polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.
  • the polymerizable compound is also preferably a compound containing one or more ethylenically unsaturated groups and having a boiling point of 100 ° C. or higher under normal pressure.
  • compounds described in JP-A-2013-29760, paragraph 0227, and JP-A-2008-292970, paragraphs 0254 to 0257 can be referred to, the contents of which are incorporated herein.
  • Polymerizable compounds include dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product, manufactured by Nippon Kayaku), di Pentaerythritol penta (meth) acrylate (commercially available product is KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available products are KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., A-DPH- 12E, manufactured by Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acryloyl groups are mediated by an ethylene glycol residue or a propylene glycol residue (for example, SR454, SR499 commercially available from Sartomer) are
  • oligomer types can also be used.
  • NK ester A-TMMT penentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd.
  • Preferred embodiments of the polymerizable compound are 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 non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
  • a polymerizable compound having a group is more preferable, and in this ester, the aliphatic polyhydroxy compound is more preferably pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.
  • the acid value of the polymerizable compound containing an acid group is preferably from 0.1 to 40 mgKOH / g, more preferably from 5 to 30 mgKOH / g.
  • the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development dissolution properties are good, and when it is 40 mgKOH / g or less, it is advantageous in production and / or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.
  • the polymerizable compound is also preferably a compound containing a caprolactone structure.
  • the compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule.
  • trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipenta ⁇ -caprolactone-modified polyfunctional (meta ) Acrylates Among these, a compound containing a caprolactone structure represented by the following formula (Z-1) is 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
  • “*” represents a bond
  • a compound represented by the following formula (Z-4) or (Z-5) can also be used.
  • each E independently represents — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) —.
  • Y represents each independently an integer of 0 to 10
  • each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
  • the total number of (meth) acryloyl groups is 3 or 4
  • each m independently represents an integer of 0 to 10
  • the total of each m is an integer of 0 to 40.
  • the total number of (meth) acryloyl groups is 5 or 6
  • each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.
  • m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and further preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, 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.
  • — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) — represents an oxygen atom side.
  • a form in which the terminal of X is bonded to X is preferred.
  • the compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more.
  • all six Xs are acryloyl groups
  • all six Xs are acryloyl groups
  • among six Xs The aspect which is a mixture with the compound whose at least 1 is a hydrogen atom is preferable. With such a configuration, the developability can be further improved.
  • the total content of the compound represented by the formula (Z-4) or the formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
  • pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
  • the polymerizable compound may contain a cardo skeleton.
  • a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferable.
  • Examples of the polymerizable compound containing a cardo skeleton include, but are not limited to, oncoat EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).
  • the polymerizable compound has a double bond equivalent (content of ethylenically unsaturated group. More specifically, ethylenic unsaturation in the polymerizable compound from the point that the retention defect suppression property of the obtained cured film is more excellent.
  • the value obtained by dividing the number of groups by the molecular weight (g / mol) of the polymerizable compound is intended to be 7.0 mmol / g or more, and more preferably 11.0 mmol / g or more.
  • the upper limit is not particularly limited, but is generally 20.0 mmol / g or less.
  • the mass ratio of each polymerizable compound in the total polymerizable compound and each polymerizable compound It is preferable that the sum of the products of the compound and the double bond equivalent is within the above range.
  • the double bond equivalent may be referred to as “C ⁇ C value”.
  • require by calculating C C value
  • a solid component (black pigment or the like) in the curable composition is precipitated by a centrifugal separation method, and the remaining liquid component is collected. Furthermore, the polymerizable compound is separated from the obtained liquid component by a liquid chromatography method, and the structure of the polymerizable compound is specified by analysis using an NMR (nuclear magnetic resonance) method, a GPC method, or the like.
  • NMR nuclear magnetic resonance
  • GPC GPC method
  • the curable composition of the present invention contains resin A.
  • Resin A is a resin that satisfies any one of the requirements ((Requirement 1) that the acid value is 120 to 350 mgKOH / g) and ((Requirement 2) that the weight average molecular weight is 3000 to 7500). is there. Since the resin A satisfies one of the requirements 1 and 2, the curable composition of the present invention containing the resin A can obtain a cured film having good developability and excellent line width stability.
  • the resin A may be a resin that satisfies only one of the requirements 1 and 2, or a resin that satisfies both of them simultaneously. Among these, a resin that satisfies only one of the requirements 1 and 2 and does not satisfy the other requirement is preferable.
  • Resin A may contain a curable group.
  • the curable group include an ethylenically unsaturated group (for example, (meth) acryloyl group, vinyl group, and styryl group), and a cyclic ether group (for example, epoxy group, oxetanyl group, etc.)
  • an ethylenically unsaturated group is preferable as the curable group in that polymerization can be controlled by radical reaction.
  • the ethylenically unsaturated group is more preferably a (meth) acryloyl group.
  • Resin A is not particularly limited as long as it satisfies either requirement 1 or requirement 2, but preferably contains a repeating unit derived from a (meth) acrylic monomer.
  • the content of the repeating unit derived from the (meth) acrylic monomer of the resin A is preferably 10 mol% or more, more preferably 50 mol% or more, still more preferably 75 mol% or more, based on all repeating units. More than 90 mol% is particularly preferred.
  • a repeating unit derived from the (meth) acrylic monomer for example, a repeating unit represented by the following general formula (AA) is preferable.
  • R M represents a hydrogen atom or a methyl group.
  • L represents a single bond or a divalent linking group.
  • the divalent linking group include a hydrocarbon group which may have a substituent (which may be linear or branched, and may have a cyclic structure. And the substituent is preferably a hydroxyl group. Among these, an alkylene group having 1 carbon atom is preferable.
  • X represents a hydrogen atom or a substituent.
  • substituents examples include an aromatic ring group (preferably a phenyl group), an alkyl group (preferably having a carbon number of 1 to 3), a (meth) acryloyl group, a (meth) acryloyloxy group, a hydroxyl group, and a carboxy group. It is done.
  • X is preferably a hydrogen atom or a phenyl group.
  • the repeating unit derived from the (meth) acrylic monomer contained in the resin A may be one kind, two kinds or more, and two kinds or more. It is preferable. When there are two or more, at least one is preferably a repeating unit derived from (meth) acrylic acid.
  • a repeating unit derived from benzyl (meth) acrylate is preferable.
  • Resin A preferably contains both the repeating unit derived from the benzyl (meth) acrylate and the repeating unit derived from the (meth) acrylic acid, the repeating unit derived from the benzyl (meth) acrylate, and the above More preferably, it consists only of a combination of repeating units derived from (meth) acrylic acid.
  • the resin A is preferably a copolymer of benzyl (meth) acrylate and (meth) acrylic acid.
  • Examples of other repeating units that are assumed to be contained in the main chain of the resin A include a repeating unit derived from a styrene monomer (such as hydroxystyrene) and a repeating unit derived from an ether dimer.
  • Examples of the ether dimer include a compound represented by the following general formula (ED1) and a compound represented by the following general formula (ED2).
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • ED2 general formula (ED2)
  • JP 2010-168539 A the description in JP 2010-168539 A can be referred to.
  • ether dimer for example, paragraph 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used.
  • Resin A that satisfies Requirement 1
  • Resin A (resin A satisfying requirement 1) having an acid value of 120 to 350 mgKOH / g is prepared in an appropriate range.
  • the acid value of the resin satisfying the requirement 1 is preferably 170 to 300 mgKOH / g, more preferably 200 to 270 mgKOH / g, from the viewpoint of more excellent line width stability and undercut suppression of the obtained cured film.
  • the resin A satisfying the requirement 1 has a weight average molecular weight of preferably more than 7500, more preferably 8000 to 30000, and further preferably 10000 to 15000.
  • the resin A having a weight average molecular weight of 3000 to 7500 (resin A satisfying the requirement 2) is prepared in an appropriate molecular weight range.
  • the weight average molecular weight of the resin satisfying the requirement A is preferably from 3000 to 6500, more preferably from 3000 to 5000, more preferably from 4000 to 2000, because the cured film has more excellent line width stability, undercut suppression and residue suppression. 5000 is more preferable.
  • the acid value of the resin A satisfying the requirement 2 is preferably less than 120 mgKOH / g, more preferably 30 to 110 mgKOH / g, and more preferably 60 to 100 mgKOH / g.
  • Resin A may be used individually by 1 type, or may use 2 or more types together.
  • the curable composition may contain both the resin A satisfying the requirement 1 and the resin A satisfying the requirement 2.
  • the content of the resin A in the curable composition is not particularly limited, but is preferably 1 to 30% by mass and more preferably 5 to 15% by mass with respect to the total solid content of the curable composition. When using 2 or more types of resin A, it is preferable that total content is in the said range.
  • the presence or absence of the resin A in the curable composition and the content thereof can be measured by the following method.
  • a solid component (black pigment or the like) in the curable composition is precipitated by a centrifugal separation method, and the remaining liquid component is collected. Further, from the obtained liquid component, a component having a weight average molecular weight of more than 2000 is separated by GPC method, and this is used as a resin to be measured.
  • the resin is defined as resin A satisfying requirement 2, and the content relative to the total solid content of the curable composition is obtained.
  • the acid value is measured by an ordinary method (such as JISK5601-2-1 or JISK0070) to confirm whether the acid value is 120 to 350 mgKOH / g.
  • an ordinary method such as JISK5601-2-1 or JISK0070
  • the content of A can be determined. Further, the content of the resin A in the curable composition may be obtained by calculation when the blending of the curable composition and the acid value and the weight average molecular weight of the raw material to be used are known.
  • the curable composition may contain a resin other than the resin A described above.
  • the resin other than the resin A include a resin B from the viewpoint of obtaining a cured film having a reduced reflectance.
  • the resin B is a resin different from the resin A, and is a resin having one or more groups selected from the group consisting of oxyalkylene groups and oxyalkylenecarbonyl groups.
  • the resin B is preferably a resin that acts as a so-called pigment dispersant.
  • the content of the resin B in the curable composition is not particularly limited, but is preferably 2 to 40% by mass and more preferably 5 to 30% by mass with respect to the total solid content of the curable composition.
  • Resin B may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of resin B together, it is preferable that total content is in the said range.
  • the form in which at least one group selected from the group consisting of an oxyalkylene group and an oxyalkylenecarbonyl group in resin B is present is not particularly limited.
  • the alkylene moiety in the oxyalkylene group and oxyalkylenecarbonyl group may have a substituent, may be linear or branched, and may have a cyclic structure. Especially, it is preferable that the said alkylene part is unsubstituted.
  • the number of carbon atoms of the alkylene portion in the oxyalkylene group is preferably 1 to 10, and more preferably 2 to 3. Further, the number of carbon atoms of the alkylene moiety in the oxyalkylenecarbonyl group is preferably 2 to 8, and more preferably 4 to 6.
  • the resin B has a polyoxyalkylene structure in which a plurality of oxyalkylene groups are continuously bonded (preferably 3 or more, more preferably 10 or more) or a plurality of oxyalkylenecarbonyl groups (preferably 3). Or more, more preferably 10 or more) preferably having a bonded polyoxyalkylenecarbonyl structure.
  • Resin B is a polymer compound [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer Combined and naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, pigment derivative, and the like.
  • the polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
  • the polymer compound may contain a curable group.
  • the curable group include an ethylenically unsaturated group (for example, (meth) acryloyl group, vinyl group, styryl group, etc.), a cyclic ether group (for example, epoxy group, oxetanyl group, etc.) and the like.
  • an ethylenically unsaturated group is preferable as the curable group in that polymerization can be controlled by radical reaction.
  • the ethylenically unsaturated group is more preferably a (meth) acryloyl group.
  • the resin containing a curable group may contain an oxyalkylene group (preferably a polyoxyalkylene structure) and / or an oxyalkylene carbonyl group (preferably a polyoxyalkylene carbonyl structure) in the main chain.
  • the graft chain is an oxyalkylene group (preferably a polyoxyalkylene structure) and / or an oxyalkylenecarbonyl group (preferably a polyoxyalkylene structure). (Oxyalkylenecarbonyl structure) may be contained.
  • the said graft chain contains an oxyalkylene carbonyl group.
  • the polymer compound preferably contains a structural unit containing a graft chain.
  • structural unit is synonymous with “repeating unit”. Since the polymer compound containing a structural unit containing such a graft chain has an affinity for a solvent by the graft chain, the dispersibility of pigments, etc., and the dispersion stability after time (stability over time) It is excellent. Further, due to the presence of the graft chain, the polymer compound containing the structural unit containing the graft chain has an affinity with a polymerizable compound or other resin that can be used in combination. As a result, it becomes difficult to produce a residue by alkali development.
  • the graft chain When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility of the pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorptive power to the pigment or the like is lowered, and the dispersibility of the pigment or the like tends to be lowered. Therefore, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and the number of 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 a 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.
  • a polymer structure include a poly (meth) acrylate structure (for example, poly (meth) acrylic structure), a polyester structure (preferably, polyoxyalkylenecarbonyl). Structure), polyurethane structure, polyurea structure, polyamide structure, and polyether structure (preferably, polyoxyalkylene structure).
  • the graft chain is composed of a polyoxyalkylene carbonyl structure, a polyoxyalkylene structure, and a poly (meth) acrylate structure.
  • a graft chain containing at least one selected from the group is preferred, and a graft chain containing at least one of a polyoxyalkylenecarbonyl structure and a polyoxyalkylene structure is more preferred.
  • the macromonomer containing such a graft chain (a monomer having a polymer structure and bound to the main chain of the copolymer to constitute the graft chain) is not particularly limited, but includes a reactive double bond group.
  • the containing macromonomer can be used conveniently.
  • AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (trade name, manufactured by Toagosei Co., Ltd.), AB-6 (trade name, manufactured by Toagosei Co., Ltd.), AS-6 (trade name, manufactured by Toagosei Co., Ltd.) Synthetic Co., Ltd.), AN-6 (trade name, manufactured by Toagosei Co., Ltd.), or Bremer PME-4000 (trade name, manufactured by NOF Corporation) is preferable.
  • the resin B preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester, and includes polymethyl acrylate and polymethacrylic acid. More preferably, it contains at least one structure selected from the group consisting of methyl and chain polyester, and includes 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 resin B is a resin other than the resin A and has the above structure in one resin B as long as it has at least one group selected from the group consisting of an oxyalkylene group and an oxyalkylenecarbonyl group.
  • the resin B contained alone may be used, or the resin B containing a plurality of these structures in one resin B may be used.
  • 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. These correspond to one embodiment of the polyoxyalkylene carbonyl structure.
  • Specific examples of the repeating unit constituting the polycaprolactone structure contained in the resin B include a repeating unit in which j and k in the following formula (1) and the following formula (2) are 5.
  • the repeating unit which comprises the polyvalerolactone structure which resin B contains the repeating unit whose j and k in following formula (1) and following formula (2) are 4 is mentioned.
  • Specific examples of the repeating unit constituting the polymethyl acrylate structure contained in the resin B include a repeating unit in which X 5 in the following formula (4) is a hydrogen atom and R 4 is a methyl group.
  • the resin B contains, as specific examples of the repeating units constituting the polymethyl methacrylate structure is X 5 is a methyl group in the formula (4) include the repeating units R 4 is a methyl group .
  • the polymer compound preferably contains a structural unit represented by any of the following formulas (1) to (4) as a structural unit containing a graft chain. It is more preferable to contain the structural unit represented by either (1A), the following formula (2A), the following formula (3A), the following formula (3B), or the following (4).
  • the polymer compound preferably contains at least one of structural units represented by any of the following formulas (1) to (3).
  • the structural unit represented by Formula (1) and the structural unit represented by Formula (2) are structural units containing an oxyalkylene carbonyl group.
  • the structural unit represented by Formula (3) is a structural unit containing an oxyalkylene group.
  • W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH.
  • W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
  • X 1 , X 2 , X 3 , X 4 and X 5 each independently represent a hydrogen atom or a monovalent organic group.
  • X 1 , X 2 , X 3 , X 4 , and X 5 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (the number of carbon atoms) from the viewpoint of restrictions on synthesis. It is preferably each independently a hydrogen atom or a methyl group, more preferably a methyl group.
  • Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure.
  • Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following linking groups (Y-1) to (Y-21). It is done.
  • a and B each represent a binding site in formulas (1) to (4). Of the structures shown below, (Y-2) or (Y-13) is more preferable because of the ease 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, and 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 containing a steric repulsion effect is particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 carbon atoms.
  • an alkyl group or an alkoxy group having ⁇ 24 is preferable, and among them, a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable. 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 resin B contains a polycaprolactone structure and a polyvalerolactone structure
  • the sum of the number of repetitions of the polycaprolactone structure and the number of repetitions of the polyvalerolactone is preferably an integer of 10 or more, An integer is more preferable.
  • R 3 represents a branched or straight chain 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, a plurality of R 3 may be the same 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 terms of structure.
  • R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom or 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.
  • a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is still more preferable.
  • a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
  • the polymer compound can contain structural units containing graft chains that have two or more different structures. That is, in the molecule of the polymer compound, structural units represented by the formulas (1) to (4) having different structures from each other may be contained, and in the formulas (1) to (4), n, m , P, and q each represent an integer of 2 or more, in Formulas (1) and (2), j and k may contain structures different from each other in the side chain, and Formula (3) And (4), a plurality of R 3 , R 4 and X 5 present in the molecule may be the same 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 temporal stability and developability of the composition.
  • a structural unit represented by Formula (2) it is more preferable that it is a structural unit represented by following formula (2A) from a viewpoint of temporal stability of a composition and developability.
  • the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or formula (3B) from the viewpoint of the temporal stability and developability of the composition. .
  • the polymer compound contains a structural unit represented by the formula (1A) as a structural unit containing a graft chain.
  • the structural unit containing a graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is 2 to 90% by mass in terms of mass with respect to the total mass of the polymer compound. Preferably, it is contained in the range of 5 to 30% by mass.
  • the total content of the structural units represented by the above formulas (1) to (3) is preferably included in the range of 2 to 80% by mass with respect to the total mass of the polymer compound, and 5 to 25% by mass. It is more preferable that it is included in the range.
  • the structural unit containing a graft chain is included within this range, the dispersibility of the pigment is high, and the developability when forming a cured film is good.
  • a high molecular compound contains the hydrophobic structural unit different from the structural unit containing a graft chain (namely, it does not correspond to the structural unit containing a graft chain).
  • a hydrophobic structural unit is a structural unit which does not have an 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 structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, and is a structural unit derived from a compound having a ClogP value of 1.2 to 8 It is more preferable. Thereby, the effect of this invention can be expressed more reliably.
  • ClogP values can be obtained from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In this specification, the ClogP value calculated by the program CLOGP v4.82 is used. A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B.
  • log P means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
  • 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 one or more structural units selected from structural units derived from monomers represented by the following formulas (i) to (iii) as hydrophobic structural units.
  • R 1 , R 2 , and R 3 are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or An alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.) is represented.
  • R 1 , R 2 and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.
  • R 2 and R 3 are more preferably a hydrogen atom.
  • X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • L is a single bond or a divalent linking group.
  • a divalent aliphatic group for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group
  • divalent aromatic group for example, arylene group
  • Substituted arylene group divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 Are 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 aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • 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-membered ring or a 6-membered ring as the heterocyclic ring.
  • Another heterocyclic ring, an aliphatic ring, or an aromatic ring may be condensed with the heterocyclic ring.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is aliphatic. Group, aromatic group, or heterocyclic group), aliphatic group, aromatic group, and heterocyclic group.
  • 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 two or more oxyalkylene structures.
  • the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
  • the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z includes an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, and a substituted unsaturated alkyl group), an aromatic group (for example, an aryl group, a substituted aryl group, an arylene group, and Substituted arylene groups, etc.), heterocyclic groups, or combinations thereof.
  • These groups include an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR 31 —, wherein R 31 is an aliphatic group, an aromatic group Group or heterocyclic group) or a carbonyl group (—CO—) may be contained.
  • the aliphatic group may have a cyclic structure or a branched structure.
  • the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -A cyclohexylphenyl group and the like are included.
  • bridged cyclic hydrocarbon ring examples include 2 such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.).
  • Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredan, 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 .
  • the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed, such as a perhydrophenalene ring, is also included.
  • a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed, such as a perhydrophenalene ring, is also included.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
  • the carbon number of the aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.
  • a heterocyclic group contains a 5-membered ring or a 6-membered ring as a heterocyclic ring.
  • Another heterocyclic ring, aliphatic ring or aromatic ring may be condensed with the heterocyclic ring.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is aliphatic. Group, aromatic group or heterocyclic group), aliphatic group, aromatic group, and heterocyclic group.
  • the heterocyclic group does not have an acid group as a substituent.
  • R 4 , R 5 , and R 6 are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1-6.
  • An alkyl group for example, a methyl group, an ethyl group, a propyl group, etc.
  • Z, or LZ is represented.
  • L and Z are as defined above.
  • R 4 , R 5 and R 6 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 1 , R 2 , and R 3 are a hydrogen atom or a methyl group, and L contains a single bond, an alkylene group, or an oxyalkylene structure.
  • a compound that is a divalent linking group, X is an oxygen atom or imino group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferable.
  • R 1 is a hydrogen atom or a methyl group
  • L is an alkylene group
  • Z is an aliphatic group, a heterocyclic group, or an aromatic group. Compounds that are groups are preferred.
  • R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Compounds that are groups are preferred.
  • Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
  • Examples of typical compounds represented by formulas (i) to (iii) compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are described in the present specification. Incorporated into.
  • the hydrophobic structural unit is preferably contained in a range of 10 to 90%, more preferably in a range of 20 to 80% with respect to the total mass of the polymer compound in terms of mass. When the content is in the above range, sufficient pattern formation can be obtained.
  • 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 coordination group, and a reactive functional group.
  • the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as the acid group, developability for pattern formation by alkali development can be imparted to the polymer compound. That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound as the resin B that contributes to the dispersion of pigments and the like has alkali solubility in the composition.
  • the curable composition containing such a polymer compound has excellent light shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
  • a high molecular compound contains the structural unit containing an acid group
  • a high molecular compound becomes easy to become compatible with a solvent, and there exists a tendency for applicability
  • the acid group in the structural unit containing an acid group easily interacts with the pigment and the like, and the polymer compound stably disperses the pigment and the like, and the viscosity of the polymer compound that disperses the pigment and the like decreases. This is presumably because the polymer compound itself is easily dispersed stably.
  • the structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the structural unit containing the graft chain or a different structural unit.
  • the structural unit containing a soluble group is a structural unit different from the hydrophobic structural unit described above (that is, does not correspond to the hydrophobic structural unit described above).
  • Examples of the acid group that is a functional group capable of forming an interaction with a pigment include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and a carboxylic acid group, a sulfonic acid group, and
  • the phosphoric acid group is preferably at least one, and more preferably a carboxylic acid group.
  • Carboxylic acid groups have good adsorptive power to pigments and the like, and have high dispersibility. That is, the polymer compound preferably further contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
  • the polymer compound may have one or more structural units containing an acid group.
  • the polymer compound may or may not contain a structural unit containing an acid group.
  • the content of the structural unit containing an acid group is calculated by mass conversion to the total mass of the polymer compound.
  • 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 alkali development.
  • Examples of the basic group which is a functional group capable of forming an interaction with a pigment include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, and an amide
  • a preferable basic group is a tertiary amino group in that it has a good adsorptive power to pigments and has 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 amount of the polymer compound in terms of mass. The amount is preferably 0.01 to 50% by weight, and more preferably 0.01 to 30% by weight from the viewpoint of inhibiting the development inhibition.
  • Examples of the coordinating group that is a functional group capable of forming an interaction with a pigment and the reactive functional group include, for example, acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, and acidification Thing etc. are mentioned.
  • a preferred functional group is an acetylacetoxy group in that it has a good adsorptive power to pigments and has 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 reactive functional group, but if it contains, the content of these structural units Is preferably 10 to 80% by mass in terms of mass, and more preferably 20 to 60% by mass from the viewpoint of inhibiting developability inhibition.
  • the polymer compound contains a functional group capable of forming an interaction with a pigment or the like other than the graft chain
  • the polymer compound only needs to contain a functional group capable of forming an interaction with the various pigments or the like, although how these functional groups are introduced is not particularly limited, the polymer compound is selected from structural units derived from monomers represented by the following formulas (iv) to (vi): It is preferable to contain more than one type of structural unit.
  • R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number 1 to 6 alkyl groups (for example, a methyl group, an ethyl group, and a propyl group) are represented.
  • R 11 , R 12 , and R 13 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently a hydrogen atom or methyl More preferably, it is a group.
  • R 12 and R 13 are each more preferably a hydrogen atom.
  • X 1 in the formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • Y in the formula (v) represents a methine group or a nitrogen atom.
  • L 1 represents a single bond or a divalent linking group.
  • the definition of the divalent linking group is the same as the definition of the divalent linking group represented by L in the above-described formula (i).
  • L 1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L 1 may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
  • the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n —, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z 1 represents a functional group capable of forming an interaction with a pigment other than the graft chain, and is preferably a carboxylic acid group or a tertiary amino group, More preferably, it is an acid group.
  • R 14 , R 15 , and R 16 are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl having 1 to 6 carbon atoms group (e.g., methyl group, ethyl group, and propyl group), - represents a Z 1, or -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 14 , R 15 and R 16 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 11 , R 12 and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or a divalent oxyalkylene structure.
  • a compound in which X 1 is an oxygen atom or an imino group and Z 1 is a carboxylic acid group is 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. Is preferred.
  • R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group, L 1 is a single bond or an alkylene group, and Z A compound in which 1 is a carboxylic acid group is preferred.
  • monomers represented by formulas (iv) to (vi).
  • monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction containing a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride.
  • reaction product a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride, a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride Reaction product, a reaction product of a compound containing an addition polymerizable double bond and hydroxyl group in the molecule and trimellitic anhydride, a compound containing an addition polymerizable double bond and hydroxyl group in the molecule and pyromellitic anhydride Reaction products with acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4 Hydroxyphenyl methacrylamide.
  • the content of the structural unit containing a functional group capable of forming an interaction with the pigment, etc. is the total mass of the polymer compound from the viewpoint of the interaction with the pigment, the stability over time, and the permeability to the developer. On the other hand, it is preferably 0.05 to 90% by mass, more preferably 1.0 to 80% by mass, and still more preferably 10 to 70% by mass.
  • 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.
  • Other structural units having various functions different from structural units containing functional groups capable of forming an interaction with the like for example, structural units containing functional groups having affinity with a solvent to be described later
  • Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
  • the polymer compound may use one or more of these other structural units, and its content is preferably 0 to 80% by mass, based on the total mass of the polymer compound, in terms of mass. 60 mass% or less is more preferable. When the content is in the above range, sufficient pattern formability is maintained.
  • the acid value of the polymer compound is preferably in the range of 10 to less than 110 mgKOH / g, more preferably in the range of 20 to 100 mgKOH / g, and still more preferably in the range of 30 to 70 mgKOH / g.
  • the acid value of the polymer compound is 110 mgKOH / g or less, pattern peeling during development when forming a cured film is more effectively suppressed.
  • the acid value of a high molecular compound is 10 mgKOH / g or more, alkali developability will become more favorable.
  • the acid value of a high molecular compound is 20 mgKOH / g or more, precipitation of a pigment etc. can be suppressed more, the number of coarse particles can be decreased more, and the temporal stability of a composition can be improved more.
  • the acid value can be calculated from, for example, the average content of acid groups in the compound.
  • the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of resin.
  • the weight average molecular weight of the polymer compound is preferably more than 7,000 and not more than 300,000, more preferably 8000 to 200,000, still more preferably 9000 to 100,000, and 10,000 to 50. Is particularly preferred.
  • the polymer compound can be synthesized based on a known method.
  • polymer compound examples include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, not corresponding to resin A, Polyethylene glycol distearate can also be used.
  • Specific examples of commercially available polymer compounds include “Solsperse 12000” manufactured by Nippon Lubrizol.
  • amphoteric resin containing an acid group and a basic group.
  • the amphoteric resin is preferably a resin having an acid value of 5 mgKOH / g or more and an amine value of 5 mgKOH / g or more. These polymer compounds may be used alone or in combination of two or more.
  • polymer compound As specific examples of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification.
  • a graft copolymer described in JP 2010-106268 A paragraphs 0037 to 0115 (corresponding to paragraphs 0075 to 0133 in US2011 / 0124824) can be used. Is incorporated herein by reference. In addition to the above, it contains a side chain structure in which acidic groups in paragraphs 0028 to 0084 of JP 2011-153283 A (corresponding paragraphs 0075 to 0133 of US2011 / 0279759) are bonded via a linking group.
  • Polymeric compounds containing components can be used, the contents of which can be incorporated and incorporated herein.
  • the curable composition of this invention may contain resin which does not correspond to any of resin A and resin B.
  • the curable composition contains a photopolymerization initiator.
  • a photoinitiator if a superposition
  • the photopolymerization initiator for example, a photopolymerization initiator having photosensitivity from the ultraviolet region to the visible light region is preferable.
  • it may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, and an initiator that initiates cationic polymerization according to the type of the polymerizable compound (radical polymerization initiator). It may be.
  • the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least 50 within a 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 is preferably 0.5 to 20% by mass with respect to the total solid content of the curable composition.
  • a photoinitiator may be used individually by 1 type, or may use 2 or more types. When using 2 or more types of photoinitiators together, it is preferable that total content is in the said range.
  • Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those containing a triazine skeleton, those containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, Examples include oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenones.
  • paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
  • an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can be used as the photopolymerization initiator.
  • the hydroxyacetophenone compound for example, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF) can be used.
  • the aminoacetophenone compound for example, commercially available products IRGACURE-907, IRGACURE-369, or IRGACURE-379EG (trade names, all manufactured by BASF) can be used.
  • aminoacetophenone compound a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source having a wavelength of 365 nm or a wavelength of 405 nm can also be used.
  • acylphosphine compound commercially available IRGACURE-819 or IRGACURE-TPO (trade name, both manufactured by BASF) can be used.
  • an oxime ester polymerization initiator As a photoinitiator, an oxime ester polymerization initiator (oxime compound) is more preferable.
  • oxime compound a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, or a compound 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, 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 And carbonyloxyimino-1-phenylpropan-1-one.
  • J.H. C. S. Perkin II (1979) pp. 1653-1660) J.M. 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 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
  • Adeka Arcles NCI-831 Adeka Arcles NCI-930
  • N-1919 carboxymethyl methacrylate
  • An initiator manufactured 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. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety; A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at a dye site; a ketoxime compound described in International Patent Publication No. 2009-131189; and a triazine skeleton and an oxime skeleton A compound described in US Pat. No.
  • the oxime compound is preferably a compound represented by the following formula (OX-1).
  • the N—O bond of the oxime compound may be an (E) oxime compound, a (Z) oxime compound, a mixture of (E) isomer and (Z) isomer. 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 nonmetallic atomic group.
  • the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group.
  • these groups may have one or more substituents.
  • the substituent mentioned above may be further substituted by another substituent.
  • the substituent examples include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
  • the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group, and an aryl group or a heterocyclic group is More preferred. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
  • the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
  • An oxime compound containing a fluorine atom can also be used as a photopolymerization initiator.
  • Specific examples of the oxime compound containing a fluorine atom include compounds described in JP2010-262028; compounds 24 and 36 to 40 described in JP-T-2014-500852; and JP2013-164471A (C-3); and the like. This content is incorporated herein.
  • photopolymerization initiator compounds represented by the following general formulas (1) to (4) can also be used.
  • R 1 and R 2 are each independently 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 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 each other 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 , —CN, a halogen atom, or a hydroxyl group
  • R 6 is 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 20 represents a heterocyclic group
  • X represents a direct bond or a carbonyl group
  • a represents an integer of 0 to 4.
  • R 1 represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms.
  • R 3 and R 4 each independently 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 carbon atom.
  • 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, 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 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.
  • 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 formula (1) and formula (2) include compounds described in paragraphs 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.
  • oxime compounds preferably used in the curable composition are shown below.
  • the oxime compound represented by the general formula (A) (hereinafter also referred to as “specific photopolymerization initiator”) is preferable from the viewpoint of more excellent peeling inhibition of the obtained cured film.
  • specific photopolymerization initiator IRGACURE-OXE03 (manufactured by BASF) can be mentioned.
  • the oxime compound the compound described in Table 1 of International Publication No. 2015-036910 can also be used, and the above contents are incorporated in the present specification.
  • the oxime compound preferably has a maximum absorption wavelength in a wavelength region of 350 to 500 nm, more preferably has a maximum absorption wavelength in a wavelength region of 360 to 480 nm, and further preferably has high absorbance at wavelengths of 365 nm and 405 nm. .
  • the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200,000 from the viewpoint of sensitivity. More preferably, it is 000.
  • a known method can be used to determine the molar extinction coefficient of the compound.
  • the molar extinction coefficient is measured at a concentration of 0.01 g / L using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent. It is preferable. You may use a photoinitiator in combination of 2 or more type as needed.
  • the curable composition contains a polymerization inhibitor. It does not restrict
  • the polymerization inhibitor include phenol-based polymerization inhibitors (for example, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-ditert-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 (for example, , Hydroquinone, 2,6-di-tert-butylhydroquinone, etc.); quinone polymerization inhibitors (eg, benzoquinone, etc.); free radical polymerization inhibitors (eg, 2,2,6,6-tetramethylpiperidine 1- Oxyl free radical,
  • Nitrobenzene-based polymerization inhibitor e.g., nitrobenzene, 4-nitrotoluene, etc.
  • phenothiazine-based polymerization inhibitor e.g., phenothiazine, 2-methoxy phenothiazine, etc.
  • a phenol polymerization inhibitor or a free radical polymerization inhibitor is preferable in that the curable composition has a more excellent effect.
  • 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 with respect to the total solid content of the curable composition, preferably 0.001 to 0.2. % By mass is more preferable, and 0.008 to 0.05% by mass is even more preferable.
  • a polymerization inhibitor may be used individually by 1 type, or may use 2 or more types together. When two or more polymerization inhibitors are used in combination, the total content is preferably within the above range.
  • the ratio of the content of the polymerization inhibitor to the content of the polymerizable compound in the curable composition is more than 0.0005.
  • 0.0006 to 0.02 is more preferable, and 0.0006 to 0.005 is still more preferable.
  • the curable composition may contain a surfactant.
  • Surfactant contributes to the applicability
  • 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.
  • Surfactant may be used individually by 1 type, or may use 2 or more types together. When two or more surfactants are used in combination, the total amount is preferably within the above range.
  • surfactant examples include a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant.
  • the liquid properties (particularly fluidity) of the curable composition are further improved. That is, in the case of forming a film using a curable composition containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid. The applicability to the coated surface is improved. For this reason, even when a thin film of about several ⁇ m is formed with a small amount of liquid, it is effective in that a film having a uniform thickness with small thickness unevenness can be more suitably formed.
  • the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass.
  • a fluorosurfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and / or liquid-saving properties, and has good solubility in the curable composition. .
  • fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, and F781 (above, manufactured by DIC); Florard FC430, FC431, and FC171 (above, manufactured by Sumitomo 3M); Surflon S-382, SC-101, SC -103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (above, manufactured by Asahi Glass); and PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc. are mentioned.
  • a block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A No. 2011-89090.
  • the curable composition may contain an ultraviolet absorber.
  • an ultraviolet absorber As the ultraviolet absorber, salicylate, benzophenone, benzotriazole, substituted acrylonitrile and triazine ultraviolet absorbers can be used.
  • compounds of paragraphs 0137 to 0142 corresponding to paragraphs 0251 to 0254 of US2012 / 0068292) of JP2012-068418A can be used, and the contents thereof can be incorporated and incorporated in the present specification. .
  • a diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) and the like are also preferably used.
  • the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
  • the content of the ultraviolet absorber is preferably 0.001 to 15% by mass with respect to the total solid content of the curable composition.
  • the curable composition may contain a silane coupling agent.
  • a silane coupling agent is a compound containing a hydrolyzable group and other functional groups in the molecule.
  • a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
  • the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction.
  • Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group.
  • the hydrolyzable group contains a carbon atom
  • the number of carbon atoms is preferably 6 or less, and 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 (however, excluding silicon atoms to which hydrolyzable groups are bonded) Is preferably not included, fluorine atom, silicon atom (excluding the 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, and 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 with respect to the total solid content in the curable composition.
  • 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 should just be in the said range.
  • silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, Examples include vinyltrimethoxysilane and vinyltriethoxysilane.
  • the curable composition preferably contains a solvent.
  • the solvent is not particularly limited and a known solvent can be used.
  • the content of the solvent in the curable composition is not particularly limited, but is preferably adjusted so that the solid content of the curable composition is 10 to 90% by mass, and 15 to 50% by mass. More preferably, it is adjusted.
  • solid content intends components other than a solvent.
  • a solvent may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of solvent together, it is preferable to adjust so that the total solid of a curable composition may become in the said range.
  • Examples of the solvent include water and an organic solvent.
  • Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 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 Chill ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, butyl acetate, Examples include, but are not limited to, methyl lactate, N-methyl-2-pyrrolidone, and ethyl lactate.
  • the curable composition is preferably prepared by first preparing a dispersion composition in which a black color material is dispersed, and further mixing the obtained dispersion composition with other components to obtain a curable composition.
  • the dispersion composition is preferably prepared by mixing a black color material, resin B, and a solvent.
  • it is also preferable to make a dispersion composition contain a polymerization inhibitor.
  • the dispersion composition can be prepared by mixing the above components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser, or the like).
  • each component may be blended at once, or each component may be blended sequentially after being dissolved or dispersed in a solvent.
  • the order of input and the working conditions when blending are not particularly limited.
  • the curable composition is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects.
  • a filter if it is a filter conventionally used for the filtration use etc., it can be used without being specifically limited. Examples include filters made of fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (containing high density and ultra high molecular weight). It is done. Among these materials, polypropylene (containing high density polypropylene) and 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.
  • different filters may be combined.
  • the filtering by the first filter may be performed only once or may be performed twice or more.
  • the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering.
  • the pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, it can select from the various filters which Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (former Japan Microlith Co., Ltd.), KITZ micro filter, etc. provide, for example.
  • As the second filter a filter formed of the same material or the like as the first filter described above can be used.
  • 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.
  • a curable composition does not contain impurities, such as a metal, the metal salt containing a halogen, an acid, and an alkali.
  • 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 free (below the detection limit of the measuring device). Is most preferable.
  • the impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).
  • a curable composition layer (composition layer) formed using the curable composition can be cured to obtain a patterned cured film.
  • limit especially as a manufacturing method of a cured film
  • each process is demonstrated.
  • a curable composition layer formation process is a process of forming a curable composition layer using the said curable composition.
  • a process of forming a curable composition layer using a curable composition the process of apply
  • the type of the substrate is not particularly limited, but when used as a solid-state imaging device, for example, a silicon substrate is used, and when used as a color filter (including a color filter for a solid-state imaging device), a glass substrate or the like is used. .
  • the curable composition on the substrate various coating methods such as spin coating, slit coating, ink jet method, spray coating, spin coating, cast coating, roll coating, and screen printing are applied. be able to.
  • the curable composition applied on the substrate is usually dried at 70 to 150 ° C. for about 1 to 4 minutes to form a curable composition layer.
  • the curable composition layer formed in the curable composition layer forming step is exposed by irradiating with actinic rays or radiation, and the curable composition layer irradiated with light is cured.
  • the light irradiation method is not particularly limited, but light irradiation is preferably performed through a photomask having a patterned opening.
  • the exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are particularly preferable, and a high-pressure mercury lamp is preferable as a light source.
  • the irradiation intensity is preferably 5 ⁇ 1500mJ / cm 2, more preferably 10 ⁇ 1000mJ / cm 2.
  • a curable composition contains a thermal-polymerization initiator, you may heat a curable composition layer in the said exposure process.
  • the heating temperature is not particularly limited, but is preferably 80 to 250 ° C.
  • the heating time is not particularly limited, but is preferably 30 to 300 seconds.
  • the method for producing a cured film may not include the post-heating step.
  • development processing is performed to elute the light non-irradiated portion in the exposure step into the developer.
  • An alkaline developer may be used as the developer.
  • an organic alkali developer is preferably used.
  • the development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
  • Examples of the alkaline aqueous solution (alkali developer) include inorganic alkali developers and organic alkali developers.
  • an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, and sodium metaoxalate is used at a concentration of 0.001 to 10% by mass (preferably An alkaline aqueous solution dissolved so as to be 0.005 to 0.5% by mass).
  • Organic alkaline developers include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline , Pyrrole, piperidine, and alkaline compounds such as 1,8-diazabicyclo- [5,4,0] -7-undecene at a concentration of 0.001 to 10% by mass (preferably 0.005 to 0.5% by mass) %) Dissolved in an alkaline aqueous solution.
  • a water-soluble organic solvent such as methanol and ethanol, and / or a surfactant, for example, can be added to the alkaline aqueous solution.
  • a developer composed of such an alkaline aqueous solution is used, the cured film is generally washed (rinsed) with pure water after development.
  • the manufacturing method of a cured film may contain another process.
  • the other steps include a substrate surface treatment step, a preheating step (pre-baking step), and a post-heating step (post-baking step).
  • pre-baking step pre-baking step
  • post-baking step post-heating step
  • a manufacturing method of the said cured film it is preferable to contain the process (post-heating process) of heating the curable composition layer after exposure between an exposure process and a image development process.
  • the heating temperature in the preheating step and the postheating step is preferably 80 to 250 ° C.
  • the upper limit is more preferably 200 ° C. or less, and further preferably 150 ° C. or less.
  • the lower limit is more preferably 90 ° C. or higher.
  • the heating time in the preheating step and the postheating step is preferably 30 to 300 seconds.
  • the upper limit is more preferably 240 seconds and even more preferably 180 seconds or less.
  • the lower limit is more preferably 60 seconds or more.
  • the cured film obtained using the curable composition of the present invention has an excellent light-shielding property, and has an optical density (OD: Optical Density) per film thickness of 1.0 ⁇ m in a wavelength region of 400 to 1200 nm of 2. 0.0 or more is preferable, and 3.0 or more is more preferable.
  • the upper limit is not particularly limited, but is generally preferably 10 or less.
  • the cured film can be preferably used as a light shielding film. In this specification, the optical density per 1.0 ⁇ m thickness in the wavelength region of 400 to 1200 nm is 3.0 or more.
  • a method of measuring the optical density of a cured film first, a cured film is formed on a glass substrate, and measured using a transmission densitometer (X-rite 361T (visual) densitometer). The film thickness at the location is also measured, and the optical density per predetermined film thickness is calculated.
  • the cured film preferably has a surface uneven structure. By doing so, the reflectance of the cured film can be reduced when the cured film is a light shielding film. Even if the surface of the cured film itself has an uneven structure, another layer may be provided on the cured film to provide the uneven structure.
  • the shape of the surface concavo-convex structure is not particularly limited, but the surface roughness is preferably in the range of 0.55 ⁇ m to 1.5 ⁇ m.
  • the reflectance of the cured film is preferably less than 7%, more preferably less than 5%, and still more preferably less than 3%.
  • the method for producing the surface uneven structure is not particularly limited.
  • a cured film or other layer by a method containing an organic filler and / or an inorganic filler in a cured film or other layer, a lithography method utilizing exposure and development, or an etching method, a sputtering method, a nanoimprint method, etc. A method of roughening the surface of the layer may be used.
  • the method of reducing the reflectance of the cured film includes 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 And a method of forming a low optical density layer and a high optical density layer described in JP-A-2015-1654.
  • the cured film is composed of portable devices such as personal computers, tablets, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as printer multifunction devices and scanners; surveillance cameras, barcode readers, cash Industrial equipment such as automated teller machines (ATMs), high-speed cameras, and devices with personal authentication using facial image authentication; in-vehicle camera equipment; endoscopes, capsule endoscopes, And medical camera equipment such as catheters; and biosensors, biosensors, military reconnaissance cameras, stereoscopic map cameras, weather and ocean observation cameras, land resource exploration cameras, and space astronomy 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 cured film can also be used for applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode).
  • the cured film is suitable for members that provide a light shielding function or an antireflection function, in addition to optical filters and optical films used in micro LEDs and micro OLEDs.
  • Examples of the micro LED and the micro OLED include those described in JP-T-2015-500562 and JP-T-2014-533890.
  • the cured film is also suitable as an optical filter and an optical film used for quantum dot sensors and quantum dot solid-state imaging devices. Moreover, it is suitable as a member which provides a light shielding function and an antireflection function. Examples of the quantum dot sensor and the quantum dot solid-state imaging device include those described in US Patent Application Publication No. 2012/37789 and International Publication No. 2008/131313 pamphlet.
  • the cured film is also preferably used for a light shielding member and / or a light shielding film of a headlight unit used for a vehicle headlamp such as an automobile. Moreover, it is also preferable to use it for an antireflection member, an antireflection film, or the like.
  • the cured film obtained using the curable composition of the present invention is also preferably used as a so-called light-shielding film.
  • a light shielding film is also preferably used for a solid-state imaging device.
  • a light shielding film is one of the preferable forms in the cured film obtained using the curable composition of this invention. That is, the cured film of the present invention is also preferably a light shielding film.
  • the manufacturing method of the cured film which is a light shielding film can be similarly performed by the method described as the manufacturing method of the above-described cured film.
  • a light-shielding film can be produced by applying a curable composition to a substrate to form a curable composition layer, and exposing and developing.
  • the present invention also includes an invention of an optical element.
  • the optical element of the present invention is an optical element having the cured film (light-shielding film).
  • the optical element include an optical element used in an optical apparatus such as a camera, binoculars, a microscope, and a semiconductor exposure apparatus.
  • the said optical element is a solid-state image sensor mounted in a camera etc., for example.
  • the solid-state imaging device of the present invention contains the cured film (light-shielding film).
  • the form in which the solid-state image sensor includes a cured film (light-shielding film) is not particularly limited.
  • a plurality of photodiodes that form a light receiving area of a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) on a substrate.
  • 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 color adjusting pixel) or the opposite side of the forming surface.
  • the solid-state imaging device contains the solid-state imaging element.
  • the solid-state imaging device 100 includes a rectangular solid-state imaging element 101 and a transparent cover glass 103 that is held above the solid-state imaging element 101 and seals the solid-state imaging element 101. Yes. Further, a lens layer 111 is provided on the cover glass 103 with a spacer 104 interposed therebetween.
  • the lens layer 111 includes a support body 113 and a lens material 112. The lens layer 111 may have a configuration in which the support 113 and the lens material 112 are integrally formed.
  • the peripheral region of the lens layer 111 is shielded from light by providing a light shielding film 114.
  • a cured film obtained using the curable composition 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 a light receiving surface thereof and outputs it 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 includes a rectangular chip substrate 106 and a circuit substrate 107 having the same size, and the circuit substrate 107 is laminated on the back surface of the chip substrate 106.
  • the material of the substrate used as the chip substrate 106 is not particularly limited, and a known material can be used.
  • An imaging unit 102 is provided at the center of the surface of the chip substrate 106. Further, when stray light is incident on the peripheral area of the imaging unit 102, dark current (noise) is generated from a circuit in the peripheral area. Therefore, the peripheral area is shielded from light by providing a light shielding film 115. A cured film obtained using the curable composition is preferably used as the light shielding film 115.
  • a plurality of electrode pads 108 are provided on the surface edge of the chip substrate 106.
  • the electrode pad 108 is electrically connected to the imaging unit 102 via a signal line (not shown) provided on the surface of the chip substrate 106 (which may be a bonding wire).
  • External connection terminals 109 are provided on the back surface of the circuit board 107 at positions substantially below the electrode pads 108, respectively. Each external connection terminal 109 is connected to an electrode pad 108 via a through electrode 110 that vertically penetrates the multilayer substrate 105. Each external connection terminal 109 is connected to a control circuit that controls driving of the solid-state image sensor 101, an image processing circuit that performs image processing on an image signal output from the solid-state image sensor 101, and the like via a wiring (not shown). Has been.
  • the imaging unit 102 is configured by each unit provided on a substrate 204 such as a light receiving element 201, a color filter 202, and a 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 using the curable composition of the present invention can also be used as the black matrix 205bm.
  • a p-well layer 206 is formed on the surface layer of the substrate 204.
  • light receiving elements 201 which are n-type layers and generate and store signal charges by photoelectric conversion, are arranged in a square lattice pattern.
  • a vertical transfer path 208 made of an n-type layer is formed via a readout gate portion 207 on the surface layer of the p-well layer 206.
  • a vertical transfer path 208 belonging to an adjacent pixel is formed on the other side of the light receiving element 201 via an element isolation region 209 made of a p-type layer.
  • the read gate unit 207 is a channel region for reading signal charges accumulated in the light receiving element 201 to the vertical transfer path 208.
  • a gate insulating film 210 made of an ONO (Oxide-Nitride-Oxide) film is formed on the surface of the substrate 204.
  • a vertical transfer electrode 211 made of polysilicon or amorphous silicon is formed 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.
  • 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 signal charges.
  • the signal charges are sequentially transferred from the vertical transfer path 208 to a horizontal transfer path (not shown) and an output unit (floating diffusion amplifier), and then output as a voltage signal.
  • a light shielding film 212 is formed on the vertical transfer electrode 211 so as to cover the surface thereof.
  • the light shielding film 212 has an opening at a position directly above the light receiving element 201 and shields light from other areas.
  • a cured film obtained using the curable composition of the present invention can also be used as the light shielding film 212.
  • an insulating film 213 made of BPSG (borophosphosilicate glass), an insulating film (passivation film) 214 made of P-SiN, and a transparent intermediate layer made of a planarizing film 215 made of transparent resin or the like are provided on the light shielding film 212.
  • BPSG borophosphosilicate glass
  • passivation film insulating film
  • a transparent intermediate layer made of a planarizing film 215 made of transparent resin or the like are provided. ing.
  • the color filter 202 is formed on the intermediate layer.
  • the cured film obtained using the curable composition of the present invention is also preferably 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.
  • As the black matrix those already described above; a black edge provided at the peripheral portion of an image display device such as a liquid crystal display device; a lattice between red, blue, and green pixels, and / or stripes A black part of the shape; a dot-like and / or a linear black pattern for TFT (thin film transistor) light shielding; and the like.
  • the black matrix improves the display contrast, and in the case of an active matrix driving type liquid crystal display device using thin film transistors (TFTs), in order to prevent image quality deterioration due to light current leakage, it has a high light shielding property (with an optical density OD). 3 or more).
  • TFTs thin film transistors
  • the production method of the black matrix is not particularly limited, but can be produced by the same method as the production method of the cured film.
  • a curable composition can be applied to a substrate to form a curable composition layer, and 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 with respect to visible light (wavelength 400 to 800 nm).
  • Specific examples of such materials include glass such as soda lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester resins and polyolefin resins; and the like. In view of chemical resistance and heat resistance, alkali-free glass or quartz glass is preferable.
  • the cured film obtained using the curable composition of the present invention is also preferably contained in a color filter.
  • the form in which the color filter contains a cured film is not particularly limited, and examples thereof include a color filter including a substrate and the black matrix. That is, a color filter including red, green, and blue colored pixels formed in the openings of the black matrix formed on the substrate can be exemplified.
  • a color filter containing a black matrix can be produced, for example, by the following method.
  • a coating film (resin composition layer) of a resin composition containing a pigment corresponding to each colored pixel of a color filter is formed in an opening of a patterned black matrix formed on a substrate.
  • the resin composition for each color is not particularly limited, and a known resin composition can be used.
  • the black pigment is replaced with a colorant corresponding to each pixel. Things may be used.
  • it exposes with respect to the resin composition layer through the photomask which has a pattern corresponding to the opening part of a black matrix.
  • the colored pixels can be formed in the openings of the black matrix by baking.
  • a color filter having red, green, and blue pixels can be manufactured by performing a series of operations using, for example, resin compositions for each color containing red, green, and blue pigments.
  • the color filter as described above is also preferably used for a liquid crystal display device, for example.
  • a liquid crystal display device for example.
  • a curable composition was prepared using the components shown below.
  • Dispersion composition and black dye solution The following dispersion composition (dispersion) and black dye solution were prepared and used for the preparation of the curable composition.
  • A-1 Titanium black dispersion (A-1)
  • a titanium black dispersion (A-1) was obtained using the following raw materials. ⁇ Titanium black (a-1) (details will be described later) ⁇ Resin (X-1) (equivalent to Resin B) ⁇ PGMEA (propylene glycol monomethyl ether acetate)
  • the structure of the resin (X-1) is as follows.
  • the acid value was 58 and the weight average molecular weight was 32,000.
  • subjected to each repeating unit shows the molar ratio of each unit.
  • Resin (X-1) (5.5 parts by mass) was added to titanium black (a-1) (20 parts by mass), and PGMEA was further added so that the solid content concentration was 35% by mass.
  • the obtained dispersion was sufficiently stirred with a stirrer and premixed.
  • the obtained dispersion was subjected to a dispersion treatment using NPM Pilot manufactured by Shinmaru Enterprises under the following dispersion conditions to obtain a titanium black dispersion (A-1).
  • a uniform mixture aqueous solution was obtained by treatment at several 1360 rpm and a rotational speed of 1047 rpm for 20 minutes.
  • This aqueous solution is filled in a quartz container, heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.), then the atmosphere is replaced with nitrogen, and ammonia gas is kept at 100 mL / min for 5 hours at the same temperature.
  • the nitriding reduction treatment was carried out by flowing.
  • the recovered powder was pulverized in a mortar to obtain titanium black (a-1) containing Si atoms and having a powdery specific surface area of 73 m 2 / g.
  • a carbon black dispersion (A-2) was obtained using the raw materials shown below.
  • ⁇ Coated carbon black (details will be described later)
  • Resin (X-1) (equivalent to Resin B, the same as that used for the preparation of titanium black dispersion (A-1))
  • Solsperse 12000 (pigment derivative, manufactured by Lubrizol)
  • PGMEA propylene glycol monomethyl ether acetate
  • Resin (X-1) (4.5 parts by mass) and Solsperse 12000 (1 part by mass) are added to the coated carbon black (20 parts by mass), and the solid content concentration is further 35% by mass.
  • PGMEA was added.
  • the obtained mixed liquid was sufficiently stirred with a stirrer and premixed.
  • the dispersion was subjected to a dispersion treatment under the following dispersion conditions using an Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. to obtain a dispersion composition. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a carbon black dispersion (A-2).
  • Carbon black was produced by a normal oil furnace method. However, as the raw material oil, an ethylene bottom oil having a small Na content, Ca content, and S content was used, and combustion was performed using gas fuel. Furthermore, pure water treated with an ion exchange resin was used as the reaction stop water. Using a homomixer, the obtained carbon black (540 g) was stirred with pure water (14500 g) at 5,000 to 6,000 rpm for 30 minutes to obtain a slurry.
  • the slurry was transferred to a container with a screw type stirrer, and toluene (600 g) in which an epoxy resin “Epicoat 828” (manufactured by Japan Epoxy Resin) (60 g) was dissolved was added little by little while mixing at about 1,000 rpm. In about 15 minutes, the entire amount of carbon black dispersed in water moved to the toluene side and became particles of about 1 mm. Next, after draining with a 60 mesh wire net, the separated particles were put into a vacuum dryer and dried at 70 ° C. for 7 hours to remove toluene and water. The resin coating amount of the obtained coated carbon black was 10% by mass with respect to the total amount of carbon black and resin.
  • a black dye solution (A-3) was obtained using the following raw materials. ⁇ VALIFAST BLACK 3804 (black dye, manufactured by Orient Chemical Industries) ⁇ PGMEA (propylene glycol monomethyl ether acetate)
  • a black dye solution (A-3) was prepared by adding PGMEA (73.2 parts by mass) to VALIFAST BLACK 3804 (manufactured by Orient Chemical Industries) (26.8 parts by mass) and dissolving it.
  • Resin solutions (B-1) to (B-9) containing a resin represented by the following structure 1 or structure 2 were used for the preparation of the curable composition.
  • the numbers given to each repeating unit (X and Y are also numbers) intend the content (molar ratio) in the resin of each repeating unit.
  • the ratio of X and Y was appropriately changed so that the acid value of each resin would be the value shown in Table 1.
  • C-1 IRGACURE OXE-03 (manufactured by BASF)
  • C-2 IRGACURE OXE-02 (BASF)
  • C-3 IRGACURE 369 (BASF)
  • C-1 and C-2 are oxime ester polymerization initiators.
  • C-1 has the following structure.
  • D-1 a compound represented by “C— (CH 2 OOC—CH ⁇ CH 2 ) 4 ”.
  • D-2 the following compound (5-6 functional, double bond equivalent 10.1 mmol / g)
  • D-3 The following compound (tetrafunctional, double bond equivalent 7.6 mmol / g)
  • the value of the above “functionality” indicates the number of ethylenically unsaturated groups that one molecule of the polymerizable compound has.
  • the double bond equivalent (the weighted average value of the double bond equivalents of the hexafunctional polymerizable compound and the pentafunctional polymerizable compound) as a whole of D-2 is 10.1 mmol / g.
  • the exposure amount was adjusted so that the average value (the average value of 100 points) of the width (line width) of the line portion of the pattern obtained after development was 50 ⁇ m.
  • a developing device AD-1200, manufactured by Mikasa
  • development was performed by a paddle method for 15 seconds with a developer (CD-2060, manufactured by FUJIFILM Electronics Materials). Further, it was washed with pure water for 30 seconds using a shower nozzle to form a patterned cured film (also simply referred to as “pattern”) on the substrate.
  • the line width of the pattern was measured using an optical microscope (100 points), and the line width variation (3 ⁇ ) was evaluated from the following viewpoints.
  • a pattern was formed on the substrate in the same manner as in the line width measurement test. Using a scanning electron microscope (S-4800 (Hitachi High-Technologies Corporation)), the portion of the substrate where the curable composition layer was removed in the development process was observed and evaluated from the following viewpoints.
  • A Level where no residue is observed and no problem
  • B Partial residue is observed but there is no problem in practical use
  • C Level in which a large amount of residue is observed and practical problem
  • a cured film-formed substrate having a cured film on the substrate was produced in the same manner as in the line width measurement test except that light was irradiated without using a mask during exposure. Measured by using a spectroscope manufactured by JASCO Corporation (product name: V7200, combined with an absolute reflectance measurement unit) and incident light with a wavelength of 500 nm on an incident angle of 5 ° on the produced cured film forming substrate.
  • the reflectance was evaluated from the following viewpoints. A smaller reflectance is preferable.
  • A The rate of change in reflectivity is less than 5%, and there is no problem.
  • B A problem level when the reflectance change rate is 5% or more.
  • A The change rate of the line width is less than 5% and no problem.
  • B A problem level when the change rate of the line width is 5% or more.
  • the following table shows the composition of the curable compositions used in each Example and Comparative Example, and the test results. In addition, in the compounds of Comparative Examples 1 and 4, a pattern could not be formed.
  • the “content” column indicates the content (% by mass) of each component in each curable composition.
  • the description of “balance” as the content of the solvent indicates that a necessary amount of the solvent was added so that the total content of each component described in the table was 100. For example, it shows that the curable composition of Example 1 contains 63% by mass of the titanium black dispersion (A-1).
  • the column “Resin acid value” indicates the acid value of the resin contained in the resin solution used in the curable composition.
  • the column of “molecular weight of resin” indicates the weight average molecular weight of the resin contained in the resin solution used in the curable composition.
  • the column “Resin B” indicates whether or not the curable composition contains the resin B.
  • the case where the above requirements were satisfied was designated as A, and the case where the above requirements were not satisfied was designated as B.
  • the column of “oxime photopolymerization initiator” indicates whether or not the photopolymerization initiator contained in the curable composition is an oxime ester polymerization initiator. The case where the above requirements were satisfied was designated as A, and the case where the above requirements were not satisfied was designated as B.
  • the column of “specific photopolymerization initiator” indicates whether or not the photopolymerization initiator contained in the curable composition is a specific polymerization initiator.
  • the case where the above requirements were satisfied was designated as A, and the case where the above requirements were not satisfied was designated as B.
  • the column “type of black color material” indicates the type of black color material contained in the curable composition.
  • TB is intended for titanium black (titanium nitride)
  • CB is intended for carbon black
  • black dye is intended for black dye.
  • the column “number of functional groups of polymerizable compound” indicates the number of ethylenically unsaturated groups that the polymerizable compound contained in the curable composition has.
  • the curable composition of the present invention if used, a cured film (containing a patterned cured film) having excellent line width stability can be formed. Moreover, in the curable composition of Comparative Example 5 containing no polymerization inhibitor, there was no problem with the temporal stability of the line width of the resulting cured film, but there was a problem with the temporal stability of the reflectance. On the other hand, the curable composition of the present invention containing a polymerization inhibitor also had good stability over time of the reflectance of the resulting cured film. When the curable composition contained the resin B, it was confirmed that the reflectance of the cured film was more excellent (comparison between Examples 5 and 6).
  • the reflectance of the cured film is more excellent (comparison with Examples 5 and 6). Further, when the black pigment is titanium black (titanium nitride), the cured film is peeled off. It was confirmed that the inhibitory properties were more excellent (comparison between Examples 1 and 5).
  • the acid value of the resin A satisfying the requirement 1 is 170 to 300 mgKOH / g, it was confirmed that the cured film had more excellent line width stability, undercut suppression, and reflectance (Example 1 and Comparison with 8).
  • the weight average molecular weight of the resin A satisfying Requirement 2 is 6500 or less, the residual suppression of the cured film is more excellent (comparison with Examples 9 and 10).
  • the weight average molecular weight is 3000 to 5000, the line width of the cured film It was confirmed that the stability, the undercut suppressing property, and the reflectance were more excellent (comparison between Examples 1 and 9).
  • the photopolymerizable compound is an oxime photopolymerization initiator, the cured film has more excellent line width stability and undercut suppression (comparison with Examples 3 and 12), and is a specific photopolymerization initiator. Further, it was confirmed that the cured film was more excellent in inhibition of peeling (comparison between Examples 1 and 3).
  • the cured film has more excellent reflectivity (comparison between Example 7 and other examples), and further the double bond of the polymerizable compound When the equivalent was 11.0 mmol / g or more, it was confirmed that the line width stability, the undercut suppressing property, the peeling suppressing property, and the reflectance of the cured film were more excellent (Comparison with Examples 1 and 11). ).
  • DESCRIPTION OF SYMBOLS 100 Solid-state imaging device 101 ... Solid-state image sensor 102 ... Imaging part 103 ... Cover glass 104 ... Spacer 105 ... Laminated substrate 106 ... Chip substrate 107 ... Circuit board 108 ... Electrode pad 109 ... External connection terminal 110 ... Penetration electrode 111 ... Lens layer 112 ... Lens material 113 ... Supports 114, 115 ... Curing film 201 ... Light receiving element 202 ... Color filter 201 ... Light receiving element 202 ... Color filter 203 ... Micro lens 204 ... Substrate 205b ... Blue pixel 205r ... Red pixel 205g ... Green pixel 205bm ... Black matrix 206... P well layer 207... Readout gate portion 208... Vertical transfer path 209. Over gate insulating film 211 ... vertical transfer electrodes 212 ... cured film 213 ... insulating film 215 ... flattening film

Abstract

Provided is a curable composition which is capable of producing a cured film that has excellent line width stability. Also provided are: a cured film which is formed using such a curable composition; and a color filter, an optical element and a solid-state imaging element, each of which comprises this cured film. A curable composition according to the present invention contains a black colorant, a polymerizable compound, a resin A, a photopolymerization initiator and a polymerization inhibitor. With respect to this curable composition, the resin A satisfies one of the following requirements: the acid value thereof is 120-350 mgKOH/g; and the weight average molecular weight thereof is 3,000-7,500.

Description

硬化性組成物、硬化膜、光学素子、固体撮像素子、カラーフィルタCurable composition, cured film, optical element, solid-state image sensor, color filter
　本発明は、硬化性組成物、硬化膜、光学素子、固体撮像素子、及び、カラーフィルタに関する。 The present invention relates to a curable composition, a cured film, an optical element, a solid-state imaging element, and a color filter.
　固体撮像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。典型的には、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。 A method for producing a cured film used in a solid-state imaging device or the like is generally a method in which a curable composition layer is formed on a substrate and then cured. Typically, the curable composition layer is irradiated with light through a predetermined mask pattern, and then development processing is performed.
　例えば、特許文献１には、光重合性樹脂層等が積層された光重合性樹脂積層体であって、光重合性樹脂層が、アルカリ可溶性高分子、エチレン性不飽和結合を有する光重合性化合物、光重合性開始剤、及び黒色顔料を含有する光重合性樹脂組成物からなる光重合性樹脂積層体が開示されている。 For example, Patent Document 1 discloses a photopolymerizable resin laminate in which a photopolymerizable resin layer and the like are laminated, and the photopolymerizable resin layer has an alkali-soluble polymer and an ethylenically unsaturated bond. A photopolymerizable resin laminate comprising a photopolymerizable resin composition containing a compound, a photopolymerizable initiator, and a black pigment is disclosed.
再表２００８／０７８７０７号Reissue 2008/078707
　本発明者が、特許文献１に開示された光重合性樹脂組成物について検討したところ、この光重合性樹脂組成物には、パターン状に硬化膜を形成した場合における線幅の安定性（以下、単に「線幅安定性」又は「硬化膜の線幅安定性」ともいう）について改善の余地があることを知見した。 When this inventor examined the photopolymerizable resin composition disclosed by patent document 1, in this photopolymerizable resin composition, when the cured film was formed in pattern shape, stability (below) The inventors have found that there is room for improvement in terms of “line width stability” or “line width stability of cured film”.
　そこで、本発明は、線幅安定性に優れる硬化膜を製造できる硬化性組成物を提供することを課題とする。また、本発明は、このような硬化性組成物を用いて形成される、硬化膜、並びに、この硬化膜を有する、カラーフィルタ、光学素子、及び、固体撮像素子を提供することも課題とする。 Therefore, an object of the present invention is to provide a curable composition capable of producing a cured film having excellent line width stability. Another object of the present invention is to provide a cured film formed using such a curable composition, and a color filter, an optical element, and a solid-state imaging device having the cured film. .
　〔１〕
　黒色色材、重合性化合物、樹脂Ａ、光重合開始剤、及び、重合禁止剤を含有し、
　上記樹脂Ａが、酸価が１２０～３５０ｍｇＫＯＨ／ｇであること、及び、重量平均分子量が３０００～７５００であることのいずれか一方の要件を満たす、硬化性組成物。
　〔２〕
　上記重合性化合物の含有量に対する、上記重合禁止剤の含有量の質量比が、０．０００５超である、〔１〕に記載の硬化性組成物。
　〔３〕
　更に、上記樹脂Ａとは異なる樹脂であって、オキシアルキレン基及びオキシアルキレンカルボニル基からなる群から選択される１種以上の基を有する樹脂である樹脂Ｂを含有する、〔１〕又は〔２〕に記載の硬化性組成物。
　〔４〕
　上記重合性化合物が、４個のエチレン性不飽和基を有する、〔１〕～〔３〕のいずれかに記載の硬化性組成物。
　〔５〕
　上記樹脂Ａの酸価が１７０～３００ｍｇＫＯＨ／ｇである、〔１〕～〔４〕のいずれかに記載の硬化性組成物。
　〔６〕
　上記樹脂Ａの重量平均分子量が３０００～５０００である、〔１〕～〔５〕のいずれかに記載の硬化性組成物。
　〔７〕
　上記樹脂Ａの全繰り返し単位中、（メタ）アクリル系単量体由来の繰り返し単位の含有量が５０モル％以上である、〔１〕～〔６〕のいずれかに記載の硬化性組成物。
　〔８〕
　上記樹脂Ａが、ベンジル（メタ）アクリレート及び（メタ）アクリル酸の共重合体である、〔１〕～〔７〕のいずれかに記載の硬化性組成物。
　〔９〕
　上記重合性化合物の二重結合当量が、１１．０ｍｍｏｌ／ｇ以上である、〔１〕～〔８〕のいずれかに記載の硬化性組成物。
　〔１０〕
　上記光重合開始剤が、オキシムエステル系重合開始剤である、〔１〕～〔９〕のいずれかに記載の硬化性組成物。
　〔１１〕
　上記光重合開始剤が、後述する一般式（Ａ）で表される化合物である、〔１〕～〔１０〕のいずれかに記載の硬化性組成物。
　〔１２〕
　上記黒色色材が、黒色顔料である、〔１〕～〔１１〕のいずれかに記載の硬化性組成物。
　〔１３〕
　〔１〕～〔１２〕のいずれかに記載の硬化性組成物を用いて形成される、硬化膜。
　〔１４〕
　遮光膜である、〔１３〕に記載の硬化膜。
　〔１５〕
　〔１３〕又は〔１４〕に記載の硬化膜を有する、光学素子。
　〔１６〕
　〔１３〕又は〔１４〕に記載の硬化膜を有する、固体撮像素子。
　〔１７〕
　〔１３〕又は〔１４〕に記載の硬化膜を有する、カラーフィルタ。 [1]
Contains black color material, polymerizable compound, resin A, photopolymerization initiator, and polymerization inhibitor,
A curable composition, wherein the resin A satisfies any one of an acid value of 120 to 350 mgKOH / g and a weight average molecular weight of 3000 to 7500.
[2]
The curable composition according to [1], wherein a mass ratio of the content of the polymerization inhibitor to a content of the polymerizable compound is more than 0.0005.
[3]
[1] or [2] further containing a resin B which is a resin different from the resin A and has one or more groups selected from the group consisting of an oxyalkylene group and an oxyalkylenecarbonyl group. ] The curable composition as described in above.
[4]
The curable composition according to any one of [1] to [3], wherein the polymerizable compound has four ethylenically unsaturated groups.
[5]
The curable composition according to any one of [1] to [4], wherein the acid value of the resin A is 170 to 300 mgKOH / g.
[6]
The curable composition according to any one of [1] to [5], wherein the resin A has a weight average molecular weight of 3000 to 5000.
[7]
The curable composition according to any one of [1] to [6], wherein the content of repeating units derived from a (meth) acrylic monomer is 50 mol% or more in all repeating units of the resin A.
[8]
The curable composition according to any one of [1] to [7], wherein the resin A is a copolymer of benzyl (meth) acrylate and (meth) acrylic acid.
[9]
The curable composition according to any one of [1] to [8], wherein the double bond equivalent of the polymerizable compound is 11.0 mmol / g or more.
[10]
The curable composition according to any one of [1] to [9], wherein the photopolymerization initiator is an oxime ester polymerization initiator.
[11]
The curable composition according to any one of [1] to [10], wherein the photopolymerization initiator is a compound represented by the following general formula (A).
[12]
The curable composition according to any one of [1] to [11], wherein the black color material is a black pigment.
[13]
[1] A cured film formed using the curable composition according to any one of [12].
[14]
The cured film according to [13], which is a light shielding film.
[15]
[13] An optical element having the cured film according to [14].
[16]
[13] A solid-state imaging device having the cured film according to [14].
[17]
A color filter having the cured film according to [13] or [14].
　本発明によれば、線幅安定性に優れる硬化膜を製造できる硬化性組成物を提供できる。また、本発明は、このような硬化性組成物を用いて形成される、硬化膜、並びに、この硬化膜を有する、カラーフィルタ、光学素子、及び、固体撮像素子を提供できる。 According to the present invention, a curable composition capable of producing a cured film having excellent line width stability can be provided. In addition, the present invention can provide a cured film formed using such a curable composition, and a color filter, an optical element, and a solid-state imaging device having the cured film.
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.
　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包摂する範囲を意味する。 Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an 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。 In addition, in the notation of a group (atomic group) in the present specification, the notation in which neither substitution nor substitution is described includes a group containing a substituent as well as a group not containing a substituent. For example, the “alkyl group” includes not only an alkyl group not containing a 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, deep ultraviolet, extreme ultraviolet (EUV), X-ray, and electron beam. In the present specification, light means actinic rays and radiation. “Exposure” in this specification includes not only exposure with far ultraviolet rays, X-rays, EUV light, etc., but also drawing with particle beams such as electron beams and ion beams, unless otherwise specified.
　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。 In the present specification, “(meth) acrylate” represents acrylate and methacrylate. In the present specification, “(meth) acryl” represents acryl and methacryl. In the present specification, “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “(meth) acrylamide” represents acrylamide and methacrylamide. In this specification, “monomer” and “monomer” are synonymous.
　また、本明細書において、「ｐｐｍ」は「ｐａｒｔｓ－ｐｅｒ－ｍｉｌｌｉｏｎ（１０－６）」を意味し、「ｐｐｂ」は「ｐａｒｔｓ－ｐｅｒ－ｂｉｌｌｉｏｎ（１０－９）」を意味し、「ｐｐｔ」は「ｐａｒｔｓ－ｐｅｒ－ｔｒｉｌｌｉｏｎ（１０－１２）」を意味する。 Further, in the present specification, “ppm” means “parts-per-million (10 −6 )”, “ppb” means “parts-per-bilion (10 −9 )”, and “ppt” Means “parts-per-trilition (10 −12 )”.
　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 this specification, the weight average molecular weight (Mw) is a polystyrene equivalent value determined by a GPC (Gel Permeation Chromatography) method.
In this specification, the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (4.6 mm ID × 15 cm, Tosoh Corporation) as columns and THF (tetrahydrofuran) as an eluent. ).
〔硬化性組成物〕
　本発明の硬化性組成物は、黒色色材、重合性化合物、樹脂Ａ、光重合開始剤、及び、重合禁止剤を含有する。
　上記樹脂Ａは、酸価が１２０～３５０ｍｇＫＯＨ／ｇであること（以下「要件１」ともいう）、及び、重量平均分子量が３０００～７５００であること（以下「要件２」ともいう）のいずれか一方の要件を満たす樹脂である。 (Curable composition)
The curable composition of the present invention contains a black color material, a polymerizable compound, a resin A, a photopolymerization initiator, and a polymerization inhibitor.
The resin A has an acid value of 120 to 350 mg KOH / g (hereinafter also referred to as “requirement 1”) and a weight average molecular weight of 3000 to 7500 (hereinafter also referred to as “requirement 2”). It is a resin that satisfies one of the requirements.
　このような硬化性組成物を用いることで、線幅安定性に優れる硬化膜が形成できるメカニズムは必ずしも明らかではないが、本発明者らは以下のように考えている。
　硬化膜の形成においては、通常、硬化性組成物を用いて形成された硬化性組成物層が、露光を経て硬化され、更に、現像される。上記露光の際、照射された光が回折及び／又は散乱等することによって、本来の露光領域の周囲にわずかな光が漏れて、硬化性組成物層に部分的な硬化が生じることがある。このように、本来の露光領域の周囲において硬化性組成物層が部分的に硬化した箇所が、硬化膜に意図しない肥大化を生じさせ、硬化膜の線幅安定性に悪影響を及ぼす。
　対して、本発明の硬化性組成物は、重合禁止剤を含有するため、露光領域から漏れたわずかな光によって、部分的な硬化が生じるのを低減できる。また、本発明の硬化性組成物は、要件１及び要件２のいずれか一方を満たす樹脂Ａを含有するため、本発明の硬化性組成物を用いて形成される硬化性組成物層は現像性に優れ、部分的に硬化した箇所が生じても、現像時に除去される。その結果、本発明の硬化性組成物を用いることで、線幅安定性に優れる硬化膜を製造できると考えている。 The mechanism by which such a curable composition can be used to form a cured film having excellent line width stability is not necessarily clear, but the present inventors consider as follows.
In forming a cured film, a curable composition layer formed using a curable composition is usually cured through exposure and further developed. During the exposure, the irradiated light is diffracted and / or scattered, so that a slight amount of light leaks around the original exposure region, and the curable composition layer may be partially cured. As described above, the portion where the curable composition layer is partially cured around the original exposure region causes unintended enlargement of the cured film, and adversely affects the line width stability of the cured film.
On the other hand, since the curable composition of the present invention contains a polymerization inhibitor, it is possible to reduce the occurrence of partial curing due to slight light leaking from the exposed area. Moreover, since the curable composition of this invention contains resin A which satisfy | fills any one of the requirements 1 and the requirements 2, the curable composition layer formed using the curable composition of this invention is developability. Even if a partially cured portion is generated, it is removed during development. As a result, it is thought that the cured film which is excellent in line width stability can be manufactured by using the curable composition of this invention.
［硬化性組成物の成分］
　まず、本発明の硬化性組成物の成分について説明する。 [Components of curable composition]
First, the components of the curable composition of the present invention will be described.
＜黒色色材＞
　硬化性組成物は、黒色色材を含有する。
　黒色色材としては、黒色顔料及び黒色染料からなる群から選択される１種以上が挙げられる。
　黒色色材は１種単独で使用してもよく、２種以上を使用してもよい。
　硬化性組成物中における黒色色材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、１～９９質量％が好ましく、５～５５質量％がより好ましい。
　硬化性組成物の全固形分とは、硬化膜を形成する成分を意図し、溶媒は含まれない。また、硬化膜を形成する成分であれば、その性状が液体状であっても、固形分とみなす。 <Black color material>
The curable composition contains a black color material.
Examples of the black color material include one or more selected from the group consisting of black pigments and black dyes.
A black color material may be used individually by 1 type, and may use 2 or more types.
The content of the black color material in the curable composition is not particularly limited, but is preferably 1 to 99% by mass and more preferably 5 to 55% by mass with respect to the total solid content of the curable composition.
The total solid content of the curable composition intends a component that forms a cured film, and does not include a solvent. Moreover, if it is a component which forms a cured film, even if the property is a liquid state, it will be considered as solid content.
　また、単独では黒色色材として使用できない着色剤を複数組み合わせ、全体として黒色になるように調整して黒色色材としてもよい。
　例えば、単独で黒色を発現する顔料を黒色顔料とする他にも、単独では黒色以外の色を有する顔料を複数組み合わせて黒色顔料として使用してもよい。同様に、単独で黒色を発現する染料を黒色染料とする他にも、単独では黒色以外の色を有する染料を複数組み合わせて黒色染料として使用してもよい。
　なお、黒色色材とは、波長４００～７００ｎｍの全ての範囲にわたって吸収がある色材をいう。
　より具体的には、例えば、以下に説明する評価基準Ｚに適合する黒色色材が好ましい。
　まず、色材と、透明な樹脂マトリックス（アクリル樹脂等）と、溶剤とを含有し、全固形分に対する色材の含有量が６０質量％である組成物を調製する。得られた組成物を、ガラス基板上に、乾燥後の塗膜の膜厚が１μｍになるように塗布し、塗膜を形成する。乾燥後の塗膜の遮光性を、分光光度計（日立株式会社製ＵＶ－３６００等）を用いて評価する。乾燥後の塗膜の波長４００～７００ｎｍにおける透過率の最大値が１０％未満であれば、上記色材は評価基準Ｚに適合する黒色色材であると判断できる。 Alternatively, a plurality of colorants that cannot be used alone as a black color material may be combined and adjusted so as to be black as a whole to obtain a black color material.
For example, in addition to using a black pigment alone as a black pigment, a plurality of pigments having colors other than black alone may be used in combination as a black pigment. Similarly, in addition to using a black dye alone as a black dye, a single dye having a color other than black may be used in combination as a black dye.
The black color material means a color material that has absorption over the entire wavelength range of 400 to 700 nm.
More specifically, for example, a black color material that meets the evaluation standard Z described below is preferable.
First, a composition containing a coloring material, a transparent resin matrix (such as an acrylic resin) and a solvent and having a coloring material content of 60% by mass relative to the total solid content is prepared. The obtained composition is applied onto a glass substrate so that the thickness of the dried coating film is 1 μm, thereby forming a coating film. The light-shielding property of the coating film after drying is evaluated using a spectrophotometer (such as UV-3600 manufactured by Hitachi, Ltd.). If the maximum value of the transmittance at a wavelength of 400 to 700 nm of the coating film after drying is less than 10%, it can be determined that the color material is a black color material that meets the evaluation standard Z.
（黒色顔料）
　黒色色材は、反射率が低減された硬化膜を得られる点から、黒色顔料であることが好ましい。
　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。 (Black pigment)
The black color material is preferably a black pigment from the viewpoint of obtaining a cured film having a reduced reflectance.
Various known black pigments can be used as the black pigment. The black pigment may be an inorganic pigment or an organic pigment.
　黒色顔料としては、単独で黒色を発現する顔料が好ましい。
　また、黒色顔料は、例えば、赤外線を吸収する顔料が好ましい。
　ここで、赤外線を吸収する黒色顔料は、例えば、赤外領域（好ましくは、波長６５０～１３００ｎｍ）の波長領域に吸収を有する。波長６７５～９００ｎｍの波長領域に極大吸収波長を有することも好ましい。 As the black pigment, a pigment that expresses black alone is preferable.
The black pigment is preferably a pigment that absorbs infrared rays, for example.
Here, the black pigment that absorbs infrared rays has absorption in the wavelength region of the infrared region (preferably, wavelength 650 to 1300 nm), for example. It is also preferable to have a maximum absorption wavelength in the wavelength region of 675 to 900 nm.
　赤外線を吸収し、かつ、単独で黒色を発現する無機顔料としては、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。上記無機顔料には、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と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）等が挙げられる。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されてもよい。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。
　赤外線を吸収し、かつ、単独で黒色を発現する顔料としては、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。また、カーボンブラックとして、表面を樹脂で被覆したカーボンブラックを使用してもよい。 Examples of inorganic pigments that absorb infrared rays and develop black alone include Group 4 metal elements such as titanium (Ti) and zirconium (Zr), and Group 5 such as vanadium (V) and niobium (Nb). Metallic elements, cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and silver (Ag) Examples thereof include metal oxides, metal nitrides, and metal oxynitrides containing one or more metal elements selected from the group consisting of: The inorganic pigment may be subjected to a surface modification treatment. For example, inorganic particles that have been surface-modified with a surface treatment agent having both a silicone group and an alkyl group can be mentioned, such as “KTP-09” series (manufactured by Shin-Etsu Chemical Co., Ltd.). Further, the metal oxide, the metal nitride, and the metal oxynitride may be used as particles in which other atoms are mixed. For example, it may be used as a metal nitride-containing particle that further contains an atom (preferably an oxygen atom and / or a sulfur atom) selected from Group 13 to 17 elements of the periodic table.
Carbon black is also mentioned as a pigment that absorbs infrared rays and develops black alone. Specific examples of carbon black are commercially available C.I. I. Organic pigments such as CI Pigment Black 1 and C.I. I. And inorganic pigments such as CI Pigment Black 7. Carbon black whose surface is coated with a resin may be used as carbon black.
　なかでも、黒色顔料としては、硬化膜を形成する際のアンダーカットの発生を抑制できる点から、第４族の金属元素の窒化物若しくは酸化物、又は、第５族の金属元素の窒化物若しくは酸窒化物が好ましく、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、又は、ニオブの窒化物若しくは酸窒化物がより好ましく、チタンの窒化物若しくは酸窒化物が更に好ましい。
　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。 Especially, as a black pigment, from the point which can suppress generation | occurrence | production of the undercut at the time of forming a cured film, the nitride or oxide of a Group 4 metal element, or the nitride of a Group 5 metal element or Oxynitrides are preferred, titanium nitride or oxynitride, zirconium nitride or oxynitride, vanadium nitride or oxynitride, or niobium nitride or oxynitride, more preferably titanium nitride Or oxynitrides are more preferred.
The titanium nitride is titanium nitride, the zirconium nitride is zirconium nitride, the vanadium nitride is vanadium nitride, and the niobium nitride 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 Niobium.
　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）で表される低次酸化チタン、及び／又は、ＴｉＮｘＯｙ（０＜ｘ＜２．０，０．１＜ｙ＜２．０）で表され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されてもよい。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、ケイ素原子又は硫黄原子等）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されてもよい。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、ケイ素原子又は硫黄原子等）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 this specification, titanium nitride is intended for TiN, and may contain oxygen atoms that are unavoidable in production (for example, the surface of TiN particles are unintentionally oxidized).
In this specification, titanium nitride means a compound having a diffraction angle 2θ of a peak derived from the (200) plane when CuKα rays are used as an X-ray source is 42.5 ° to 42.8 °.
In this specification, titanium oxynitride is intended to be a compound having a diffraction angle 2θ of a peak derived from the (200) plane when CuKα rays are used as an X-ray source and exceeding 42.8 °. The upper limit of the diffraction angle 2θ of titanium oxynitride is not particularly limited, but is preferably 43.5 ° or less.
Examples of titanium oxynitride include titanium black. More specifically, for example, low-order titanium oxide represented by TiO 2 , Ti n O 2n-1 (1 ≦ n ≦ 20), and / or or include forms containing TiN x O y titanium oxynitride represented by (0 <x <2.0,0.1 <y <2.0). 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.
Further, titanium nitride may be used as particles in which other atoms are mixed. For example, titanium nitride may be used as titanium nitride-containing particles that further contain atoms (preferably silicon atoms or sulfur atoms) selected from Group 13-17 elements of the periodic table. The same applies to 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 further mixed. For example, the metal nitride may be used as a metal nitride-containing particle that further contains an atom (preferably a silicon atom or a sulfur atom) selected from Group 13 to 17 elements of the periodic table.
　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 rays as an X-ray source, TiN has the strongest peak, the peak derived from the (200) plane is in the vicinity of 2θ = 42.5 °, and TiO is ( The peak originating from the (200) plane is observed in the vicinity of 2θ = 43.4 °. On the other hand, although not the strongest peak, the peak derived from the (200) plane of anatase TiO 2 is in the vicinity of 2θ = 48.1 °, and the peak derived from the (200) plane of rutile TiO 2 is 2θ = 39. Observed around 2 °. Therefore, as the titanium oxynitride contains more oxygen atoms, the peak position shifts to the higher angle side with respect to 42.5 °.
　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ことが好ましい。 When titanium nitride contains titanium oxide TiO 2 , the peak derived from anatase TiO 2 (101) as the strongest peak is derived from rutile TiO 2 (110) in the vicinity of 2θ = 25.3 °. A peak is observed in the vicinity of 2θ = 27.4 °. However, since TiO 2 is white and causes a reduction in the light-shielding property of the light-shielding film obtained by curing the curable composition, it is preferably 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 constituting the titanium nitride can be determined from the half width of the peak obtained by measuring the X-ray diffraction spectrum. The crystallite size can be calculated using Scherrer'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。 The crystallite size constituting the titanium nitride is preferably 50 nm or less, and more preferably 20 nm or more. When the crystallite size is 20 to 50 nm, the cured film formed using the curable composition tends to have higher ultraviolet (especially i-line (wavelength 365 nm)) transmittance and is more curable. 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号公報）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。 The production method of the black pigment is not particularly limited, and a known production method can be used, and examples thereof include a gas phase reaction method. Examples of the gas phase reaction method include an electric furnace method, a thermal plasma method, and the like. The thermal plasma method is preferable in that impurities are less mixed, the particle diameter is easily uniformed, and productivity is high.
In the thermal plasma method, a method for generating thermal plasma is not particularly limited, and includes direct current arc discharge, multilayer arc discharge, radio frequency (RF) plasma, hybrid plasma, and the like, and there is little mixing of impurities from the electrodes. High frequency plasma is more preferred.
The specific method for producing the black pigment by the thermal plasma method is not particularly limited. For example, as a method for producing titanium nitride, a method of reacting titanium tetrachloride with ammonia gas in a plasma flame (JP-A-2-22110). No.), a method in which titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced as a carrier gas, and is nitrided and synthesized in the cooling process (Japanese Patent Laid-Open No. 61-11140), and ammonia gas is added to the periphery of the plasma. And a blowing method (Japanese Patent Laid-Open No. 63-85007).
However, the production method of the 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.
　また、上述したような金属原子の（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号公報の段落００２０、及び、段落０１２４～０１３８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。 Further, a metal pigment (oxy) nitride as described above may be coated with a silicon-containing compound to form a black pigment.
The method for coating the (oxy) nitride of the metal atom is not particularly limited, and a known method can be used. For example, it is described in JP-A No. 53-33228, page 2, lower right to page 4, upper right. Method (using (acid) nitride of metal atom instead of titanium oxide), method described in paragraphs 0015 to 0043 of JP-A-2008-69193 ((acid) of metal atom instead of fine particle titanium dioxide) And the method described in paragraphs 0020 and 0124 to 0138 of JP-A No. 2016-74870 (using (acid) nitride of metal atom instead of metal oxide fine particles). And the above content is incorporated herein.
　更に、硬化性組成物がチタンブラックを含有する場合、チタンブラックを、チタンブラック及びＳｉ原子を含む被分散体として含有することも好ましい。
　この形態において、チタンブラックは、組成物中において被分散体として含有されるものであり、被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）が質量換算で０．０５以上が好ましく、０．０５～０．５がより好ましく、０．０７～０．４が更に好ましい。
　ここで、上記被分散体は、チタンブラックが一次粒子の状態であるもの、凝集体（二次粒子）の状態であるものの双方を包含する。
　被分散体のＳｉ／Ｔｉを変更する（例えば、０．０５以上とする）ためには、以下のような手段を用いることができる。
　まず、酸化チタンとシリカ粒子とを分散機を用いて分散することにより分散物を得て、この分散物を高温（例えば、８５０～１０００℃）にて還元処理することにより、チタンブラック粒子を主成分とし、ＳｉとＴｉとを含有する被分散体を得ることができる。上記還元処理は、アンモニア等の還元性ガスの雰囲気下で行うこともできる。
　酸化チタンとしては、ＴＴＯ－５１Ｎ（商品名、石原産業製）等が挙げられる。
　シリカ粒子の市販品としては、ＡＥＲＯＳＩＬ（登録商標）９０、１３０、１５０、２００、２５５、３００、３８０（商品名、エボニック製）等が挙げられる。
　酸化チタンとシリカ粒子との分散は、分散剤を用いてもよい。分散剤としては、後述する分散剤として説明するものが挙げられる。
　上記の分散は溶剤中で行ってもよい。溶剤としては、水、有機溶剤が挙げられる。後述する有機溶剤の欄で説明するものが挙げられる。
　Ｓｉ／Ｔｉが、例えば、０．０５以上等に調整されたチタンブラックは、例えば、特開２００８－２６６０４５号公報の段落０００５及び段落００１６～００２１に記載の方法により作製することができる。 Furthermore, when a curable composition contains titanium black, it is also preferable to contain titanium black as a to-be-dispersed body containing titanium black and Si atom.
In this embodiment, titanium black is contained as a dispersion in the composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more in terms of mass. Is preferable, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is still more preferable.
Here, the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).
In order to change the Si / Ti of the object to be dispersed (for example, 0.05 or more), the following means can be used.
First, titanium oxide and silica particles are dispersed using a disperser to obtain a dispersion, and this dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.) to thereby obtain titanium black particles mainly. A dispersed material containing Si and Ti as components can be obtained. The reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia.
Examples of titanium oxide include TTO-51N (trade name, manufactured by Ishihara Sangyo).
Examples of commercially available silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name, manufactured by Evonik).
A dispersing agent may be used for the dispersion of titanium oxide and silica particles. Examples of the dispersant include those described as the dispersant described later.
The dispersion may be performed in a solvent. Examples of the solvent include water and organic solvents. What is demonstrated in the column of the organic solvent mentioned later is mentioned.
Titanium black in which Si / Ti is adjusted to, for example, 0.05 or more can be produced, for example, by the method described in paragraphs 0005 and 0016 to 0021 of JP-A-2008-266045.
　チタンブラック及びＳｉ原子を含む被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）を好適な範囲（例えば０．０５以上）に調整することで、この被分散体を含む組成物を用いて硬化膜を形成した際に、硬化膜の形成領域外における組成物由来の残渣物が低減される。なお、残渣物は、チタンブラック粒子、樹脂成分等の組成物に由来する成分を含むものである。
　残渣物が低減される理由は未だ明確ではないが、上記のような被分散体は小粒径となる傾向があり（例えば、粒径が３０ｎｍ以下）、更に、この被分散体のＳｉ原子が含まれる成分が増すことにより、膜全体の下地との吸着性が低減される。これが、硬化膜の形成における未硬化の組成物（特に、チタンブラック）の現像除去性の向上に寄与すると推測される。
　また、チタンブラックは、紫外光から赤外光までの広範囲にわたる波長領域の光に対する遮光性に優れることから、上記したチタンブラック及びＳｉ原子を含む被分散体（好ましくはＳｉ／Ｔｉが質量換算で０．０５以上であるもの）を用いて形成された遮光膜は優れた遮光性を発揮する。
　なお、被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）は、例えば、特開２０１３－２４９４１７号公報の段落００３３に記載の方法（１－１）または方法（１－２）を用いて測定できる。
　また、組成物を硬化して得られた硬化膜に含有される被分散体について、その被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）が０．０５以上か否かを判断する際は、特開２０１３－２４９４１７号公報の段落００３５に記載の方法（２）を用いる。 The composition containing this dispersion by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to a suitable range (for example, 0.05 or more). When a cured film is formed using a product, a residue derived from the composition outside the region where the cured film is formed is reduced. In addition, a residue contains the component derived from compositions, such as a titanium black particle and a resin component.
The reason why the residue is reduced is not yet clear, but the above-mentioned dispersed material tends to have a small particle size (for example, a particle size of 30 nm or less). By increasing the components contained, the adsorptivity of the entire film with the base is reduced. This is presumed to contribute to the improvement of the development removability of an uncured composition (particularly titanium black) in the formation of a cured film.
In addition, titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet light to infrared light, and thus the above-described dispersion to be dispersed containing titanium black and Si atoms (preferably Si / Ti is in terms of mass). A light-shielding film formed using a material having a thickness of 0.05 or more exhibits excellent light-shielding properties.
The content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A ).
Whether or not the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more with respect to the dispersion to be contained in the cured film obtained by curing the composition Is determined using the method (2) described in paragraph 0035 of JP2013-249417A.
　チタンブラック及びＳｉ原子を含む被分散体において、チタンブラックは、上記したものを使用できる。
　以下、被分散体にＳｉ原子を導入する際に用いられる材料について述べる。被分散体にＳｉ原子を導入する際には、シリカ等のＳｉ含有物質を用いればよい。
　用いうるシリカとしては、沈降シリカ、フュームドシリカ、コロイダルシリカ、合成シリカ等を挙げることができ、これらを適宜選択して使用すればよい。
　更に、シリカ粒子の粒径が遮光膜（硬化膜）を形成した際に膜厚よりも小さい粒径であると遮光性がより優れるため、シリカ粒子として微粒子タイプのシリカを用いることが好ましい。なお、微粒子タイプのシリカの例としては、例えば、特開２０１３－２４９４１７号公報の段落００３９に記載のシリカが挙げられ、これらの内容は本明細書に組み込まれる。 In the dispersion containing titanium black and Si atoms, the above-described titanium black can be used.
Hereinafter, materials used for introducing Si atoms into the dispersion will be described. When Si atoms are introduced into the dispersion, a Si-containing material such as silica may be used.
Examples of silica that can be used include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These can be selected and used as appropriate.
Furthermore, when the particle size of the silica particles is smaller than the film thickness when the light shielding film (cured film) is formed, the light shielding property is more excellent. Therefore, it is preferable to use fine particle type silica as the silica particles. Examples of the fine particle type silica include silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.
　更に、上述したように、単独では黒色以外の色を有する顔料を複数組み合わせて黒色顔料として使用してもよい。
　このように単独では黒色以外の色を有する顔料は、無機顔料であっても有機顔料であってもよい。単独では黒色以外の色を有する顔料としては、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。 Furthermore, as described above, a plurality of pigments having a color other than black alone may be combined and used as a black pigment.
Thus, the pigment having a color other than black alone may be an inorganic pigment or an organic pigment. As a pigment having a color other than black alone, for example, chromatic pigments (chromatic pigments) such as R (red), G (green), and B (blue) can also be used.
　単独では黒色以外の色を有する無機顔料としては、特に制限されず、公知の無機顔料を使用できる。
　上記無機顔料としては、例えば、酸化チタン、酸化クロム、酸化鉄、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、サーモンピンク等から選択できる。
　上記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）等が挙げられる。 The inorganic pigment having a color other than black alone is not particularly limited, and a known inorganic pigment can be used.
Examples of the inorganic pigment include titanium oxide, chromium oxide, iron oxide, red lead, iron oxide red, yellow lead, zinc yellow (zinc yellow 1 type, zinc yellow 2 type), ultramarine blue, prussian blue (ferrocyanian). (Chemical ferric) Zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, Victoria green, bitumen (unrelated to Prussian blue), vanadium zirconium blue, chrome tin pink, ceramic red, and salmon pink .
The inorganic pigment may be subjected to a surface modification treatment. 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 “KTP-09” series (manufactured by Shin-Etsu Chemical Co., Ltd.).
　単独では黒色以外の色を有する有機顔料としては、例えば、下記有機顔料から選択される。
　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。 The organic pigment having a color other than black alone is selected from, for example, the following organic pigments.
Color Index (CI) Pigment Yellow 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, Etc. 72,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214;
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 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, 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, 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, and the like.
　顔料は、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、単独で黒色を発現する顔料、及び／又は、単独では黒色以外の色を有する顔料等に、赤色、緑色、黄色、オレンジ色、紫色、及び、ブルー等の有彩色顔料若しくは後述する染料を混ぜてもよい。
　また、赤外線を吸収し、かつ、単独で黒色を発現する顔料に、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ことも好ましく、赤色顔料を混合することがより好ましい。
　更に、後述する赤外線吸収剤を加えてもよい。 The pigment may be used in combination with a dye described later.
In order to adjust the color tone and improve the light-shielding property in a desired wavelength region, for example, a pigment that expresses black alone and / or a pigment that has a color other than black alone, red, green, You may mix chromatic pigments, such as yellow, orange, purple, and blue, or the dye mentioned later.
Moreover, it is also preferable to mix a red pigment or dye, or a violet pigment or dye with the pigment which absorbs infrared rays and develops black alone, and more preferably a red pigment.
Furthermore, you may add the infrared absorber mentioned later.
　また、単独では黒色以外の色を有する顔料であって、赤外線を吸収する顔料として、タングステン化合物、及び、金属ホウ化物等も使用できる。中でも、赤外領域の波長における遮光性に優れる点からは、タングステン化合物が好ましい。タングステン化合物は、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。 Further, a tungsten compound, a metal boride, or the like can be used as a pigment having a color other than black by itself and absorbing infrared rays. Among these, a tungsten compound is preferable from the viewpoint of excellent light blocking properties at wavelengths in the infrared region. The tungsten compound is excellent in the light absorption wavelength region of the oxime polymerization initiator related to the curing efficiency by exposure and the translucency in the visible light region.
　ハンドリング性を考慮すると、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。黒色顔料が複数種類の顔料の組み合わせからなる場合、黒色顔料を構成する顔料の１種以上が上記範囲内にあることが好ましく、黒色顔料を構成する顔料の全種が上記範囲内にあることがより好ましい。 In consideration of handling properties, the average primary particle size of the black pigment is preferably 0.01 to 0.1 μm, more preferably 0.01 to 0.05 μm. When the black pigment is composed of a combination of plural kinds of pigments, it is preferable that one or more of the pigments constituting the black pigment are within the above range, and that all the pigments constituting the black pigment are within the above range. More preferred.
　なお、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、顔料の平均一次粒子径とする。 In addition, the average primary particle diameter of a pigment can be measured using a transmission electron microscope (Transmission Electron Microscope, TEM). As the transmission electron microscope, for example, a transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
Maximum length of a particle image obtained using a transmission electron microscope (Dmax: maximum length at two points on the contour of the particle image), and maximum vertical length (DV-max: two straight lines parallel to the maximum length) When the image is sandwiched between the two lines, the shortest length connecting the two straight lines is measured, and the geometric mean value (Dmax × DV−max) ½ is taken as the particle diameter. The particle diameter of 100 particles is measured by this method, and the arithmetic average value thereof is taken as the average particle diameter to obtain the average primary particle diameter of the pigment.
（黒色染料）
　黒色染料としては、単独で黒色を発現する染料を使用できる。更に、上述の通り、単独では黒色以外の色を有する染料を複数組み合わせて黒色染料として使用してもよい。
　このような着色染料としては、例えば、Ｒ（レッド）、Ｇ（グリーン）、及び、Ｂ（ブルー）等の有彩色系の染料（有彩色染料）の他、特開２０１４－４２３７５の段落００２７～０２００に記載の着色剤も使用できる。 (Black dye)
As the black dye, a dye that expresses black alone can be used. Furthermore, as described above, a single dye having a color other than black may be used in combination as a black dye.
Examples of such coloring dyes include chromatic dyes (chromatic dyes) such as R (red), G (green), and B (blue), and paragraphs 0027 to 375 of JP-A-2014-42375. Colorants described in 0200 can also be used.
　また、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。 Examples of the dye include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Tokuho 2592207, US Pat. No. 4,808,501. No. 5, U.S. Pat. No. 5,667,920, U.S. Pat. No. 505950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, and JP-A-6-194828. The pigment | dye currently disclosed by the gazette etc. can be used. Pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, or pyrrolopyrazole azomethines A compound etc. can be used. A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A. Moreover, you may use the polymerizable dye which has polymerizability in a molecule | numerator, As a commercial item, the RDW series by Wako Pure Chemical Industries Ltd. is mentioned, for example.
（赤外線吸収剤）
　黒色色材は、更に、単独では黒色以外の色を有する色材として、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 black color material may further contain an infrared absorber as a color material having a color other than black by itself.
The infrared absorber means a compound having absorption in the wavelength region of the infrared region (preferably, wavelength 650 to 1300 nm). As the infrared absorber, a compound having a maximum absorption wavelength in a wavelength region of 675 to 900 nm is preferable.
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, squarylium compounds, naphthalocyanine compounds, quaterylenes. Examples include compounds, dithiol metal complex compounds, and croconium compounds.
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 2010-1111750 A may be used. Embedded in the book. As the cyanine compound, for example, “functional pigment, Shin Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein.
　上記分光特性を有する着色剤として、特開平０７－１６４７２９号公報の段落０００４～００１６に開示の化合物及び／又は特開２００２－１４６２５４号公報の段落００２７～００６２に開示の化合物、特開２０１１－１６４５８３号公報の段落００３４～００６７に開示のＣｕ及び／又はＰを含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 the colorant having the above-mentioned 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-2011-16483 It is also possible to use near-infrared absorbing particles comprising a crystallite of an oxide containing Cu and / or P disclosed in paragraphs 0034 to 0067 of the publication 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ことが好ましく、２５℃の水に１０質量％以上溶解する化合物がより好ましい。このような化合物を用いることで、耐溶剤性が良化する。
　ピロロピロール化合物は、特開２０１０－２２２５５７号公報の段落００４９～００６２を参酌でき、この内容は本明細書に組み込まれる。シアニン化合物及びスクアリリウム化合物は、国際公開２０１４／０８８０６３号公報の段落００２２～００６３、国際公開２０１４／０３０６２８号公報の段落００５３～０１１８、特開２０１４－５９５５０号公報の段落００２８～００７４、国際公開２０１２／１６９４４７号公報の段落００１３～００９１、特開２０１５－１７６０４６号公報の段落００１９～００３３、特開２０１４－６３１４４号公報の段落００５３～００９９、特開２０１４－５２４３１号公報の段落００８５～０１５０、特開２０１４－４４３０１号公報の段落００７６～０１２４、特開２０１２－８５３２号公報の段落００４５～００７８、特開２０１５－１７２１０２号公報の段落００２７～００６７、特開２０１５－１７２００４号公報の段落００２９～００６７、特開２０１５－４０８９５号公報の段落００２９～００８５、特開２０１４－１２６６４２号公報の段落００２２～００３６、特開２０１４－１４８５６７号公報の段落００１１～００１７、特開２０１５－１５７８９３号公報の段落００１０～００２５、特開２０１４－０９５００７号公報の段落００１３～００２６、特開２０１４－８０４８７号公報の段落００１３～００４７、及び、特開２０１３－２２７４０３号公報の段落０００７～００２８等を参酌でき、この内容は本明細書に組み込まれる。 The compound having the maximum absorption wavelength in the wavelength region of 675 to 900 nm is preferably at least one selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound.
Further, the infrared absorber is preferably a compound that dissolves 1% by mass or more in 25 ° C. water, and more preferably a compound that dissolves 10% by mass or more in 25 ° C. water. By using such a compound, the solvent resistance is improved.
As for the pyrrolopyrrole compound, paragraphs 0049 to 0062 of JP 2010-222557 A can be referred to, the contents of which are incorporated herein. The cyanine compounds and squarylium compounds are disclosed in paragraphs 0022 to 0063 of International Publication No. 2014/088063, paragraphs 0053 to 0118 of International Publication No. 2014/030628, paragraphs 0028 to 0074 of JP 2014-59550 A, and International Publication No. 2012/0074. 169447, paragraphs 0013 to 0091, JP2015-176046, paragraphs 0019 to 0033, JP2014-63144, paragraphs 0053 to 00099, JP201452431, paragraphs 0085 to 0150, JP Paragraphs 0076 to 0124 of Japanese Patent Application Laid-Open No. 2014-44301, Paragraphs 0045 to 0078 of Japanese Patent Application Laid-Open No. 2012-8532, Paragraphs 0027 to 0067 of Japanese Patent Application Laid-Open No. 2015-172102, and Paragraph 002 of Japanese Patent Application Laid-Open No. 2015-172004. To 0067, paragraphs 0029 to 0085 of JP-A-2015-40895, paragraphs 0022 to 0036 of JP-A-2014-126642, paragraphs 0011 to 0017 of JP-A-2014-148567, and JP-A-2015-157893. Paragraphs 0010 to 0025, paragraphs 0013 to 0026 of JP 2014-095007 A, paragraphs 0013 to 0047 of JP 2014-80487 A, paragraphs 0007 to 0028 of JP 2013-227403 A, and the like 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、後述する光重合開始剤の作用を受けて重合する化合物を意図する。 <Polymerizable compound>
The curable composition contains a polymerizable compound. In the present specification, the polymerizable compound means a compound that polymerizes under the action of a photopolymerization initiator 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％が好ましく、１０～２５質量％がより好ましく、１５～２３質量％がさらに好ましい。重合性化合物は、１種を単独で用いても、２種以上を併用してもよい。２種以上の重合性化合物を併用する場合には、合計含有量が上記範囲内であることが好ましい。
　重合性化合物の分子量は２０００以下であることが好ましい。 The content of the polymerizable compound in the curable composition is not particularly limited, but is preferably 5 to 30% by mass, more preferably 10 to 25% by mass with respect to the total solid content of the curable composition, 15 to 23 mass% is further more preferable. A polymeric compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of polymeric compounds together, it is preferable that total content is in the said range.
The molecular weight of the polymerizable compound is preferably 2000 or less.
　重合性化合物は、表面が適度に粗面化されて反射率が低減された硬化膜を得られる点から、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１～１５個含有する化合物が好ましく、３～６個含有する化合物がより好ましく、４～５個含有する化合物が更に好ましく、４個含有する化合物が特に好ましい。
　また、重合性化合物を複数種類使用する場合、エチレン性不飽和基を４～５個（好ましくは４個）含有する化合物である重合性化合物の含有量は、硬化性組成物中の全重合性化合物に対して、８０質量%以上であることが好ましく、９５質量％以上であることがより好ましい。
　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 a group containing an ethylenically unsaturated bond (hereinafter, also simply referred to as “ethylenically unsaturated group”) from the viewpoint of obtaining a cured film having a moderately roughened surface and reduced reflectance. Are preferably 1 to 15 compounds, more preferably 3 to 6 compounds, further preferably 4 to 5 compounds, and particularly preferably 4 compounds.
Further, when a plurality of types of polymerizable compounds are used, the content of the polymerizable compound which is a compound containing 4 to 5 (preferably 4) ethylenically unsaturated groups is determined based on the total polymerizable content in the curable composition. It is preferable that it is 80 mass% or more with respect to a compound, and it is more preferable that it is 95 mass% or more.
Examples of the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
　重合性化合物としては、例えば、特開２００８－２６０９２７号公報の段落００５０、及び、特開２０１５－６８８９３号公報の段落００４０に記載されている化合物を使用でき、上記の内容は本明細書に組み込まれる。 As the polymerizable compound, for example, compounds described in paragraph 0050 of JP2008-260927A and paragraph 0040 of JP2015-68893A can be used, and the above contents are incorporated in the present specification. It is.
　重合性化合物は、例えば、モノマー、プレポリマー、オリゴマー、及び、これらの混合物、並びに、これらの多量体等の化学的形態のいずれであってもよい。
　重合性化合物は、３～１５官能の（メタ）アクリレート化合物であることが好ましく、３～６官能の（メタ）アクリレート化合物であることがより好ましい。 The polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof.
The polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, 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 containing one or more ethylenically unsaturated groups and having a boiling point of 100 ° C. or higher under normal pressure. For example, compounds described in JP-A-2013-29760, paragraph 0227, and JP-A-2008-292970, paragraphs 0254 to 0257 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。 Polymerizable compounds include dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product, manufactured by Nippon Kayaku), di Pentaerythritol penta (meth) acrylate (commercially available product is KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available products are KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., A-DPH- 12E, manufactured by Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acryloyl groups are mediated by an ethylene glycol residue or a propylene glycol residue (for example, SR454, SR499 commercially available from Sartomer) are preferable. . These oligomer types can also be used. Further, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can also be used.
Preferred embodiments of the polymerizable compound are 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、東亞合成社製の、アロニックスＴＯ－２３４９、Ｍ－３０５、Ｍ－５１０、及び、Ｍ－５２０等が挙げられる。 The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. As the polymerizable compound containing an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polymerizable compound having a group is more preferable, and in this ester, the aliphatic polyhydroxy compound is more preferably pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.
　酸基を含有する重合性化合物の酸価としては、０．１～４０ｍｇＫＯＨ／ｇが好ましく、５～３０ｍｇＫＯＨ／ｇがより好ましい。重合性化合物の酸価が０．１ｍｇＫＯＨ／ｇ以上であれば、現像溶解特性が良好であり、４０ｍｇＫＯＨ／ｇ以下であれば、製造及び／又は取扱い上、有利である。更には、光重合性能が良好で、硬化性に優れる。 The acid value of the polymerizable compound containing an acid group is preferably from 0.1 to 40 mgKOH / g, more preferably from 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development dissolution properties are good, and when it is 40 mgKOH / g or less, it is advantageous in production and / or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.
　重合性化合物は、カプロラクトン構造を含有する化合物も好ましい態様である。
　カプロラクトン構造を含有する化合物としては、分子内にカプロラクトン構造を含有する限り特に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。中でも下記式（Ｚ－１）で表されるカプロラクトン構造を含有する化合物が好ましい。 The polymerizable compound is also preferably a compound containing a caprolactone structure.
The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipenta Ε-caprolactone-modified polyfunctional (meta ) Acrylates. Among these, a compound containing a caprolactone structure represented by the following formula (Z-1) is preferable.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　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 are groups represented by the following formula (Z-2), or 1 to 5 of the six R are represented by the following formula (Z-2) And the remainder is a group represented by the following formula (Z-3).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　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-C000004
Figure JPOXMLDOC01-appb-C000004
　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。 Polymerizable compounds containing a caprolactone structure are commercially available, for example, from Nippon Kayaku as the KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (Z-1) to (Z-3), the formula (Z -2) = the number of groups represented by 2 and R 1 is all hydrogen atoms), DPCA-30 (formula, m = 1, the number of groups represented by formula (Z-2) = 3) , Compounds in which R 1 is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (Z-2) = 6, compounds in which R 1 is all hydrogen atoms), And DPCA-120 (a compound in which m = 2 in the formula, the number of groups represented by formula (Z-2) = 6, and all R 1 are hydrogen atoms).
　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-C000005
Figure JPOXMLDOC01-appb-C000005
　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。 In formulas (Z-4) and (Z-5), each E independently represents — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) —. Y represents each independently 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 number of (meth) acryloyl groups is 3 or 4, each m 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 number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.
　式（Ｚ－４）中、ｍは、０～６の整数が好ましく、０～４の整数がより好ましい。
　また、各ｍの合計は、２～４０の整数が好ましく、２～１６の整数がより好ましく、４～８の整数が更に好ましい。
　式（Ｚ－５）中、ｎは、０～６の整数が好ましく、０～４の整数がより好ましい。
　また、各ｎの合計は、３～６０の整数が好ましく、３～２４の整数がより好ましく、６～１２の整数が更に好ましい。
　また、式（Ｚ－４）又は式（Ｚ－５）中の－（（ＣＨ２）ｙＣＨ２Ｏ）－又は－（（ＣＨ２）ｙＣＨ（ＣＨ３）Ｏ）－は、酸素原子側の末端がＸに結合する形態が好ましい。 In the formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and further preferably an integer of 4 to 8.
In the formula (Z-5), n is preferably an integer of 0 to 6, 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.
In the formula (Z-4) or the formula (Z-5), — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) — represents an oxygen atom side. A form in which the terminal of X is bonded to X is preferred.
　式（Ｚ－４）又は式（Ｚ－５）で表される化合物は１種単独で用いてもよいし、２種以上併用してもよい。特に、式（Ｚ－５）において、６個のＸ全てがアクリロイル基である形態、式（Ｚ－５）において、６個のＸ全てがアクリロイル基である化合物と、６個のＸのうち、少なくとも１個が水素原子である化合物との混合物である態様が好ましい。このような構成とすることにより、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 formula (Z-5), all six Xs are acryloyl groups, in formula (Z-5), all six Xs are acryloyl groups, and among six Xs, The aspect which is a mixture with the compound whose at least 1 is a hydrogen atom is preferable. With such a configuration, the developability can be further improved.
　また、式（Ｚ－４）又は式（Ｚ－５）で表される化合物の重合性化合物中における全含有量としては、２０質量％以上が好ましく、５０質量％以上がより好ましい。
　式（Ｚ－４）又は式（Ｚ－５）で表される化合物の中でも、ペンタエリスリトール誘導体及び／又はジペンタエリスリトール誘導体がより好ましい。 Further, the total content of the compound represented by the formula (Z-4) or the formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
Among the compounds represented by 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。 The polymerizable compound may contain a cardo skeleton.
As the polymerizable compound containing a cardo skeleton, a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferable.
Examples of the polymerizable compound containing a cardo skeleton include, but are not limited to, oncoat EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).
　得られる硬化膜の引置き欠陥抑制性がより優れる点から、重合性化合物は、二重結合当量（エチレン性不飽和基の含有量。より具体的には、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）が７．０ｍｍｏｌ／ｇ以上であることが好ましく、１１．０ｍｍｏｌ／ｇ以上であることがより好ましい。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、上記範囲内にあることが好ましい。 The polymerizable compound has a double bond equivalent (content of ethylenically unsaturated group. More specifically, ethylenic unsaturation in the polymerizable compound from the point that the retention defect suppression property of the obtained cured film is more excellent. The value obtained by dividing the number of groups by the molecular weight (g / mol) of the polymerizable compound is intended to be 7.0 mmol / g or more, and more preferably 11.0 mmol / g or more. The upper limit is not particularly limited, but is generally 20.0 mmol / g or less.
In addition, when the curable composition contains a plurality of types of polymerizable compounds and the double bond equivalents are not the same, the mass ratio of each polymerizable compound in the total polymerizable compound and each polymerizable compound It is preferable that the sum of the products of the compound and the double bond equivalent is within the above range.
　本明細書において、二重結合当量のことを「Ｃ＝Ｃ価」という場合がある。
　硬化性組成物が複数種類の重合性化合物を含有しており、かつ、各重合性化合物のＣ＝Ｃ価が明らかである場合、各重合性化合物の配合比から、硬化性組成物が含有する重合性化合物全質量としてのＣ＝Ｃ価を計算して求めてもよい。
　硬化性組成物が含有する重合性化合物のＣ＝Ｃ価（エチレン性不飽和基の含有量）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、例えば、以下の方法により測定できる。
　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、液体クロマトグラフィー法で重合性化合物を分離し、ＮＭＲ（ｎｕｃｌｅａｒ　ｍａｇｎｅｔｉｃ　ｒｅｓｏｎａｎｃｅ）法、及び、ＧＰＣ法等を用いた解析により、重合性化合物の構造を特定し、Ｃ＝Ｃ価を求める。Ｃ＝Ｃ価（エチレン性不飽和基の含有量）は一分子に含まれる重合性基の個数を分子量で除した値として算出する。 In this specification, the double bond equivalent may be referred to as “C═C value”.
When the curable composition contains a plurality of types of polymerizable compounds and the C = C value of each polymerizable compound is clear, the curable composition contains from the blending ratio of each polymerizable compound. You may obtain | require by calculating C = C value | valence as a polymeric compound total mass.
When the ethylenically unsaturated group is a (meth) acryloyl group, the C = C value (content of ethylenically unsaturated group) of the polymerizable compound contained in the curable composition can be measured, for example, by the following method. .
First, a solid component (black pigment or the like) in the curable composition is precipitated by a centrifugal separation method, and the remaining liquid component is collected. Furthermore, the polymerizable compound is separated from the obtained liquid component by a liquid chromatography method, and the structure of the polymerizable compound is specified by analysis using an NMR (nuclear magnetic resonance) method, a GPC method, or the like. = Calculate C value. C = C value (content of ethylenically unsaturated groups) is calculated as a value obtained by dividing the number of polymerizable groups contained in one molecule by the molecular weight.
＜樹脂Ａ＞
　本発明の硬化性組成物は、樹脂Ａを含有する。
　樹脂Ａは、「（要件１）酸価が１２０～３５０ｍｇＫＯＨ／ｇであること」、及び、「（要件２）重量平均分子量が３０００～７５００であること」のいずれか一方の要件を満たす樹脂である。
　樹脂Ａが要件１及び要件２のいずれか一方を満たすため、樹脂Ａを含有する本発明の硬化性組成物は、現像性が良好で、線幅安定性に優れる硬化膜を得ることができる。
　なお、樹脂Ａは要件１と要件２との、一方のみを満たす樹脂であってもよいし、両方を同時に満たす樹脂であってもよい。中でも、要件１と要件２とのうちの一方のみを満たし、他の一方の要件は満たさない樹脂であることが好ましい。 <Resin A>
The curable composition of the present invention contains resin A.
Resin A is a resin that satisfies any one of the requirements ((Requirement 1) that the acid value is 120 to 350 mgKOH / g) and ((Requirement 2) that the weight average molecular weight is 3000 to 7500). is there.
Since the resin A satisfies one of the requirements 1 and 2, the curable composition of the present invention containing the resin A can obtain a cured film having good developability and excellent line width stability.
The resin A may be a resin that satisfies only one of the requirements 1 and 2, or a resin that satisfies both of them simultaneously. Among these, a resin that satisfies only one of the requirements 1 and 2 and does not satisfy the other requirement is preferable.
　樹脂Ａ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、及び、オキセタニル基等）等が挙げられるが、これらに制限されない。
　中でも、ラジカル反応で重合制御が可能な点で、硬化性基としては、エチレン性不飽和基が好ましい。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。 Resin A may contain a curable group.
Examples of the curable group include an ethylenically unsaturated group (for example, (meth) acryloyl group, vinyl group, and styryl group), and a cyclic ether group (for example, epoxy group, oxetanyl group, etc.) However, it is not limited to these.
Among these, an ethylenically unsaturated group is preferable as the curable group in that polymerization can be controlled by radical reaction. The ethylenically unsaturated group is more preferably a (meth) acryloyl group.
　樹脂Ａは、要件１と要件２とのいずれかを満たす樹脂であれば特に制限はないが、（メタ）アクリル系単量体由来の繰り返し単位を含有することが好ましい。樹脂Ａの（メタ）アクリル系単量体由来の繰り返し単位の含有量は、全繰り返し単位に対して、１０モル％以上が好ましく、５０モル％以上がより好ましく、７５モル％以上が更に好ましく、９０モル％超が特に好ましい。 Resin A is not particularly limited as long as it satisfies either requirement 1 or requirement 2, but preferably contains a repeating unit derived from a (meth) acrylic monomer. The content of the repeating unit derived from the (meth) acrylic monomer of the resin A is preferably 10 mol% or more, more preferably 50 mol% or more, still more preferably 75 mol% or more, based on all repeating units. More than 90 mol% is particularly preferred.
　上記、（メタ）アクリル系単量体由来の繰り返し単位としては、例えば、下記一般式（ＡＡ）で表される繰り返し単位が好ましい。 As the above repeating unit derived from the (meth) acrylic monomer, for example, a repeating unit represented by the following general formula (AA) is preferable.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　一般式（ＡＡ）中、ＲＭは水素原子又はメチル基を表す。
　Ｌは、単結合又は２価の連結基を表す。
　上記２価の連結基としては、例えば、置換基を有していてもよい炭化水素基（直鎖状でも、分岐鎖状でもよく、環状構造を有していてもよい。炭素数は１～５が好ましい。置換基としては水酸基が好ましい）が挙げられる。中でも、炭素数１のアルキレン基が好ましい。
　Ｘは、水素原子又は置換基を表す。
　上記置換基としては、芳香環基（好ましくはフェニル基）、アルキル基（好ましくは炭素数１～３）、（メタ）アクリロイル基、（メタ）アクリロイルオキシ基、水酸基、及び、カルボキシ基等が挙げられる。中でも、Ｘは、水素原子又はフェニル基が好ましい。 In General Formula (AA), R M represents a hydrogen atom or a methyl group.
L represents a single bond or a divalent linking group.
Examples of the divalent linking group include a hydrocarbon group which may have a substituent (which may be linear or branched, and may have a cyclic structure. And the substituent is preferably a hydroxyl group. Among these, an alkylene group having 1 carbon atom is preferable.
X represents a hydrogen atom or a substituent.
Examples of the substituent include an aromatic ring group (preferably a phenyl group), an alkyl group (preferably having a carbon number of 1 to 3), a (meth) acryloyl group, a (meth) acryloyloxy group, a hydroxyl group, and a carboxy group. It is done. Among these, X is preferably a hydrogen atom or a phenyl group.
　樹脂Ａが含有する（メタ）アクリル系単量体由来の繰り返し単位（好ましくは一般式（ＡＡ）で表される繰り返し単位）は、１種のみでも、２種以上でもよく、２種以上であることが好ましい。
　２種以上である場合、少なくとも１種は、（メタ）アクリル酸由来の繰り返し単位であることが好ましい。（メタ）アクリル酸由来の繰り返し単位以外の繰り返し単位としては、例えば、ベンジル（メタ）アクリレート由来の繰り返し単位が好ましい。 The repeating unit derived from the (meth) acrylic monomer contained in the resin A (preferably the repeating unit represented by the general formula (AA)) may be one kind, two kinds or more, and two kinds or more. It is preferable.
When there are two or more, at least one is preferably a repeating unit derived from (meth) acrylic acid. As the repeating unit other than the repeating unit derived from (meth) acrylic acid, for example, a repeating unit derived from benzyl (meth) acrylate is preferable.
　樹脂Ａは、上記ベンジル（メタ）アクリレート由来の繰り返し単位、及び、上記（メタ）アクリル酸由来の繰り返し単位の両方を含有することが好ましく、上記ベンジル（メタ）アクリレート由来の繰り返し単位、及び、上記（メタ）アクリル酸由来の繰り返し単位の組み合わせのみからなることがより好ましい。
　言い換えると、樹脂Ａは、ベンジル（メタ）アクリレート及び（メタ）アクリル酸の共重合体であることが好ましい。 Resin A preferably contains both the repeating unit derived from the benzyl (meth) acrylate and the repeating unit derived from the (meth) acrylic acid, the repeating unit derived from the benzyl (meth) acrylate, and the above More preferably, it consists only of a combination of repeating units derived from (meth) acrylic acid.
In other words, the resin A is preferably a copolymer of benzyl (meth) acrylate and (meth) acrylic acid.
　樹脂Ａの主鎖に含有されることが想定されるその他の繰り返し単位としては、例えば、スチレン系単量体（ヒドロキシスチレン等）由来の繰り返し単位、及び、エーテルダイマー由来の繰り返し単位が挙げられる。
　上記エーテルダイマーは、例えば、下記一般式（ＥＤ１）で表される化合物、及び、下記一般式（ＥＤ２）で表される化合物が挙げられる。 Examples of other repeating units that are assumed to be contained in the main chain of the resin A include a repeating unit derived from a styrene monomer (such as hydroxystyrene) and a repeating unit derived from an ether dimer.
Examples of the ether dimer include a compound represented by the following general formula (ED1) and a compound represented by the following general formula (ED2).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　一般式（ＥＤ１）中、Ｒ１及びＲ２は、それぞれ独立に、水素原子又は炭素数１～２５の炭化水素基を表す。 In general formula (ED1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　一般式（ＥＤ２）中、Ｒは、水素原子又は炭素数１～３０の有機基を表す。一般式（ＥＤ２）の具体例としては、特開２０１０－１６８５３９号公報の記載を参酌できる。 In general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), the description in JP 2010-168539 A can be referred to.
　エーテルダイマーの具体例としては、例えば、特開２０１３－２９７６０号公報の段落０３１７を参酌することができ、この内容は本明細書に組み込まれる。エーテルダイマーは、１種のみであってもよいし、２種以上であってもよい。 As a specific example of the ether dimer, for example, paragraph 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used.
（要件１を満たす樹脂Ａ）
　酸価が１２０～３５０ｍｇＫＯＨ／ｇである樹脂Ａ（要件１を満たす樹脂Ａ）は、酸価が適切な範囲に調製されている。
　得られる硬化膜の線幅安定性及びアンダーカット抑制性がより優れる点から、要件１を満たす樹脂の酸価は、１７０～３００ｍｇＫＯＨ／ｇが好ましく、２００～２７０ｍｇＫＯＨ／ｇがより好ましい。
　要件１を満たす樹脂Ａは、その重量平均分子量が、７５００超であることが好ましく、８０００～３００００であることがより好ましく、１００００～１５０００であることが更に好ましい。 (Resin A that satisfies Requirement 1)
Resin A (resin A satisfying requirement 1) having an acid value of 120 to 350 mgKOH / g is prepared in an appropriate range.
The acid value of the resin satisfying the requirement 1 is preferably 170 to 300 mgKOH / g, more preferably 200 to 270 mgKOH / g, from the viewpoint of more excellent line width stability and undercut suppression of the obtained cured film.
The resin A satisfying the requirement 1 has a weight average molecular weight of preferably more than 7500, more preferably 8000 to 30000, and further preferably 10000 to 15000.
（要件２を満たす樹脂Ａ）
　重量平均分子量が３０００～７５００である樹脂Ａ（要件２を満たす樹脂Ａ）は、分子量が適切な範囲に調製されている。
　硬化膜の線幅安定性、アンダーカット抑制性、及び、残渣抑制性がより優れる点から、要件Ａを満たす樹脂の重量平均分子量は、３０００～６５００が好ましく、３０００～５０００がより好ましく、４０００～５０００が更に好ましい。
　要件２を満たす樹脂Ａの酸価としては、１２０ｍｇＫＯＨ／ｇ未満が好ましく、３０～１１０ｍｇＫＯＨ／ｇがより好ましく、６０～１００ｍｇＫＯＨ／ｇがより好ましい。 (Resin A that satisfies Requirement 2)
The resin A having a weight average molecular weight of 3000 to 7500 (resin A satisfying the requirement 2) is prepared in an appropriate molecular weight range.
The weight average molecular weight of the resin satisfying the requirement A is preferably from 3000 to 6500, more preferably from 3000 to 5000, more preferably from 4000 to 2000, because the cured film has more excellent line width stability, undercut suppression and residue suppression. 5000 is more preferable.
The acid value of the resin A satisfying the requirement 2 is preferably less than 120 mgKOH / g, more preferably 30 to 110 mgKOH / g, and more preferably 60 to 100 mgKOH / g.
　樹脂Ａは１種を単独で用いても、２種以上を併用してもよい。例えば、硬化性組成物は、要件１を満たす樹脂Ａと要件２を満たす樹脂Ａとの両方を含有していてもよい。
　硬化性組成物中における樹脂Ａ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、５～１５質量％がより好ましい。２種以上の樹脂Ａを使用する場合には、合計含有量が上記範囲内であることが好ましい。 Resin A may be used individually by 1 type, or may use 2 or more types together. For example, the curable composition may contain both the resin A satisfying the requirement 1 and the resin A satisfying the requirement 2.
The content of the resin A in the curable composition is not particularly limited, but is preferably 1 to 30% by mass and more preferably 5 to 15% by mass with respect to the total solid content of the curable composition. When using 2 or more types of resin A, it is preferable that total content is in the said range.
　硬化性組成物中の樹脂Ａの有無及びその含有量は、以下に示す方法で測定できる。
　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。
　ここで、重量平均分子量が３０００～７５００である樹脂が検出された場合、その樹脂を、要件２を満たす樹脂Ａとして、硬化性組成物の全固形分に対する含有量を求める。
　また、重量平均分子量が３０００～７５００から外れる樹脂については、通常の方法（ＪＩＳＫ５６０１－２－１又はＪＩＳＫ００７０等）で酸価を測定して、酸価が１２０～３５０ｍｇＫＯＨ／ｇであるかを確かめる。酸価が１２０～３５０ｍｇＫＯＨ／ｇである樹脂が存在した場合、その樹脂を、要件１を満たす樹脂Ａ（かつ、要件２を満たさない樹脂Ａ）として、硬化性組成物の全固形分に対する含有量を求める。
　このようにして得られた、要件２を満たす樹脂Ａと、要件１を満たす樹脂Ａ（かつ、要件２を満たさない樹脂Ａ）との合計含有量から、硬化性組成物の全固形分に対する樹脂Ａの含有量を求めることができる。
　また、硬化性組成物中の樹脂Ａの含有量は、硬化性組成物の配合及び、使用する原料の酸価及び重量平均分子量が既知である場合は計算で求めてもよい。 The presence or absence of the resin A in the curable composition and the content thereof can be measured by the following method.
First, a solid component (black pigment or the like) in the curable composition is precipitated by a centrifugal separation method, and the remaining liquid component is collected. Further, from the obtained liquid component, a component having a weight average molecular weight of more than 2000 is separated by GPC method, and this is used as a resin to be measured.
Here, when a resin having a weight average molecular weight of 3000 to 7500 is detected, the resin is defined as resin A satisfying requirement 2, and the content relative to the total solid content of the curable composition is obtained.
For resins having a weight average molecular weight outside of 3000 to 7500, the acid value is measured by an ordinary method (such as JISK5601-2-1 or JISK0070) to confirm whether the acid value is 120 to 350 mgKOH / g. When a resin having an acid value of 120 to 350 mgKOH / g is present, the content of the resin as resin A satisfying requirement 1 (and resin A not satisfying requirement 2) with respect to the total solid content of the curable composition Ask for.
From the total content of the resin A satisfying the requirement 2 and the resin A satisfying the requirement 1 (and the resin A not satisfying the requirement 2) thus obtained, the resin relative to the total solid content of the curable composition The content of A can be determined.
Further, the content of the resin A in the curable composition may be obtained by calculation when the blending of the curable composition and the acid value and the weight average molecular weight of the raw material to be used are known.
＜樹脂Ｂ＞
　硬化性組成物は、上述の樹脂Ａ以外の樹脂を含有してもよい。
　樹脂Ａ以外の樹脂としては、反射率が低減された硬化膜を得られる点から、例えば樹脂Ｂが挙げられる。
　樹脂Ｂは、樹脂Ａとは異なる樹脂であって、オキシアルキレン基及びオキシアルキレンカルボニル基からなる群から選択される１種以上の基を有する樹脂である。
　樹脂Ｂは、いわゆる顔料分散剤として作用する樹脂であることが好ましい。
　硬化性組成物中における樹脂Ｂ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。
　樹脂Ｂ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Ｂを併用する場合には、合計含有量が上記範囲内であることが好ましい。 <Resin B>
The curable composition may contain a resin other than the resin A described above.
Examples of the resin other than the resin A include a resin B from the viewpoint of obtaining a cured film having a reduced reflectance.
The resin B is a resin different from the resin A, and is a resin having one or more groups selected from the group consisting of oxyalkylene groups and oxyalkylenecarbonyl groups.
The resin B is preferably a resin that acts as a so-called pigment dispersant.
The content of the resin B in the curable composition is not particularly limited, but is preferably 2 to 40% by mass and more preferably 5 to 30% by mass with respect to the total solid content of the curable composition.
Resin B may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of resin B together, it is preferable that total content is in the said range.
　樹脂Ｂ中のオキシアルキレン基及びオキシアルキレンカルボニル基からなる群から選択される１種以上の基が存在する形態は特に制限されない。
　オキシアルキレン基及びオキシアルキレンカルボニル基中のアルキレン部分は、置換基を有していてもよく、直鎖状でも分岐鎖状でもよく、環状構造を有していてもよい。中でも、上記アルキレン部分は、無置換であることが好ましい。
　また、オキシアルキレン基におけるアルキレン部分の炭素数は、１～１０が好ましく、２～３がより好ましい。また、オキシアルキレンカルボニル基におけるアルキレン部分の炭素数は、２～８が好ましく、４～６がより好ましい。
　一分子中に、オキシアルキレン基及び／又はオキシアルキレンカルボニル基が、複数存在する場合、複数のオキシアルキレン基及び／又はオキシアルキレンカルボニル基は、それぞれ同一でも異なっていてもよい。
　また、樹脂Ｂは、オキシアルキレン基が連続して複数（好ましくは３個以上、より好ましくは１０個以上）結合したポリオキシアルキレン構造、又は、オキシアルキレンカルボニル基が連続して複数（好ましくは３個以上、より好ましくは１０個以上）結合したポリオキシアルキレンカルボニル構造を有していることが好ましい。 The form in which at least one group selected from the group consisting of an oxyalkylene group and an oxyalkylenecarbonyl group in resin B is present is not particularly limited.
The alkylene moiety in the oxyalkylene group and oxyalkylenecarbonyl group may have a substituent, may be linear or branched, and may have a cyclic structure. Especially, it is preferable that the said alkylene part is unsubstituted.
In addition, the number of carbon atoms of the alkylene portion in the oxyalkylene group is preferably 1 to 10, and more preferably 2 to 3. Further, the number of carbon atoms of the alkylene moiety in the oxyalkylenecarbonyl group is preferably 2 to 8, and more preferably 4 to 6.
When a plurality of oxyalkylene groups and / or oxyalkylenecarbonyl groups are present in one molecule, the plurality of oxyalkylene groups and / or oxyalkylenecarbonyl groups may be the same or different from each other.
The resin B has a polyoxyalkylene structure in which a plurality of oxyalkylene groups are continuously bonded (preferably 3 or more, more preferably 10 or more) or a plurality of oxyalkylenecarbonyl groups (preferably 3). Or more, more preferably 10 or more) preferably having a bonded polyoxyalkylenecarbonyl structure.
　樹脂Ｂは、高分子化合物〔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、及び、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、並びに、顔料誘導体等であってもよい。
　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。 Resin B is a polymer compound [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer Combined and naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, pigment derivative, and the like.
The polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
・高分子化合物
　高分子化合物は、上述したような顔料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。 -High molecular compound A high molecular compound adsorb | sucks to the surface of to-be-dispersed objects, such as the above-mentioned pigment, and acts so that re-aggregation of a to-be-dispersed body may be prevented. Therefore, a terminal-modified polymer, a graft-type (containing polymer chain) polymer, or a block-type polymer containing an anchor site to the pigment surface is preferable.
　上記高分子化合物は硬化性基を含有してもよい。
　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。
　中でも、ラジカル反応で重合制御が可能な点で、硬化性基としては、エチレン性不飽和基が好ましい。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 an ethylenically unsaturated group (for example, (meth) acryloyl group, vinyl group, styryl group, etc.), a cyclic ether group (for example, epoxy group, oxetanyl group, etc.) and the like. However, it is not limited to these.
Among these, an ethylenically unsaturated group is preferable as the curable group in that polymerization can be controlled by 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、主鎖にオキシアルキレン基（好ましくはポリオキシアルキレン構造）及び／又はオキシアルキレンカルボニル基（好ましくはポリオキシアルキレンカルボニル構造）を含有していてもよい。また、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等において、上記グラフト鎖がオキシアルキレン基（好ましくはポリオキシアルキレン構造）及び／又はオキシアルキレンカルボニル基（好ましくはポリオキシアルキレンカルボニル構造）を含有していてもよい。
　上記樹脂としては、上記グラフト鎖がオキシアルキレンカルボニル基を含有することがより好ましい。 The resin containing a curable group may contain an oxyalkylene group (preferably a polyoxyalkylene structure) and / or an oxyalkylene carbonyl group (preferably a polyoxyalkylene carbonyl structure) in the main chain. As will be described later, when the resin contains a structural unit containing a graft chain, the graft chain is an oxyalkylene group (preferably a polyoxyalkylene structure) and / or an oxyalkylenecarbonyl group (preferably a polyoxyalkylene structure). (Oxyalkylenecarbonyl structure) may be contained.
As said resin, it is more preferable that the said graft chain contains an oxyalkylene carbonyl group.
　高分子化合物は、グラフト鎖を含有する構造単位を含有することが好ましい。なお、本明細書において、「構造単位」とは「繰り返し単位」と同義である。
　このようなグラフト鎖を含有する構造単位を含有する高分子化合物は、グラフト鎖によって溶剤との親和性を有するために、顔料等の分散性、及び、経時後の分散安定性（経時安定性）に優れるものである。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であることが好ましく、水素原子を除いた原子数が５０～２０００であることがより好ましく、水素原子を除いた原子数が６０～５００であることが更に好ましい。
　ここで、グラフト鎖とは、共重合体の主鎖の根元（主鎖から枝分かれしている基において主鎖に結合する原子）から、主鎖から枝分かれしている基の末端までを示す。 The polymer compound preferably contains a structural unit containing a graft chain. In the present specification, “structural unit” is synonymous with “repeating unit”.
Since the polymer compound containing a structural unit containing such a graft chain has an affinity for a solvent by the graft chain, the dispersibility of pigments, etc., and the dispersion stability after time (stability over time) It is excellent. Further, due to the presence of the graft chain, the polymer compound containing the structural unit containing the graft chain has an affinity with a polymerizable compound or other resin that can be used in combination. As a result, it becomes difficult to produce a residue by alkali development.
When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility of the pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorptive power to the pigment or the like is lowered, and the dispersibility of the pigment or the like tends to be lowered. Therefore, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and the number of 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 a 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ことが好ましく、このようなポリマー構造としては、例えば、ポリ（メタ）アクリレート構造（例えば、ポリ（メタ）アクリル構造）、ポリエステル構造（好ましくは、ポリオキシアルキレンカルボニル構造）、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（好ましくは、ポリオキシアルキレン構造）等が挙げられる。
　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、ポリオキシアルキレンカルボニル構造、ポリオキシアルキレン構造、及び、ポリ（メタ）アクリレート構造からなる群から選ばれた少なくとも１種を含有するグラフト鎖であることが好ましく、ポリオキシアルキレンカルボニル構造及びポリオキシアルキレン構造の少なくともいずれかを含有するグラフト鎖であることがより好ましい。 The graft chain preferably contains a polymer structure. Examples of such a polymer structure include a poly (meth) acrylate structure (for example, poly (meth) acrylic structure), a polyester structure (preferably, polyoxyalkylenecarbonyl). Structure), polyurethane structure, polyurea structure, polyamide structure, and polyether structure (preferably, polyoxyalkylene structure).
In order to improve the interaction between the graft chain and the solvent, thereby increasing the dispersibility of the pigment and the like, the graft chain is composed of a polyoxyalkylene carbonyl structure, a polyoxyalkylene structure, and a poly (meth) acrylate structure. A graft chain containing at least one selected from the group is preferred, and a graft chain containing at least one of a polyoxyalkylenecarbonyl structure and a polyoxyalkylene structure is more preferred.
　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 bound to the main chain of the copolymer to constitute the graft chain) is not particularly limited, but includes a reactive double bond group. The containing macromonomer can be used conveniently.
　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、東亞合成社製）、ＡＡ－１０（商品名、東亞合成社製）、ＡＢ－６（商品名、東亞合成社製）、ＡＳ－６（商品名、東亞合成社製）、ＡＮ－６（商品名、東亞合成社製）、ＡＷ－６（商品名、東亞合成社製）、ＡＡ－７１４（商品名、東亞合成社製）、ＡＹ－７０７（商品名、東亞合成社製）、ＡＹ－７１４（商品名、東亞合成社製）、ＡＫ－５（商品名、東亞合成社製）、ＡＫ－３０（商品名、東亞合成社製）、ＡＫ－３２（商品名、東亞合成社製）、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。この中でも、ＡＡ－６（商品名、東亞合成社製）、ＡＡ－１０（商品名、東亞合成社製）、ＡＢ－６（商品名、東亞合成社製）、ＡＳ－６（商品名、東亞合成社製）、ＡＮ－６（商品名、東亞合成社製）、又は、ブレンマーＰＭＥ－４０００（商品名、日油社製）が好ましい。 Corresponding to the structural unit containing a graft chain contained in the polymer compound, commercially available macromonomers suitably used for the synthesis of the polymer compound include AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10. (Trade name, manufactured by Toagosei Co., Ltd.), AB-6 (trade name, manufactured by Toagosei Co., Ltd.), AS-6 (trade name, manufactured by Toagosei Co., Ltd.), AN-6 (trade name, manufactured by Toagosei Co., Ltd.), AW -6 (trade name, manufactured by Toagosei), AA-714 (trade name, manufactured by Toagosei), AY-707 (trade name, manufactured by Toagosei), AY-714 (trade name, manufactured by Toagosei) AK-5 (trade name, manufactured by Toagosei Co., Ltd.), AK-30 (trade name, manufactured by Toagosei Co., Ltd.), AK-32 (trade name, manufactured by Toagosei Co., Ltd.), Blemmer PP-100 (trade name, NOF Corporation) Blemmer PP-500 (trade name, manufactured by NOF Corporation), Blemmer 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). Among these, AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (trade name, manufactured by Toagosei Co., Ltd.), AB-6 (trade name, manufactured by Toagosei Co., Ltd.), AS-6 (trade name, manufactured by Toagosei Co., Ltd.) Synthetic Co., Ltd.), AN-6 (trade name, manufactured by Toagosei Co., Ltd.), or Bremer PME-4000 (trade name, manufactured by NOF Corporation) is preferable.
　上記樹脂Ｂは、ポリアクリル酸メチル、ポリメタクリル酸メチル、及び、環状又は鎖状のポリエステルからなる群より選択される少なくとも１種の構造を含有することが好ましく、ポリアクリル酸メチル、ポリメタクリル酸メチル、及び、鎖状のポリエステルからなる群より選択される少なくとも１種の構造を含有することがより好ましく、ポリアクリル酸メチル構造、ポリメタクリル酸メチル構造、ポリカプロラクトン構造、及び、ポリバレロラクトン構造からなる群より選択される少なくとも１種の構造を含有することが更に好ましい。樹脂Ｂは、樹脂Ａ以外の樹脂であって、オキシアルキレン基及びオキシアルキレンカルボニル基からなる群から選択される１種以上の基を有する樹脂でさえあれば、一の樹脂Ｂ中に上記構造を単独で含有する樹脂Ｂであってもよいし、一の樹脂Ｂ中にこれらの構造を複数含有する樹脂Ｂ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。これらは、ポリオキシアルキレンカルボニル構造の一態様に当たる。
　樹脂Ｂが含有する、ポリカプロラクトン構造を構成する繰り返し単位の具体例としては、下記式（１）及び下記式（２）におけるｊ及びｋが５である繰り返し単位が挙げられる。また、樹脂Ｂが含有する、ポリバレロラクトン構造を構成する繰り返し単位の具体例としては、下記式（１）及び下記式（２）におけるｊ及びｋが４である繰り返し単位が挙げられる。
　樹脂Ｂが含有する、ポリアクリル酸メチル構造を構成する繰り返し単位の具体例としては、下記式（４）におけるＸ５が水素原子であり、Ｒ４がメチル基である繰り返し単位が挙げられる。また、樹脂Ｂが含有する、ポリメタクリル酸メチル構造を構成する繰り返し単位の具体例としては、下記式（４）におけるＸ５がメチル基であり、Ｒ４がメチル基である繰り返し単位が挙げられる。 The resin B preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester, and includes polymethyl acrylate and polymethacrylic acid. More preferably, it contains at least one structure selected from the group consisting of methyl and chain polyester, and includes 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 resin B is a resin other than the resin A and has the above structure in one resin B as long as it has at least one group selected from the group consisting of an oxyalkylene group and an oxyalkylenecarbonyl group. The resin B contained alone may be used, or the resin B containing a plurality of these structures in one resin B may be used.
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. These correspond to one embodiment of the polyoxyalkylene carbonyl structure.
Specific examples of the repeating unit constituting the polycaprolactone structure contained in the resin B include a repeating unit in which j and k in the following formula (1) and the following formula (2) are 5. Moreover, as a specific example of the repeating unit which comprises the polyvalerolactone structure which resin B contains, the repeating unit whose j and k in following formula (1) and following formula (2) are 4 is mentioned.
Specific examples of the repeating unit constituting the polymethyl acrylate structure contained in the resin B include a repeating unit in which X 5 in the following formula (4) is a hydrogen atom and R 4 is a methyl group. Further, the resin B contains, as specific examples of the repeating units constituting the polymethyl methacrylate structure is X 5 is a methyl group in the formula (4) include the repeating units R 4 is a methyl group .
・グラフト鎖を含有する構造単位
　高分子化合物は、グラフト鎖を含有する構造単位として、下記式（１）～式（４）のいずれかで表される構造単位を含有することが好ましく、下記式（１Ａ）、下記式（２Ａ）、下記式（３Ａ）、及び、下記式（３Ｂ）、及び、下記（４）のいずれかで表される構造単位を含有することがより好ましい。
　また、高分子化合物は、下記式（１）～式（３）のいずれかで表される構造単位のうちの少なくとも１種を含有することが好ましい。
　なお、式（１）で表される構造単位、及び、式（２）で表される構造単位は、オキシアルキレンカルボニル基を含有する構造単位である。式（３）で表される構造単位は、オキシアルキレン基を含有する構造単位である。 Structural unit containing a graft chain The polymer compound preferably contains a structural unit represented by any of the following formulas (1) to (4) as a structural unit containing a graft chain. It is more preferable to contain the structural unit represented by either (1A), the following formula (2A), the following formula (3A), the following formula (3B), or the following (4).
The polymer compound preferably contains at least one of structural units represented by any of the following formulas (1) to (3).
In addition, the structural unit represented by Formula (1) and the structural unit represented by Formula (2) are structural units containing an oxyalkylene carbonyl group. The structural unit represented by Formula (3) is a structural unit containing an oxyalkylene group.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　式（１）～（４）において、Ｗ１、Ｗ２、Ｗ３、及び、Ｗ４はそれぞれ独立に酸素原子又はＮＨを表す。Ｗ１、Ｗ２、Ｗ３、及び、Ｗ４は酸素原子であることが好ましい。
　式（１）～（４）において、Ｘ１、Ｘ２、Ｘ３、Ｘ４、及び、Ｘ５は、それぞれ独立に、水素原子又は１価の有機基を表す。Ｘ１、Ｘ２、Ｘ３、Ｘ４、及び、Ｘ５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ことが好ましく、それぞれ独立に、水素原子又はメチル基であることがより好ましく、メチル基が更に好ましい。 In the formulas (1) to (4), W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH. W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
In the formulas (1) to (4), X 1 , X 2 , X 3 , X 4 and X 5 each independently represent a hydrogen atom or a monovalent organic group. X 1 , X 2 , X 3 , X 4 , and X 5 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (the number of carbon atoms) from the viewpoint of restrictions on synthesis. It is preferably each independently 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）であることがより好ましい。 In formulas (1) to (4), Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure. Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following linking groups (Y-1) to (Y-21). It is done. In the structures shown below, A and B each represent a binding site in formulas (1) to (4). Of the structures shown below, (Y-2) or (Y-13) is more preferable because of the ease of synthesis.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　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。これらの中でも、Ｚ１、Ｚ２、Ｚ３、及び、Ｚ４で表される有機基としては、特に分散性向上の観点から、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、その中でも、特にそれぞれ独立に炭素数５～２４の分岐鎖状アルキル基、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. The structure of the organic group is not particularly limited, and 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 containing a steric repulsion effect is particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 carbon atoms. More preferably, an alkyl group or an alkoxy group having ˜24 is preferable, and among them, a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable. 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、樹脂Ｂ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. Further, when the resin B contains a polycaprolactone structure and a polyvalerolactone structure, the sum of the number of repetitions of the polycaprolactone structure and the number of repetitions of the polyvalerolactone is preferably an integer of 10 or more, An integer is more preferable.
　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 the formula (3), R 3 represents a branched or straight chain 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, a plurality of R 3 may be the same or different from each other.
In the formula (4), R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure. R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. 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. Preferably, a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is still more preferable. In the formula (4), when q is 2 to 500, a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
　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）で表される構造単位を含有していてもよく、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有していてもよく、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 structural units containing graft chains that have two or more different structures. That is, in the molecule of the polymer compound, structural units represented by the formulas (1) to (4) having different structures from each other may be contained, and in the formulas (1) to (4), n, m , P, and q each represent an integer of 2 or more, in Formulas (1) and (2), j and k may contain structures different from each other in the side chain, and Formula (3) And (4), a plurality of R 3 , R 4 and X 5 present in the molecule may be the same 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ことがより好ましい。
　また、式（２）で表される構造単位としては、組成物の経時安定性及び現像性の観点から、下記式（２Ａ）で表される構造単位であることがより好ましい。 The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of temporal stability and developability of the composition.
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 viewpoint of temporal stability of a composition and developability.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　式（１Ａ）中、Ｘ１、Ｙ１、Ｚ１、及び、ｎは、式（１）におけるＸ１、Ｙ１、Ｚ１、及び、ｎと同義であり、好ましい範囲も同様である。式（２Ａ）中、Ｘ２、Ｙ２、Ｚ２、及び、ｍは、式（２）におけるＸ２、Ｙ２、Ｚ２、及び、ｍと同義であり、好ましい範囲も同様である。 Wherein (1A), X 1, Y 1, Z 1 and, n is, X 1, Y 1, Z 1 in Formula (1), and has the same meaning as n, preferred ranges are also the same. Wherein (2A), X 2, Y 2, Z 2 and, m is, X 2, Y 2, Z 2 in Formula (2), and has the same meaning as m, the preferred range is also the same.
　また、式（３）で表される構造単位としては、組成物の経時安定性及び現像性の観点から、下記式（３Ａ）又は式（３Ｂ）で表される構造単位であることがより好ましい。 The structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or formula (3B) from the viewpoint of the temporal stability and developability of the composition. .
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　式（３Ａ）又は（３Ｂ）中、Ｘ３、Ｙ３、Ｚ３、及び、ｐは、式（３）におけるＸ３、Ｙ３、Ｚ３、及び、ｐと同義であり、好ましい範囲も同様である。 Wherein (3A) or (3B), X 3, Y 3, Z 3 and, p is, X 3, Y 3, Z 3 in Formula (3), and has the same meaning as p, preferred ranges are also the same It is.
　高分子化合物は、グラフト鎖を含有する構造単位として、式（１Ａ）で表される構造単位を含有することがより好ましい。 More preferably, the polymer compound contains a structural unit represented by the formula (1A) as a structural unit containing a graft chain.
　高分子化合物において、グラフト鎖を含有する構造単位（例えば、上記式（１）～（４）で表される構造単位）は、質量換算で、高分子化合物の総質量に対し２～９０質量％の範囲で含まれることが好ましく、５～３０質量％の範囲で含まれることがより好ましい。
　中でも、上記式（１）～（３）で表される構造単位の合計含有量が、高分子化合物の総質量に対し２～８０質量％の範囲で含まれることが好ましく、５～２５質量％の範囲で含まれることがより好ましい。
　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, the structural unit containing a graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is 2 to 90% by mass in terms of mass with respect to the total mass of the polymer compound. Preferably, it is contained in the range of 5 to 30% by mass.
Among them, the total content of the structural units represented by the above formulas (1) to (3) is preferably included in the range of 2 to 80% by mass with respect to the total mass of the polymer compound, and 5 to 25% by mass. It is more preferable that it is included in the range.
When the structural unit containing a graft chain is included within this range, the dispersibility of the pigment is high, and the developability when 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ことが好ましい。ただし、本明細書において、疎水性構造単位は、酸基（例えば、カルボン酸基、スルホン酸基、リン酸基、及び、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 Moreover, it is preferable that a high molecular compound contains the hydrophobic structural unit different from the structural unit containing a graft chain (namely, it does not correspond to the structural unit containing a graft chain). However, in this specification, a hydrophobic structural unit is a structural unit which does not have an 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）構造単位であることが好ましく、ＣｌｏｇＰ値が１．２～８の化合物に由来する構造単位であることがより好ましい。これにより、本発明の効果をより確実に発現できる。 The hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, and is a structural unit derived from a compound having a ClogP value of 1.2 to 8 It is more preferable. Thereby, the effect of this invention can be expressed more reliably.
　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 can be obtained from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In this specification, the ClogP value calculated by the program CLOGP v4.82 is used.
A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B. Taylor and C.M. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. et al. Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. et al. Leo. Calculating logPoch 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 the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
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 increases to a positive value across 0, the oil solubility increases. When the logP value increases to a negative value, the water solubility increases. There is a negative correlation with the water solubility of the organic compound. It is widely used as a parameter for estimating aqueous properties.
　高分子化合物は、疎水性構造単位として、下記式（ｉ）～（ｉｉｉ）で表される単量体に由来の構造単位から選択された１種以上の構造単位を含有することが好ましい。 The polymer compound preferably contains one or more structural units selected from structural units derived from monomers represented by the following formulas (i) to (iii) as hydrophobic structural units.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　上記式（ｉ）～（ｉｉｉ）中、Ｒ１、Ｒ２、及び、Ｒ３は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素原子、塩素原子、及び、臭素原子等）、又は、炭素数が１～６のアルキル基（例えば、メチル基、エチル基、及び、プロピル基等）を表す。
　Ｒ１、Ｒ２、及び、Ｒ３は、水素原子又は炭素数が１～３のアルキル基であることが好ましく、水素原子又はメチル基であることがより好ましい。Ｒ２及びＲ３は、水素原子であることが更に好ましい。
　Ｘは、酸素原子（－Ｏ－）又はイミノ基（－ＮＨ－）を表し、酸素原子であることが好ましい。 In the above formulas (i) to (iii), R 1 , R 2 , and R 3 are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or An alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.) is represented.
R 1 , R 2 and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R 2 and R 3 are more preferably a hydrogen atom.
X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
　Ｌは、単結合又は２価の連結基である。２価の連結基としては、２価の脂肪族基（例えば、アルキレン基、置換アルキレン基、アルケニレン基、置換アルケニレン基、アルキニレン基、置換アルキニレン基）、２価の芳香族基（例えば、アリーレン基、置換アリーレン基）、２価の複素環基、酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、イミノ基（－ＮＨ－）、置換イミノ基（－ＮＲ３１－、ここでＲ３１は脂肪族基、芳香族基又は複素環基）、カルボニル基（－ＣＯ－）、及び、これらの組み合わせ等が挙げられる。 L is a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group (for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group), divalent aromatic group (for example, arylene group) , Substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 Are 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ことが好ましい。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 aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group.
　２価の芳香族基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。また、芳香族基は置換基を有していてもよい。置換基の例は、ハロゲン原子、脂肪族基、芳香族基、及び、複素環基等が挙げられる。 The carbon number of the divalent aromatic group is preferably 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.
　２価の複素環基は、複素環として５員環又は６員環を含有することが好ましい。複素環に他の複素環、脂肪族環、又は、芳香族環が縮合していてもよい。また、複素環基は置換基を有していてもよい。置換基の例としては、ハロゲン原子、水酸基、オキソ基（＝Ｏ）、チオキソ基（＝Ｓ）、イミノ基（＝ＮＨ）、置換イミノ基（＝Ｎ－Ｒ３２、ここでＲ３２は脂肪族基、芳香族基、又は、複素環基）、脂肪族基、芳香族基、及び、複素環基が挙げられる。 The divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocyclic ring. Another heterocyclic ring, an aliphatic ring, or an aromatic ring may be condensed with the heterocyclic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R 32 , where 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価の連結基であることが好ましい。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ことがより好ましい。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有していてもよい。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の整数であることがより好ましい。 L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
　Ｚとしては、脂肪族基（例えば、アルキル基、置換アルキル基、不飽和アルキル基、及び、置換不飽和アルキル基等）、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、及び、置換アリーレン基等）、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。 Z includes an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, and a substituted unsaturated alkyl group), an aromatic group (for example, an aryl group, a substituted aryl group, an arylene group, and Substituted arylene groups, etc.), heterocyclic groups, or combinations thereof. These groups include an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR 31 —, wherein R 31 is an aliphatic group, an aromatic group Group or heterocyclic group) or a carbonyl group (—CO—) may be contained.
　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 aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -A cyclohexylphenyl group and the like are included. Examples of the bridged cyclic hydrocarbon ring include 2 such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.). Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredan, 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. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed, such as a perhydrophenalene ring, is also included.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
　芳香族基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。また、芳香族基は置換基を有していてもよい。置換基の例は、ハロゲン原子、脂肪族基、芳香族基及び複素環基が挙げられる。ただし、芳香族基は、置換基として酸基を有さない。 The carbon number of the aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.
　複素環基は、複素環として５員環又は６員環を含有することが好ましい。複素環に他の複素環、脂肪族環又は芳香族環が縮合していてもよい。また、複素環基は置換基を有していてもよい。置換基の例としては、ハロゲン原子、水酸基、オキソ基（＝Ｏ）、チオキソ基（＝Ｓ）、イミノ基（＝ＮＨ）、置換イミノ基（＝Ｎ－Ｒ３２、ここでＲ３２は脂肪族基、芳香族基又は複素環基）、脂肪族基、芳香族基、及び、複素環基が挙げられる。ただし、複素環基は、置換基として酸基を有さない。 It is preferable that a heterocyclic group contains a 5-membered ring or a 6-membered ring as a heterocyclic ring. Another heterocyclic ring, aliphatic ring or aromatic ring may be condensed with the heterocyclic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R 32 , where R 32 is aliphatic. Group, aromatic group or heterocyclic group), aliphatic group, aromatic group, and heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.
　上記式（ｉｉｉ）中、Ｒ４、Ｒ５、及びＲ６は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素原子、塩素原子、及び、臭素原子等）、炭素数が１～６のアルキル基（例えば、メチル基、エチル基、及び、プロピル基等）、Ｚ、又は、Ｌ－Ｚを表す。ここでＬ及びＺは、上記におけるものと同義である。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 are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1-6. An alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), Z, or LZ is represented. Here, L and Z are as defined above. R 4 , R 5 and R 6 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
　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 the monomer represented by the above formula (i), R 1 , R 2 , and R 3 are a hydrogen atom or a methyl group, and L contains a single bond, an alkylene group, or an oxyalkylene structure. A compound that is a divalent linking group, X is an oxygen atom or imino group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferable.
Further, as the monomer represented by the above formula (ii), R 1 is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Compounds that are groups are preferred. As the monomer represented by the above formula (iii), R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Compounds that are groups are preferred.
　式（ｉ）～（ｉｉｉ）で表される代表的な化合物の例としては、アクリル酸エステル類、メタクリル酸エステル類、及び、スチレン類等から選ばれるラジカル重合性化合物が挙げられる。
　なお、式（ｉ）～（ｉｉｉ）で表される代表的な化合物の例としては、特開２０１３－２４９４１７号公報の段落００８９～００９３に記載の化合物を参照でき、これらの内容は本明細書に組み込まれる。 Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
As examples of typical compounds represented by formulas (i) to (iii), compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are described in the present 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％の範囲で含まれることが好ましく、２０～８０％の範囲で含まれることがより好ましい。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%, more preferably in a range of 20 to 80% with respect to the total mass of the polymer compound in terms of mass. When the content is in the above range, sufficient pattern formation can be obtained.
・顔料等と相互作用を形成しうる官能基
　高分子化合物は、顔料等と相互作用を形成しうる官能基を導入できる。ここで、高分子化合物は、顔料等と相互作用を形成しうる官能基を含有する構造単位を更に含有することが好ましい。
　この顔料等と相互作用を形成しうる官能基としては、例えば、酸基、塩基性基、配位性基、及び、反応性を有する官能基等が挙げられる。
　高分子化合物が、酸基、塩基性基、配位性基、又は、反応性を有する官能基を含有する場合、それぞれ、酸基を含有する構造単位、塩基性基を含有する構造単位、配位性基を含有する構造単位、又は、反応性を有する構造単位を含有することが好ましい。
　特に、高分子化合物が、更に、酸基として、カルボン酸基等のアルカリ可溶性基を含有することで、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樹脂Ｂとしての高分子化合物がアルカリ可溶性を有することになる。このような高分子化合物を含有する硬化性組成物は、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 interaction with pigments, etc. In the polymer compound, a functional group capable of forming interaction with pigments or the like can be introduced. 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 coordination group, and a reactive functional group.
When the polymer compound contains an acid group, a basic group, a coordination group, or a reactive functional group, the structural unit containing an acid group, the structural unit containing a basic group, and a coordination group, respectively. It is preferable to contain a structural unit containing a coordinate 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 the acid group, developability for pattern formation by alkali development can be imparted to the polymer compound.
That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound as the resin B that contributes to the dispersion of pigments and the like has alkali solubility in the composition. The curable composition containing such a polymer compound has excellent light shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
Moreover, when a high molecular compound contains the structural unit containing an acid group, a high molecular compound becomes easy to become compatible with a solvent, and there exists a tendency for applicability | paintability to improve.
This is because the acid group in the structural unit containing an acid group easily interacts with the pigment and the like, and the polymer compound stably disperses the pigment and the like, and the viscosity of the polymer compound that disperses the pigment and the like decreases. This is presumably because the polymer compound itself is easily dispersed stably.
　ただし、酸基としてのアルカリ可溶性基を含有する構造単位は、上記のグラフト鎖を含有する構造単位と同一の構造単位であっても、異なる構造単位であってもよいが、酸基としてのアルカリ可溶性基を含有する構造単位は、上記の疎水性構造単位とは異なる構造単位である（すなわち、上記の疎水性構造単位には相当しない）。 However, the structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the structural unit containing the graft chain or a different structural unit. The structural unit containing a soluble group is a structural unit different from the hydrophobic structural unit described above (that is, does not correspond to the hydrophobic structural unit described above).
　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種であることが好ましく、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ことが好ましい。 Examples of the acid group that is a functional group capable of forming an interaction with a pigment include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and a carboxylic acid group, a sulfonic acid group, and The phosphoric acid group is preferably at least one, and more preferably a carboxylic acid group. Carboxylic acid groups have good adsorptive power to pigments and the like, and have high dispersibility.
That is, the polymer compound preferably further contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
　高分子化合物は、酸基を含有する構造単位を１種又は２種以上有してもよい。
　高分子化合物は、酸基を含有する構造単位を含有してもしなくてもよいが、含有する場合、酸基を含有する構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、５～８０質量％であることが好ましく、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. However, when it is contained, the content of the structural unit containing an acid group is calculated by mass conversion to the total mass of the polymer compound. 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 alkali development.
　顔料等と相互作用を形成しうる官能基である塩基性基としては、例えば、第１級アミノ基、第２級アミノ基、第３級アミノ基、Ｎ原子を含有するヘテロ環、及び、アミド基等があり、好ましい塩基性基は、顔料等への吸着力が良好で、かつ、分散性が高い点で、第３級アミノ基である。高分子化合物は、これらの塩基性基を１種又は２種以上、含有できる。
　高分子化合物は、塩基性基を含有する構造単位を含有してもしなくてもよいが、含有する場合、塩基性基を含有する構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、０．０１～５０質量％が好ましく、現像性阻害抑制という観点から、０．０１～３０質量％がより好ましい。 Examples of the basic group which is a functional group capable of forming an interaction with a pigment include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, and an amide A preferable basic group is a tertiary amino group in that it has a good adsorptive power to pigments and has 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 amount of the polymer compound in terms of mass. The amount is preferably 0.01 to 50% by weight, and more preferably 0.01 to 30% by weight from the viewpoint of inhibiting the development 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。 Examples of the coordinating group that is a functional group capable of forming an interaction with a pigment and the reactive functional group include, for example, acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, and acidification Thing etc. are mentioned. A preferred functional group is an acetylacetoxy group in that it has a good adsorptive power to pigments and has 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 reactive functional group, but if it contains, the content of these structural units Is preferably 10 to 80% by mass in terms of mass, and more preferably 20 to 60% by mass from the viewpoint of inhibiting developability 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ことが好ましい。 When the polymer compound contains a functional group capable of forming an interaction with a pigment or the like other than the graft chain, the polymer compound only needs to contain a functional group capable of forming an interaction with the various pigments or the like, Although how these functional groups are introduced is not particularly limited, the polymer compound is selected from structural units derived from monomers represented by the following formulas (iv) to (vi): It is preferable to contain more than one type of structural unit.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　式（ｉｖ）～（ｖｉ）中、Ｒ１１、Ｒ１２、及びＲ１３は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素原子、塩素原子、及び、臭素原子等）、又は炭素数が１～６のアルキル基（例えば、メチル基、エチル基、及び、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ことが好ましく、それぞれ独立に水素原子又はメチル基であることがより好ましい。一般式（ｉｖ）中、Ｒ１２及びＲ１３は、それぞれ水素原子であることが更に好ましい。 In formulas (iv) to (vi), R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number 1 to 6 alkyl groups (for example, a methyl group, an ethyl group, and a propyl group) are represented.
In formulas (iv) to (vi), R 11 , R 12 , and R 13 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently a hydrogen atom or methyl More preferably, it is a group. In general formula (iv), R 12 and R 13 are each 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、酸素原子であることが好ましい。
　また、式（ｖ）中のＹは、メチン基又は窒素原子を表す。 X 1 in the formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
Y in the formula (v) represents a methine group or a nitrogen atom.
　また、式（ｉｖ）～（ｖ）中のＬ１は、単結合又は２価の連結基を表す。２価の連結基の定義は、上述した式（ｉ）中のＬで表される２価の連結基の定義と同じである。 In the formulas (iv) to (v), L 1 represents a single bond or a divalent linking group. The definition of the divalent linking group is the same as the definition of the divalent linking group represented by L in the above-described formula (i).
　Ｌ１は、単結合、アルキレン基又はオキシアルキレン構造を含有する２価の連結基であることが好ましい。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ことがより好ましい。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有していてもよい。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の整数であることがより好ましい。 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 contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n —, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
　式（ｉｖ）～（ｖｉ）中、Ｚ１は、グラフト鎖以外に顔料等と相互作用を形成しうる官能基を表し、カルボン酸基、及び、第３級アミノ基であることが好ましく、カルボン酸基であることがより好ましい。 In the formulas (iv) to (vi), Z 1 represents a functional group capable of forming an interaction with a pigment other than the graft chain, and is preferably a carboxylic acid group or a tertiary amino group, More preferably, it 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、及び、臭素原子等）、炭素数が１～６のアルキル基（例えば、メチル基、エチル基、及び、プロピル基等）、－Ｚ１、又は－Ｌ１－Ｚ１を表す。ここでＬ１及びＺ１は、上記におけるＬ１及びＺ１と同義であり、好ましい例も同様である。Ｒ１４、Ｒ１５、及び、Ｒ１６としては、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 the formula (vi), R 14 , R 15 , and R 16 are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl having 1 to 6 carbon atoms group (e.g., methyl group, ethyl group, and propyl group), - represents a Z 1, or -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 14 , R 15 and R 16 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
　式（ｉｖ）で表される単量体として、Ｒ１１、Ｒ１２、及びＲ１３がそれぞれ独立に水素原子又はメチル基であって、Ｌ１がアルキレン基又はオキシアルキレン構造を含有する２価の連結基であって、Ｘ１が酸素原子又はイミノ基であって、Ｚ１がカルボン酸基である化合物が好ましい。
　また、式（ｖ）で表される単量体として、Ｒ１１が水素原子又はメチル基であって、Ｌ１がアルキレン基であって、Ｚ１がカルボン酸基であって、Ｙがメチン基である化合物が好ましい。
　更に、式（ｖｉ）で表される単量体として、Ｒ１４、Ｒ１５、及びＲ１６がそれぞれ独立に水素原子又はメチル基であって、Ｌ１が単結合又はアルキレン基であって、Ｚ１がカルボン酸基である化合物が好ましい。 As the monomer represented by the formula (iv), R 11 , R 12 and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or a divalent oxyalkylene structure. A compound in which X 1 is an oxygen atom or an imino group and Z 1 is a carboxylic acid group is preferable.
As the monomer represented by the formula (v), R 11 is a hydrogen atom or a methyl group, L 1 is an alkylene group, Z 1 is a carboxylic acid group, and Y is a methine group. Is preferred.
Furthermore, as a monomer represented by the formula (vi), R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group, L 1 is a single bond or an alkylene group, and Z A compound in which 1 is a carboxylic acid group is 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。 The following are typical examples of monomers (compounds) represented by formulas (iv) to (vi).
Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction containing a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride. Product, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride, a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride Reaction product, a reaction product of a compound containing an addition polymerizable double bond and hydroxyl group in the molecule and trimellitic anhydride, a compound containing an addition polymerizable double bond and hydroxyl group in the molecule and pyromellitic anhydride Reaction products with acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4 Hydroxyphenyl methacrylamide.
　顔料等と相互作用を形成しうる官能基を含有する構造単位の含有量は、顔料等との相互作用、経時安定性、及び現像液への浸透性の観点から、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 the pigment, etc. is the total mass of the polymer compound from the viewpoint of the interaction with the pigment, the stability over time, and the permeability to the developer. On the other hand, it is preferably 0.05 to 90% by mass, more preferably 1.0 to 80% by mass, and still more preferably 10 to 70% by mass.
・その他の構造単位
　更に、高分子化合物は、画像強度等の諸性能を向上する目的で、本発明の効果を損なわない限りにおいて、グラフト鎖を含有する構造単位、疎水性構造単位、及び、顔料等と相互作用を形成しうる官能基を含有する構造単位とは異なる、種々の機能を有する他の構造単位（例えば、後述する溶剤との親和性を有する官能基等を含有する構造単位）を更に有していてもよい。
　このような、他の構造単位としては、例えば、アクリロニトリル類、及び、メタクリロニトリル類等から選ばれるラジカル重合性化合物に由来の構造単位が挙げられる。
　高分子化合物は、これらの他の構造単位を１種又は２種以上使用でき、その含有量は、質量換算で、高分子化合物の総質量に対して、０～８０質量％が好ましく、１０～６０質量％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, for the purpose of improving various performances such as image strength, 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. Other structural units having various functions different from structural units containing functional groups capable of forming an interaction with the like (for example, structural units containing functional groups having affinity with a solvent to be described later) Furthermore, you may have.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
The polymer compound may use one or more of these other structural units, and its content is preferably 0 to 80% by mass, based on the total mass of the polymer compound, in terms of mass. 60 mass% or less is more preferable. When the content is in the above range, sufficient pattern formability is maintained.
・高分子化合物の物性
　高分子化合物の酸価は、１０～１１０ｍｇＫＯＨ／ｇ未満の範囲であることが好ましく、２０～１００ｍｇＫＯＨ／ｇの範囲がより好ましく、３０～７０ｍｇＫＯＨ／ｇの範囲が更に好ましい。
　高分子化合物の酸価が１１０ｍｇＫＯＨ／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 property of polymer compound The acid value of the polymer compound is preferably in the range of 10 to less than 110 mgKOH / g, more preferably in the range of 20 to 100 mgKOH / g, and still more preferably in the range of 30 to 70 mgKOH / g.
When the acid value of the polymer compound is 110 mgKOH / g or less, pattern peeling during development when forming a cured film is more effectively suppressed. Moreover, if the acid value of a high molecular compound is 10 mgKOH / g or more, alkali developability will become more favorable. Moreover, if the acid value of a high molecular compound is 20 mgKOH / g or more, precipitation of a pigment etc. can be suppressed more, the number of coarse particles can be decreased more, and the temporal stability of a composition can be improved more.
　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 this specification, the acid value can be calculated from, for example, the average content of acid groups in the compound. Moreover, the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of resin.
　高分子化合物の重量平均分子量は、７０００超３００，０００以下であることが好ましく、８０００～２００，０００であることがより好ましく、９０００～１００，０００であることが更に好ましく、１０，０００～５０，０００であることが特に好ましい。
　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 more than 7,000 and not more than 300,000, more preferably 8000 to 200,000, still more preferably 9000 to 100,000, and 10,000 to 50. Is particularly preferred.
The polymer compound can be synthesized based on a known method.
　高分子化合物の例としては、樹脂Ａに該当しない、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、及び、ポリエチレングリコールジステアレートも使用できる。
　高分子化合物の具体的な市販品としては、例えば、日本ルーブリゾール製「ソルスパース１２０００」が挙げられる。 Examples of the polymer compound include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, not corresponding to resin A, Polyethylene glycol distearate can also be used.
Specific examples of commercially available polymer compounds include “Solsperse 12000” manufactured by Nippon Lubrizol.
　また、酸基及び塩基性基を含有する両性樹脂を使用することも好ましい。両性樹脂は、酸価が５ｍｇＫＯＨ／ｇ以上で、かつ、アミン価が５ｍｇＫＯＨ／ｇ以上である樹脂が好ましい。
　これらの高分子化合物は、１種を単独で用いても、２種以上を併用してもよい。 It is also preferable to use an amphoteric resin containing an acid group and a basic group. The amphoteric resin is preferably a resin having an acid value of 5 mgKOH / g or more and an amine value of 5 mgKOH / g or more.
These polymer compounds may be used alone or in combination of two or more.
　なお、高分子化合物の具体例の例としては、特開２０１３－２４９４１７号公報の段落０１２７～０１２９に記載の高分子化合物を参照でき、これらの内容は本明細書に組み込まれる。 As specific examples of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification.
　また、樹脂Ｂ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）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。 As the resin B, in addition to the above-described polymer compound, a graft copolymer described in JP 2010-106268 A, paragraphs 0037 to 0115 (corresponding to paragraphs 0075 to 0133 in US2011 / 0124824) can be used. Is incorporated herein by reference.
In addition to the above, it contains a side chain structure in which acidic groups in paragraphs 0028 to 0084 of JP 2011-153283 A (corresponding paragraphs 0075 to 0133 of US2011 / 0279759) are bonded via a linking group. Polymeric compounds containing components can be used, the contents of which can be incorporated and incorporated herein.
　なお、本発明の硬化性組成は、樹脂Ａ及び樹脂Ｂのいずれにも該当しない樹脂を含有していてもよい。 In addition, the curable composition of this invention may contain resin which does not correspond to any of resin A and resin B.
＜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。
　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（ラジカル重合開始剤）であってもよい。
　また、光重合開始剤は、３００～８００ｎｍ（３３０～５００ｎｍがより好ましい。）の範囲内に少なくとも５０のモル吸光係数を有する化合物を、少なくとも１種含有していることが好ましい。 <Photopolymerization initiator>
The curable composition contains a photopolymerization initiator.
As a photoinitiator, if a superposition | polymerization of a polymeric compound can be started, it will not restrict | limit, A well-known photoinitiator can be used. As the photopolymerization initiator, for example, a photopolymerization initiator having photosensitivity from the ultraviolet region to the visible light region is preferable. In addition, it may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, and an initiator that initiates cationic polymerization according to the type of the polymerizable compound (radical polymerization initiator). It may be.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least 50 within a 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種以上を使用してもよい。２種以上の光重合開始剤を併用する場合には、合計含有量が上記範囲内であることが好ましい。 The content of the photopolymerization initiator in the curable composition is not particularly limited, but is preferably 0.5 to 20% by mass with respect to the total solid content of the curable composition. A photoinitiator may be used individually by 1 type, or may use 2 or more types. 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。 Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those containing a triazine skeleton, those containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, Examples include oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenones.
As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A 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, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can be used as the photopolymerization initiator.
As the hydroxyacetophenone compound, for example, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF) can be used.
As the aminoacetophenone compound, for example, commercially available products IRGACURE-907, IRGACURE-369, or IRGACURE-379EG (trade names, all manufactured by BASF) can be used. As the aminoacetophenone compound, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source having a wavelength of 365 nm or a wavelength of 405 nm can also be used.
As the acylphosphine compound, commercially available IRGACURE-819 or IRGACURE-TPO (trade name, both manufactured by BASF) can be used.
・オキシム化合物
　光重合開始剤として、オキシムエステル系重合開始剤（オキシム化合物）がより好ましい。
　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 polymerization initiator (oxime compound) is more preferable.
As specific examples of the oxime compound, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, or a compound 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, 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 And carbonyloxyimino-1-phenylpropan-1-one.
In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995), pp. 156-162. Examples include compounds described in 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797, and JP-A 2006-342166. It is done.
Among the commercially available products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), or IRGACURE-OXE04 (manufactured by BASF) is also preferable. Also, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831, Adeka Arcles NCI-930 (manufactured by ADEKA), or N-1919 (carbazole oxime ester-containing light An initiator (manufactured 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. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety; A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at a dye site; a ketoxime compound described in International Patent Publication No. 2009-131189; and a triazine skeleton and an oxime skeleton A compound described in US Pat. No. 7,556,910 contained in the same molecule; a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source; Good.
For example, paragraphs 0274 to 0275 of JP2013-29760 can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The N—O bond of the oxime compound may be an (E) oxime compound, a (Z) oxime compound, a mixture of (E) isomer and (Z) isomer. 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ことが好ましい。
　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、複素環基がより好ましい。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 the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In the formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group, and an aryl group or a heterocyclic group is More preferred. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
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. Examples of the substituent include the above-described substituents.
　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。 An oxime compound containing a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound containing a fluorine atom include compounds described in JP2010-262028; compounds 24 and 36 to 40 described in JP-T-2014-500852; and JP2013-164471A (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。 As the photopolymerization initiator, compounds represented by the following general formulas (1) to (4) can also be used.
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 are each independently 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 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 each other 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 , —CN, a halogen atom, or a hydroxyl group, and R 6 is 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 20 represents a heterocyclic group, X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.
　式（３）において、Ｒ１は、炭素数１～２０のアルキル基、炭素数４～２０の脂環式炭化水素基、炭素数６～３０のアリール基、又は、炭素数７～３０のアリールアルキル基を表し、Ｒ３及びＲ４は、それぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基、又は、炭素数４～２０の複素環基を表し、Ｘは、直接結合又はカルボニル基を示す。 In Formula (3), R 1 represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms. R 3 and R 4 each independently 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 carbon atom. Represents a heterocyclic group of formula 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, 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. 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、特開２０１４－１３７４６６号公報の段落００７６～００７９に記載された化合物が挙げられる。この内容は本明細書に組み込まれることとする。 In the above formulas (1) and (2), R 1 and R 2 are 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.
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 formula (1) and formula (2) include compounds described in paragraphs 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.
　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。下記具体例の中でも、得られる硬化膜の剥がれ抑制性がより優れる点から、一般式（Ａ）で表されるオキシム化合物（以下「特定光重合開始剤」ともいう」）が好ましい。特定光重合開始剤の市販品としては、ＩＲＧＡＣＵＲＥ－ＯＸＥ０３（ＢＡＳＦ社製）が挙げられる。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。 Specific examples of oxime compounds preferably used in the curable composition are shown below. Among the following specific examples, the oxime compound represented by the general formula (A) (hereinafter also referred to as “specific photopolymerization initiator”) is preferable from the viewpoint of more excellent peeling inhibition of the obtained cured film. As a commercial product of the specific photopolymerization initiator, IRGACURE-OXE03 (manufactured by BASF) can be mentioned. As the oxime compound, the compound described in Table 1 of International Publication No. 2015-036910 can also be used, and the above contents are incorporated in the present specification.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
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ことが好ましく、３６０～４８０ｎｍの波長領域に極大吸収波長を有することがより好ましく、３６５ｎｍ及び４０５ｎｍの波長の吸光度が高いことが更に好ましい。
　オキシム化合物の３６５ｎｍ又は４０５ｎｍにおけるモル吸光係数は、感度の観点から、１，０００～３００，０００であることが好ましく、２，０００～３００，０００であることがより好ましく、５，０００～２００，０００であることが更に好ましい。
　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の濃度で測定することが好ましい。
　光重合開始剤は、必要に応じて２種以上を組み合わせて使用してもよい。 The oxime compound preferably has a maximum absorption wavelength in a wavelength region of 350 to 500 nm, more preferably has a maximum absorption wavelength in a wavelength region of 360 to 480 nm, and further preferably has high absorbance at wavelengths of 365 nm and 405 nm. .
The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200,000 from the viewpoint of sensitivity. More preferably, it is 000.
A known method can be used to determine the molar extinction coefficient of the compound. For example, the molar extinction coefficient is measured at a concentration of 0.01 g / L using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent. It is preferable.
You may use a photoinitiator in combination of 2 or more type as needed.
　また、光重合開始剤としては、特開第２００８－２６０９２７号公報の段落００５２、特開第２０１０９７２１０号公報の段落００３３～００３７、特開第２０１５－６８８９３号公報の段落００４４に記載の化合物も使用でき、上記の内容は本明細書に組み込まれる。 As the photopolymerization initiator, compounds described in paragraph 0052 of JP-A-2008-260927, paragraphs 0033-0037 of JP-A-201097210, and paragraph 0044 of JP-A-2015-68893 are also used. And 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。
　重合禁止剤としては特に制限されず、公知の重合禁止剤を使用できる。重合禁止剤としては、例えば、フェノール系重合禁止剤（例えば、ｐ－メトキシフェノール、２，５－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、２，６－ジｔｅｒｔ－ブチル－４－メチルフェノール、４，４’－チオビス（３－メチル－６－ｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、４－メトキシナフトール等）；ハイドロキノン系重合禁止剤（例えば、ハイドロキノン、２，６－ジ－ｔｅｒｔ－ブチルハイドロキノン等）；キノン系重合禁止剤（例えば、ベンゾキノン等）；フリーラジカル系重合禁止剤（例えば、２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル等）；ニトロベンゼン系重合禁止剤（例えば、ニトロベンゼン、４－ニトロトルエン等）；及び、フェノチアジン系重合禁止剤（例えば、フェノチアジン、２－メトキシフェノチアジン等）；等が挙げられる。
　中でも、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 contains a polymerization inhibitor.
It does not restrict | limit especially as a polymerization inhibitor, A well-known polymerization inhibitor can be used. Examples of the polymerization inhibitor include phenol-based polymerization inhibitors (for example, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-ditert-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 (for example, , Hydroquinone, 2,6-di-tert-butylhydroquinone, etc.); quinone 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 these, a phenol polymerization inhibitor or a free radical polymerization inhibitor is preferable in that the curable composition has a more excellent effect.
　重合禁止剤は、硬化性基を含有する樹脂と共に用いる場合にその効果が顕著である。
　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％がより好ましく、０．００８～０．０５質量％が更に好ましい。重合禁止剤は、１種を単独で用いても、２種以上を併用してもよい。２種以上の重合禁止剤を併用する場合には、合計含有量が上記範囲内であることが好ましい。
　また、硬化性組成物中の重合性化合物の含有量に対する、重合禁止剤の含有量の比（重合禁止剤の含有量／重合性化合物の含有量（質量比））は、０．０００５超が好ましく、０．０００６～０．０２がより好ましく、０．０００６～０．００５が更に好ましい。 The effect of the polymerization inhibitor is remarkable when 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 with respect to the total solid content of the curable composition, preferably 0.001 to 0.2. % By mass is more preferable, and 0.008 to 0.05% by mass is even more preferable. A polymerization inhibitor may be used individually by 1 type, or may use 2 or more types together. When two or more polymerization inhibitors are used in combination, the total content is preferably within the above range.
In addition, the ratio of the content of the polymerization inhibitor to the content of the polymerizable compound in the curable composition (the content of the polymerization inhibitor / the content of the polymerizable compound (mass ratio)) is more than 0.0005. Preferably, 0.0006 to 0.02 is more preferable, and 0.0006 to 0.005 is still more preferable.
＜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ことが好ましい。 <Surfactant>
The curable composition may contain a surfactant. Surfactant contributes to the applicability | paintability improvement of a 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.
Surfactant may be used individually by 1 type, or may use 2 or more types together. When two or more surfactants are used in combination, the total amount is preferably within the above range.
　界面活性剤としては、例えば、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、及び、シリコーン系界面活性剤等が挙げられる。 Examples of the surfactant include a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant.
　例えば、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 fluorosurfactant, the liquid properties (particularly fluidity) of the curable composition are further improved. That is, in the case of forming a film using a curable composition containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid. The applicability to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that a film having a uniform thickness with small thickness unevenness can be more suitably formed.
　フッ素系界面活性剤中のフッ素含有率は、３～４０質量％が好ましく、５～３０質量％がより好ましく、７～２５質量％が更に好ましい。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性及び／又は省液性の点で効果的であり、硬化性組成物中における溶解性も良好である。 The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and / or liquid-saving properties, and has good solubility in the curable composition. .
　フッ素系界面活性剤としては、例えば、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７６、同Ｆ１７７、同Ｆ１４１、同Ｆ１４２、同Ｆ１４３、同Ｆ１４４、同Ｒ３０、同Ｆ４３７、同Ｆ４７５、同Ｆ４７９、同Ｆ４８２、同Ｆ５５４、同Ｆ７８０、及び、同Ｆ７８１（以上、ＤＩＣ製）；フロラードＦＣ４３０、同ＦＣ４３１、及び、同ＦＣ１７１（以上、住友スリーエム製）；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、旭硝子製）；並びに、ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、及び、ＰＦ７００２（ＯＭＮＯＶＡ社製）等が挙げられる。
　フッ素系界面活性剤としてブロックポリマーも使用でき、具体例としては、例えば特開第２０１１－８９０９０号公報に記載されたが化合物が挙げられる。 Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, and F781 (above, manufactured by DIC); Florard FC430, FC431, and FC171 (above, manufactured by Sumitomo 3M); Surflon S-382, SC-101, SC -103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (above, manufactured by Asahi Glass); and PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc. are mentioned.
A block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A No. 2011-89090.
＜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）等も好適に用いられる。
　紫外線吸収剤としては、特開２０１２－３２５５６号公報の段落０１３４～０１４８に例示される化合物が挙げられる。
　紫外線吸収剤の含有量は、硬化性組成物の全固形分に対して、０．００１～１５質量％が好ましい。 <Ultraviolet absorber>
The curable composition may contain an ultraviolet absorber. Thereby, the shape of the pattern of a cured film can be made into the more excellent (fine) shape.
As the ultraviolet absorber, salicylate, benzophenone, benzotriazole, substituted acrylonitrile and triazine ultraviolet absorbers can be used. As specific examples of these, compounds of paragraphs 0137 to 0142 (corresponding to paragraphs 0251 to 0254 of US2012 / 0068292) of JP2012-068418A can be used, and the contents thereof can be incorporated and incorporated in the present specification. .
In addition, a diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) and the like are also preferably used.
Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
The content of the ultraviolet absorber is preferably 0.001 to 15% by mass with respect to the total solid content of the curable composition.
＜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以下であることが好ましく、４以下であることがより好ましい。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）を含まないことが好ましく、フッ素原子、珪素原子（ただし、加水分解性基が結合した珪素原子は除く）、珪素原子で置換されたアルキレン基、炭素数８以上の直鎖状アルキル基、及び、炭素数３以上の分岐鎖状アルキル基は含まないことが望ましい。 <Silane coupling agent>
The curable composition may contain a silane coupling agent.
A silane coupling agent is a compound containing a hydrolyzable group and other functional groups in the molecule. Note that a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group contains a carbon atom, the number of carbon atoms is preferably 6 or less, and 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.
In addition, when forming a cured film on the substrate, the silane coupling agent improves the adhesion between the substrate and the cured film, so fluorine atoms and silicon atoms (however, excluding silicon atoms to which hydrolyzable groups are bonded) Is preferably not included, fluorine atom, silicon atom (excluding the 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, and 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種単独で含有していてもよく、２種以上を含有していてもよい。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 with respect to the total solid content in the curable composition.
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 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。 Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, Examples include vinyltrimethoxysilane and vinyltriethoxysilane.
＜溶剤＞
　硬化性組成物は、溶剤を含有することが好ましい。
　溶剤としては特に制限されず公知の溶剤を使用できる。
　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ことが好ましく、１５～５０質量％となるように調整されることがより好ましい。なお、固形分とは、溶剤以外の成分を意図する。
　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ことが好ましい。 <Solvent>
The curable composition preferably contains a solvent.
The solvent is not particularly limited and a known solvent can be used.
The content of the solvent in the curable composition is not particularly limited, but is preferably adjusted so that the solid content of the curable composition is 10 to 90% by mass, and 15 to 50% by mass. More preferably, it is adjusted. In addition, solid content intends components other than a solvent.
A solvent may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of solvent 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。 Examples of the solvent include water and an organic solvent.
Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 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 Chill 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 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、黒色色材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ことが好ましい。
　分散組成物は、黒色色材、樹脂Ｂ、及び、溶剤を混合して調製することが好ましい。また、分散組成物に重合禁止剤を含有させることも好ましい。 [Method for producing curable composition]
The curable composition is preferably prepared by first preparing a dispersion composition in which a black color material is dispersed, and further mixing the obtained dispersion composition with other components to obtain a curable composition.
The dispersion composition is preferably prepared by mixing a black color material, resin B, and a solvent. Moreover, it is also preferable to make a dispersion composition contain a polymerization inhibitor.
　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 components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser, 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 preparing the curable composition, each component may be blended at once, or each component may be blended sequentially after being dissolved or dispersed in a solvent. Moreover, the order of input and the working conditions when blending are not particularly limited.
　硬化性組成物は、異物の除去及び欠陥の低減等の目的で、フィルタで濾過することが好ましい。フィルタとしては、従来からろ過用途等に用いられているフィルタであれば特に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、超高分子量を含有する）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有する）、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、顔料のろ過詰まりを抑えつつ、顔料に含まれる不純物及び凝集物等、微細な異物を確実に除去できるようになる。
　フィルタを使用する際、異なるフィルタを組み合わせてもよい。その際、第１のフィルタでのフィルタリングは、１回のみでもよいし、２回以上行ってもよい。異なるフィルタを組み合わせて２回以上フィルタリングを行う場合は１回目のフィルタリングの孔径より２回目以降の孔径が同じ、又は、大きい方が好ましい。また、上述した範囲内で異なる孔径の第１のフィルタを組み合わせてもよい。ここでの孔径は、フィルタメーカーの公称値を参照できる。市販のフィルタとしては、例えば、日本ポール株式会社、アドバンテック東洋株式会社、日本インテグリス株式会社（旧日本マイクロリス株式会社）、及び、株式会社キッツマイクロフィルタ等が提供する各種フィルタの中から選択できる。
　第２のフィルタは、上述した第１のフィルタと同様の材料等で形成されたフィルタを使用できる。第２のフィルタの孔径は、０．２～１０．０μｍが好ましく、０．２～７．０μｍがより好ましく、０．３～６．０μｍが更に好ましい。
　硬化性組成物は、金属、ハロゲンを含有する金属塩、酸、アルカリ等の不純物を含まないことが好ましい。これら材料に含まれる不純物の含有量としては、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 with a filter for the purpose of removing foreign substances and reducing defects. As a filter, if it is a filter conventionally used for the filtration use etc., it can be used without being specifically limited. Examples include filters made of fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (containing high density and ultra high molecular weight). It is done. Among these materials, polypropylene (containing 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 it within this range, fine foreign matters such as impurities and aggregates contained in the pigment can be surely removed while suppressing filtration clogging of the pigment.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, it can select from the various filters which Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (former Japan Microlith Co., Ltd.), KITZ micro filter, etc. provide, for example.
As the second filter, a filter formed of the same material or the like as the first filter described above can be used. 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.
It is preferable that a curable composition does not contain impurities, such as a metal, the metal salt containing a halogen, an acid, and an alkali. 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 free (below the detection limit of the measuring device). Is most preferable.
The impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).
［硬化膜を製造する手順］
　上記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。
　硬化膜の製造方法としては特に制限されないが、以下の工程を含有することが好ましい。
・硬化性組成物層形成工程
・露光工程
・現像工程
　以下、各工程について説明する。 [Procedure for manufacturing cured film]
A curable composition layer (composition layer) formed using the curable composition can be cured to obtain a patterned cured film.
Although it does not restrict | limit especially as a manufacturing method of a cured film, It is preferable to contain the following processes.
-Curable composition layer formation process-Exposure process-Development process Hereinafter, each process is demonstrated.
＜硬化性組成物層形成工程＞
　硬化性組成物層形成工程は、上記硬化性組成物を用いて、硬化性組成物層を形成する工程である。硬化性組成物を用いて、硬化性組成物層を形成する工程としては、例えば、基板上に、硬化性組成物を塗布して、硬化性組成物層を形成する工程が挙げられる。
　基板の種類は特に制限されないが、固体撮像素子として用いる場合は、例えば、ケイ素基板が挙げられ、カラーフィルタ（固体撮像素子用カラーフィルタを含有する）として用いる場合には、ガラス基板等が挙げられる。
　基板上への硬化性組成物の塗布方法としては、スピンコート、スリット塗布、インクジェット法、スプレー塗布、回転塗布、流延塗布、ロール塗布、及び、スクリーン印刷法等の各種の塗布方法を適用することができる。
　基板上に塗布された硬化性組成物は、通常、７０～１５０℃で１～４分程度の条件下で乾燥され、硬化性組成物層が形成される。 <Curable composition layer forming step>
A curable composition layer formation process is a process of forming a curable composition layer using the said curable composition. As a process of forming a curable composition layer using a curable composition, the process of apply | coating a curable composition on a board | substrate and forming a curable composition layer is mentioned, for example.
The type of the substrate is not particularly limited, but when used as a solid-state imaging device, for example, a silicon substrate is used, and when used as a color filter (including a color filter for a solid-state imaging device), a glass substrate or the like is used. .
As a coating method of the curable composition on the substrate, various coating methods such as spin coating, slit coating, ink jet method, spray coating, spin coating, cast coating, roll coating, and screen printing are applied. be able to.
The curable composition applied on the substrate is usually dried at 70 to 150 ° C. for about 1 to 4 minutes to form a curable composition layer.
＜露光工程＞
　露光工程では、硬化性組成物層形成工程において形成された硬化性組成物層に活性光線又は放射線を照射することにより露光し、光照射された硬化性組成物層を硬化させる。
　光照射の方法としては特に制限されないが、パターン状の開口部を有するフォトマスクを介して光照射することが好ましい。
　本発明の硬化性組成物を使用することで、照射された光の回折及び／又は散乱等することによって生じる硬化膜の線幅安定性の劣化を抑制できる。特に、プロキシミティ露光では回折光の影響が生じやすいため、本発明の硬化性組成物を使用する利点が大きい。
　露光は放射線の照射により行うことが好ましく、露光に際して用いることができる放射線としては、特に、ｇ線、ｈ線、及び、ｉ線等の紫外線が好ましく、光源としては高圧水銀灯が好ましい。照射強度は５～１５００ｍＪ／ｃｍ２が好ましく、１０～１０００ｍＪ／ｃｍ２がより好ましい。
　なお、硬化性組成物が、熱重合開始剤を含有する場合、上記露光工程において、硬化性組成物層を加熱してもよい。加熱の温度として特に制限されないが、８０～２５０℃が好ましい。また、加熱の時間としては特に制限されないが、３０～３００秒が好ましい。
　なお、露光工程において、硬化性組成物層を加熱する場合、後述する後加熱工程を兼ねてもよい。言い換えれば、露光工程において、硬化性組成物層を加熱する場合、硬化膜の製造方法は後加熱工程を含有しなくてもよい。 <Exposure process>
In the exposure step, the curable composition layer formed in the curable composition layer forming step is exposed by irradiating with actinic rays or radiation, and the curable composition layer irradiated with light is cured.
The light irradiation method is not particularly limited, but light irradiation is preferably performed through a photomask having a patterned opening.
By using the curable composition of the present invention, it is possible to suppress deterioration of the line width stability of the cured film caused by diffraction and / or scattering of the irradiated light. In particular, the effect of using the curable composition of the present invention is great because proximity exposure is likely to be affected by diffracted light.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are particularly preferable, and a high-pressure mercury lamp is preferable as a light source. The irradiation intensity is preferably 5 ~ 1500mJ / cm 2, more preferably 10 ~ 1000mJ / cm 2.
In addition, when a curable composition contains a thermal-polymerization initiator, you may heat a curable composition layer in the said exposure process. The heating temperature is not particularly limited, but is preferably 80 to 250 ° C. The heating time is not particularly limited, but is preferably 30 to 300 seconds.
In addition, in an exposure process, when heating a curable composition layer, you may serve as the post-heating process mentioned later. In other words, when the curable composition layer is heated in the exposure step, the method for producing a cured film may not include the post-heating step.
＜現像工程＞
　露光工程に次いで、現像処理（現像工程）を行い、露光工程における光未照射部分を現像液に溶出させる。これにより、光硬化した部分だけが残る。
　現像液としては、アルカリ現像液を用いてもよい。その場合は、有機アルカリ現像液を用いることが好ましい。現像温度としては通常２０～３０℃であり、現像時間は２０～９０秒である。
　アルカリ水溶液（アルカリ現像液）としては、無機アルカリ現像液及び有機アルカリ現像液が挙げられる。
　無機アルカリ現像液としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、硅酸ナトリウム、及び、メタ硅酸ナトリウム等のアルカリ性化合物を、濃度が０．００１～１０質量％（好ましくは０．００５～０．５質量％）となるように溶解したアルカリ水溶液が挙げられる。
　また、有機アルカリ現像液としては、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ド、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－ウンデセン等のアルカリ性化合物を、濃度が０．００１～１０質量％（好ましくは０．００５～０．５質量％）となるように溶解したアルカリ水溶液が挙げられる。
　アルカリ水溶液には、例えば、メタノール、エタノール等の水溶性有機溶剤、及び／又は、界面活性剤等を適量添加することもできる。なお、このようなアルカリ水溶液からなる現像液を使用した場合には、一般に現像後に硬化膜を純水で洗浄（リンス）する。 <Development process>
Subsequent to the exposure step, development processing (development step) is performed to elute the light non-irradiated portion in the exposure step into the developer. Thereby, only the photocured part remains.
An alkaline developer may be used as the developer. In that case, an organic alkali developer is preferably used. The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
Examples of the alkaline aqueous solution (alkali developer) include inorganic alkali developers and organic alkali developers.
As the inorganic alkaline developer, an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, and sodium metaoxalate is used at a concentration of 0.001 to 10% by mass (preferably An alkaline aqueous solution dissolved so as to be 0.005 to 0.5% by mass).
Organic alkaline developers include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline , Pyrrole, piperidine, and alkaline compounds such as 1,8-diazabicyclo- [5,4,0] -7-undecene at a concentration of 0.001 to 10% by mass (preferably 0.005 to 0.5% by mass) %) Dissolved in an alkaline aqueous solution.
An appropriate amount of a water-soluble organic solvent such as methanol and ethanol, and / or a surfactant, for example, can be added to the alkaline aqueous solution. When a developer composed of such an alkaline aqueous solution is used, the cured film is generally washed (rinsed) with pure water after development.
　なお、硬化膜の製造方法は、その他の工程を含有してもよい。
　その他の工程としては、特に制限はなく、目的に応じて適宜選択することができる。
　その他の工程としては、例えば、基材の表面処理工程、前加熱工程（プリベーク工程）、後加熱工程（ポストベーク工程）等が挙げられる。
　上記硬化膜の製造方法としては、露光工程と、現像工程との間に、露光後の硬化性組成物層を加熱する工程（後加熱工程）を含有することが好ましい。
　上記前加熱工程、及び後加熱工程における加熱温度は、８０～２５０℃が好ましい。
上限は、２００℃以下がより好ましく、１５０℃以下が更に好ましい。下限は９０℃以上がより好ましい。
　前加熱工程及び後加熱工程における加熱時間は、３０～３００秒が好ましい。上限は、２４０秒がより好ましく、１８０秒以下が更に好ましい。下限は６０秒以上がより好ましい。 In addition, the manufacturing method of a cured film may contain another process.
There is no restriction | limiting in particular as another process, According to the objective, it can select suitably.
Examples of the other steps include a substrate surface treatment step, a preheating step (pre-baking step), and a post-heating step (post-baking step).
As a manufacturing method of the said cured film, it is preferable to contain the process (post-heating process) of heating the curable composition layer after exposure between an exposure process and a image development process.
The heating temperature in the preheating step and the postheating step is preferably 80 to 250 ° C.
The upper limit is more preferably 200 ° C. or less, and further preferably 150 ° C. or less. The lower limit is more preferably 90 ° C. or higher.
The heating time in the preheating step and the postheating step is preferably 30 to 300 seconds. The upper limit is more preferably 240 seconds and even more preferably 180 seconds or less. The lower limit is more preferably 60 seconds or more.
［硬化膜の物性、及び、硬化膜の用途］
＜硬化膜の物性＞
　本発明の硬化性組成物を用いて得られる硬化膜は、優れた遮光性を有する点で、４００～１２００ｎｍの波長領域における膜厚１．０μｍあたりの光学濃度（ＯＤ：Ｏｐｔｉｃａｌ　Ｄｅｎｓｉｔｙ）が、２．０以上が好ましく、３．０以上がより好ましい。なお、上限値は特に制限されないが、一般に１０以下が好ましい。上記硬化膜は、遮光膜として好ましく用いることができる。
　また、本明細書において、４００～１２００ｎｍの波長領域における膜厚１．０μｍあたりの光学濃度が、３．０以上とは、波長４００～１２００ｎｍの全域において、膜厚１．０μｍあたりの光学濃度が３．０以上であることを意図する。
　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。 [Physical properties of cured film and uses of cured film]
<Physical properties of cured film>
The cured film obtained using the curable composition of the present invention has an excellent light-shielding property, and has an optical density (OD: Optical Density) per film thickness of 1.0 μm in a wavelength region of 400 to 1200 nm of 2. 0.0 or more is preferable, and 3.0 or more is more preferable. The upper limit is not particularly limited, but is generally preferably 10 or less. The cured film can be preferably used as a light shielding film.
In this specification, the optical density per 1.0 μm thickness in the wavelength region of 400 to 1200 nm is 3.0 or more. The optical density per 1.0 μm thickness in the entire wavelength range of 400 to 1200 nm. Intended to be 3.0 or higher.
In this specification, as a method of measuring the optical density of a cured film, first, a cured film is formed on a glass substrate, and measured using a transmission densitometer (X-rite 361T (visual) densitometer). The film thickness at the location is also measured, and the optical density per predetermined film thickness is calculated.
　また、上記硬化膜は、表面凹凸構造を有することも好ましい。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以下の範囲であることが好ましい。
　硬化膜の反射率は、７％未満が好ましく、５％未満がより好ましく、３％未満が更に好ましい。
　表面凹凸構造を作製する方法は特に限定されない。例えば、上述の通り、硬化性組成物中の重合性化合物が含有するエチレン性不飽和基の数を所定の範囲に調製することでも、硬化膜の表面を適度に粗面化されて、表面凹凸構造を得ることができる。
　他にも、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有する方法、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等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。 The cured film preferably has a surface uneven structure. By doing so, the reflectance of the cured film can be reduced when the cured film is a light shielding film. Even if the surface of the cured film itself has an uneven structure, another layer may be provided on the cured film to provide the uneven structure. The shape of the surface concavo-convex structure is not particularly limited, but the surface roughness is preferably in the range of 0.55 μm to 1.5 μm.
The reflectance of the cured film is preferably less than 7%, more preferably less than 5%, and still more preferably less than 3%.
The method for producing the surface uneven structure is not particularly limited. For example, as described above, even if the number of ethylenically unsaturated groups contained in the polymerizable compound in the curable composition is adjusted within a predetermined range, the surface of the cured film is appropriately roughened, A structure can be obtained.
In addition, a cured film or other layer by a method containing an organic filler and / or an inorganic filler in a cured film or other layer, a lithography method utilizing exposure and development, or an etching method, a sputtering method, a nanoimprint method, etc. A method of roughening the surface of the layer may be used.
In addition to the above, the method of reducing the reflectance of the cured film includes 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 And a method of forming a low optical density layer and a high optical density layer 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 composed of portable devices such as personal computers, tablets, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as printer multifunction devices and scanners; surveillance cameras, barcode readers, cash Industrial equipment such as automated teller machines (ATMs), high-speed cameras, and devices with personal authentication using facial image authentication; in-vehicle camera equipment; endoscopes, capsule endoscopes, And medical camera equipment such as catheters; and biosensors, biosensors, military reconnaissance cameras, stereoscopic map cameras, weather and ocean observation cameras, land resource exploration cameras, and space astronomy 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）等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 cured film can also be used for applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). The cured film is suitable for members that provide a light shielding function or an antireflection function, in addition to optical filters and optical films used in micro LEDs and micro OLEDs.
Examples of the micro LED and the micro OLED include those described in JP-T-2015-500562 and JP-T-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。
　上記硬化膜は、自動車等の車両用前照灯に用いられるヘッドライトユニットの遮光部材及び／又は遮光膜に使用することも好ましい。また、反射防止部材及び反射防止膜等に使用することも好ましい。 The cured film is also suitable as an optical filter and an optical film used for quantum dot sensors and quantum dot solid-state imaging devices. Moreover, it is suitable as a member which provides a light shielding function and an antireflection function. Examples of the quantum dot sensor and the quantum dot solid-state imaging device include those described in US Patent Application Publication No. 2012/37789 and International Publication No. 2008/131313 pamphlet.
The cured film is also preferably used for a light shielding member and / or a light shielding film of a headlight unit used for a vehicle headlamp such as an automobile. Moreover, it is also preferable to use it for an antireflection member, an antireflection film, or the like.
＜遮光膜、光学素子、並びに、固体撮像素子及び固体撮像装置＞
　本発明の硬化性組成物を用いて得られた硬化膜は、いわゆる遮光膜として使用することも好ましい。このような遮光膜は、固体撮像素子に使用することも好ましい。
　なお、遮光膜は、本発明の硬化性組成物を用いて得られる硬化膜における好ましい形態の１つである。つまり、本発明の硬化膜が、遮光膜であることも好ましい。
　遮光膜である硬化膜の製造方法は、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。 <Light-shielding film, optical element, solid-state imaging device, and solid-state imaging device>
The cured film obtained using the curable composition of the present invention is also preferably used as a so-called light-shielding film. Such a light shielding film is also preferably used for a solid-state imaging device.
In addition, a light shielding film is one of the preferable forms in the cured film obtained using the curable composition of this invention. That is, the cured film of the present invention is also preferably a light shielding film.
The manufacturing method of the cured film which is a light shielding film can be similarly performed by the method described as the manufacturing method of the above-described cured film. Specifically, a light-shielding film can be produced by applying a curable composition to a substrate to form a curable composition layer, and exposing and developing.
　本発明は、光学素子の発明をも含有する。本発明の光学素子は、上記硬化膜（遮光膜）を有する光学素子である。光学素子としては、例えば、カメラ、双眼鏡、顕微鏡、及び、半導体露光装置等の光学機器に使用される光学素子が挙げられる。
　中でも、上記光学素子は、例えば、カメラ等に搭載される固体撮像素子であることが好ましい。
　上述の通り、本発明の固体撮像素子は、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。 The present invention also includes an invention of an optical element. The optical element of the present invention is an optical element having the cured film (light-shielding film). Examples of the optical element include an optical element used in an optical apparatus such as a camera, binoculars, a microscope, and a semiconductor exposure apparatus.
Especially, it is preferable that the said optical element is a solid-state image sensor mounted in a camera etc., for example.
As described above, the solid-state imaging device of the present invention contains the cured film (light-shielding film). The form in which the solid-state image sensor includes a cured film (light-shielding film) is not particularly limited. For example, a plurality of photodiodes that form a light receiving area of a solid-state image sensor (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 color adjusting pixel) or the opposite side of the forming surface. Can be mentioned.
The solid-state imaging device contains the solid-state imaging element.
　固体撮像装置、及び、固体撮像素子の構成例を図１及び２を参照して説明する。なお、図１及び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。本発明の硬化性組成物を用いて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 the solid-state imaging device and the solid-state imaging element will be described with reference to FIGS. In FIGS. 1 and 2, in order to clarify each part, the ratio of the thickness and / or width is disregarded and a part is exaggerated.
As shown in FIG. 1, the solid-state imaging device 100 includes a rectangular solid-state imaging element 101 and a transparent cover glass 103 that is held above the solid-state imaging element 101 and seals the solid-state imaging element 101. Yes. Further, a lens layer 111 is provided on the cover glass 103 with a spacer 104 interposed therebetween. The lens layer 111 includes a support body 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, the effect of condensing light on the lens material 112 is weakened due to light diffusion, and light reaching the imaging unit 102 is reduced. In addition, noise is generated due to stray light. Therefore, the peripheral region of the lens layer 111 is shielded from light by providing a light shielding film 114. A cured film obtained using the curable composition 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 a light receiving surface thereof and outputs it 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 includes a rectangular chip substrate 106 and a circuit substrate 107 having the same size, and the circuit substrate 107 is laminated on the back surface of the chip substrate 106.
　チップ基板１０６として用いられる基板の材料としては特に制限されず、公知の材料を使用できる。 The material of the substrate used as the chip substrate 106 is not particularly limited, and a known material can be used.
　チップ基板１０６の表面中央部には、撮像部１０２が設けられている。また、撮像部１０２の周縁領域に迷光が入射すると、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。硬化性組成物を用いて得られる硬化膜は遮光膜１１５として用いることが好ましい。 An imaging unit 102 is provided at the center of the surface of the chip substrate 106. Further, when stray light is incident on the peripheral area of the imaging unit 102, dark current (noise) is generated from a circuit in the peripheral area. Therefore, the peripheral area is shielded from light by providing a light shielding film 115. A cured film obtained using the curable composition 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 on the surface edge of the chip substrate 106. The electrode pad 108 is electrically connected to the imaging unit 102 via a signal line (not shown) provided on the surface of the chip substrate 106 (which may be a bonding wire).
　回路基板１０７の裏面には、各電極パッド１０８の略下方位置にそれぞれ外部接続端子１０９が設けられている。各外部接続端子１０９は、積層基板１０５を垂直に貫通する貫通電極１１０を介して、それぞれ電極パッド１０８に接続されている。また、各外部接続端子１０９は、図示しない配線を介して、固体撮像素子１０１の駆動を制御する制御回路、及び固体撮像素子１０１から出力される撮像信号に画像処理を施す画像処理回路等に接続されている。 External connection terminals 109 are provided on the back surface of the circuit board 107 at positions substantially below the electrode pads 108, respectively. Each external connection terminal 109 is connected to an electrode pad 108 via a through electrode 110 that vertically penetrates the multilayer substrate 105. Each external connection terminal 109 is connected to a control circuit that controls driving of the solid-state image sensor 101, an image processing circuit that performs image processing on an image signal output from the solid-state image sensor 101, and the like via a wiring (not shown). Has been.
　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。本発明の硬化性組成物を用いて得られる硬化膜は、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 is configured by each unit provided on a substrate 204 such as a light receiving element 201, a color filter 202, and a 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 using the curable composition of the present invention can also be used as the black matrix 205bm.
　基板２０４の材料としては、前述のチップ基板１０６と同様の材料を使用できる。基板２０４の表層にはｐウェル層２０６が形成されている。このｐウェル層２０６内には、ｎ型層からなり光電変換により信号電荷を生成して蓄積する受光素子２０１が正方格子状に配列形成されている。 As the material of the substrate 204, the same material as that of the above-described chip substrate 106 can be used. A p-well layer 206 is formed on the surface layer of the substrate 204. In the p-well layer 206, light receiving elements 201, which are n-type layers and generate and store signal charges by photoelectric conversion, are arranged in a square lattice pattern.
　受光素子２０１の一方の側方には、ｐウェル層２０６の表層の読み出しゲート部２０７を介して、ｎ型層からなる垂直転送路２０８が形成されている。また、受光素子２０１の他方の側方には、ｐ型層からなる素子分離領域２０９を介して、隣接画素に属する垂直転送路２０８が形成されている。読み出しゲート部２０７は、受光素子２０１に蓄積された信号電荷を垂直転送路２０８に読み出すためのチャネル領域である。 On one side of the light receiving element 201, a vertical transfer path 208 made of an n-type layer is formed via a readout gate portion 207 on the surface layer of the p-well layer 206. A vertical transfer path 208 belonging to an adjacent pixel is formed on the other side of the light receiving element 201 via an element isolation region 209 made of a p-type layer. The read gate unit 207 is a channel region for reading signal charges accumulated in the light receiving element 201 to the vertical transfer path 208.
　基板２０４の表面上には、ＯＮＯ（Ｏｘｉｄｅ－Ｎｉｔｒｉｄｅ－Ｏｘｉｄｅ）膜からなるゲート絶縁膜２１０が形成されている。このゲート絶縁膜２１０上には、垂直転送路２０８、読み出しゲート部２０７、及び、素子分離領域２０９の略直上を覆うように、ポリシリコン又はアモルファスシリコンからなる垂直転送電極２１１が形成されている。垂直転送電極２１１は、垂直転送路２０８を駆動して電荷転送を行わせる駆動電極と、読み出しゲート部２０７を駆動して信号電荷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. 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 signal charges. The signal charges are sequentially transferred from the vertical transfer path 208 to a horizontal transfer path (not shown) and an output unit (floating diffusion amplifier), and then output as a voltage signal.
　垂直転送電極２１１上には、その表面を覆うように遮光膜２１２が形成されている。遮光膜２１２は、受光素子２０１の直上位置に開口部を有し、それ以外の領域を遮光している。本発明の硬化性組成物を用いて得られる硬化膜は、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 directly above the light receiving element 201 and shields light from other areas. A cured film obtained using the curable composition of the present invention can also be used as the light shielding film 212.
On the light shielding film 212, an insulating film 213 made of BPSG (borophosphosilicate glass), an insulating film (passivation film) 214 made of P-SiN, and a transparent intermediate layer made of a planarizing film 215 made of transparent resin or the like are provided. ing. The color filter 202 is formed on the intermediate layer.
＜ブラックマトリクス＞
　本発明の硬化性組成物を用いて得られる硬化膜は、ブラックマトリクスに含有されることも好ましい。ブラックマトリクスは、カラーフィルタ、固体撮像素子、及び、液晶表示装置等の画像表示装置に含有される場合がある。
　ブラックマトリクスとしては、上記で既に説明したもの；液晶表示装置等の画像表示装置の周縁部に設けられた黒色の縁；赤、青、及び、緑の画素間の格子状、及び／又は、ストライプ状の黒色の部分；ＴＦＴ（ｔｈｉｎ　ｆｉｌｍ　ｔｒａｎｓｉｓｔｏｒ）遮光のためのドット状、及び／又は、線状の黒色パターン；等が挙げられる。このブラックマトリクスの定義については、例えば、菅野泰平著、「液晶ディスプレイ製造装置用語辞典」、第２版、日刊工業新聞社、１９９６年、ｐ．６４に記載がある。
　ブラックマトリクスは表示コントラストを向上させるため、また薄膜トランジスタ（ＴＦＴ）を用いたアクティブマトリックス駆動方式の液晶表示装置の場合には光の電流リークによる画質低下を防止するため、高い遮光性（光学濃度ＯＤで３以上）を有することが好ましい。 <Black matrix>
The cured film obtained using the curable composition of the present invention is also preferably 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; a black edge provided at the peripheral portion of an image display device such as a liquid crystal display device; a lattice between red, blue, and green pixels, and / or stripes A black part of the shape; a dot-like and / or a linear black pattern for TFT (thin film transistor) light shielding; and the like. For the definition of this black matrix, see Taihei Kanno, “Liquid Crystal Display Manufacturing Dictionary”, 2nd edition, Nikkan Kogyo Shimbun, 1996, p. 64.
The black matrix improves the display contrast, and in the case of an active matrix driving type liquid crystal display device using thin film transistors (TFTs), in order to prevent image quality deterioration due to light current leakage, it has a high light shielding property (with an optical density OD). 3 or more).
　ブラックマトリクスの製造方法としては特に制限されないが、上記の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 production method of the black matrix is not particularly limited, but can be produced by the same method as the production method of the cured film. Specifically, a curable composition can be applied to a substrate to form a curable composition layer, and 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ことが好ましい。このような材料としては、具体的には、例えば、ソーダライムガラス、無アルカリガラス、石英ガラス、及び、ホウケイ酸ガラス等のガラス；ポリエステル系樹脂、及び、ポリオレフィン系樹脂等のプラスチック；等が挙げられ、耐薬品性、及び、耐熱性の観点から、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 with respect to visible light (wavelength 400 to 800 nm). Specific examples of such materials include glass such as soda lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester resins and polyolefin resins; and the like. In view of chemical resistance and heat resistance, alkali-free glass or quartz glass is preferable.
＜カラーフィルタ＞
　本発明の硬化性組成物を用いて得られる硬化膜は、カラーフィルタに含有されることも好ましい。
　カラーフィルタが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>
The cured film obtained using the curable composition of the present invention is also preferably contained in a color filter.
The form in which the color filter contains a cured film is not particularly limited, and examples thereof include a color filter including a substrate and the black matrix. That is, a color filter including red, green, and blue colored pixels formed in the openings of the black matrix formed on the substrate can be exemplified.
　ブラックマトリクス（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してもよい。
　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。 A color filter containing a black matrix (cured film) can be produced, for example, by the following method.
First, a coating film (resin composition layer) of a resin composition containing a pigment corresponding to each colored pixel of a color filter is formed in an opening of a patterned black matrix formed on a substrate. The resin composition for each color is not particularly limited, and a known resin composition can be used. In the curable composition described in this specification, the black pigment is replaced with a colorant corresponding to each pixel. Things may be used.
Next, it exposes with respect to the resin composition layer through the photomask which has a pattern corresponding to the opening part of a black matrix. Next, after removing the unexposed portions by development processing, the colored pixels can be formed in the openings of the black matrix by baking. A color filter having red, green, and blue pixels can be manufactured by performing a series of operations using, for example, resin compositions for each color containing red, green, and blue pigments.
　上述したようなカラーフィルタは、例えば、液晶表示装置に使用されることも好ましい。
　その他、本発明の硬化性組成物を用いて得られる硬化膜（遮光膜）の用途に制限はなく、例えば、赤外線センサに使用してもよい。 The color filter as described above is also preferably used for a liquid crystal display device, for example.
In addition, there is no restriction | limiting in the use of the cured film (light-shielding film) obtained using the curable composition of this invention, For example, you may use for an infrared sensor.
　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, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the examples shown below.
〔硬化性組成物の調製〕
　以下に示す成分を使用して硬化性組成物を調製した。 (Preparation of curable composition)
A curable composition was prepared using the components shown below.
＜分散組成物及び黒色染料溶液＞
　以下の分散組成物（分散液）及び黒色染料溶液を作製して、硬化性組成物の調製に用いた。 <Dispersion composition and black dye solution>
The following dispersion composition (dispersion) and black dye solution were prepared and used for the preparation of the curable composition.
（Ａ－１：チタンブラック分散液（Ａ－１））
　下記に示す原料を使用してチタンブラック分散液（Ａ－１）を得た。
・チタンブラック（ａ－１）（詳細は後述する）
・樹脂（Ｘ－１）（樹脂Ｂに相当）
・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） (A-1: Titanium black dispersion (A-1))
A titanium black dispersion (A-1) was obtained using the following raw materials.
・ Titanium black (a-1) (details will be described later)
・ Resin (X-1) (equivalent to Resin B)
・ PGMEA (propylene glycol monomethyl ether acetate)
　上記樹脂（Ｘ－１）の構造は以下のとおりである。酸価は５８で、重量平均分子量は３２０００であった。また、各繰り返し単位に付した数字は、各ユニットのモル比を示す。 The structure of the resin (X-1) is as follows. The acid value was 58 and the weight average molecular weight was 32,000. Moreover, the number attached | subjected to each repeating unit shows the molar ratio of each unit.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　チタンブラック（ａ－１）（２０質量部）に対し、樹脂（Ｘ－１）（５．５質量部）を加え、更に、固形分濃度が３５質量％となるようにＰＧＭＥＡを加えた。
　得られた分散物を攪拌機により十分に攪拌し、プレミキシングを行った。得られた分散物に対し、シンマルエンタープライゼス製のＮＰＭ　Ｐｉｌｏｔを使用して下記分散条件にて分散処理を行い、チタンブラック分散液（Ａ－１）を得た。 Resin (X-1) (5.5 parts by mass) was added to titanium black (a-1) (20 parts by mass), and PGMEA was further added so that the solid content concentration was 35% by mass.
The obtained dispersion was sufficiently stirred with a stirrer and premixed. The obtained dispersion was subjected to a dispersion treatment using NPM Pilot manufactured by Shinmaru Enterprises under the following dispersion conditions to obtain a titanium black dispersion (A-1).
（分散条件）
・ビーズ径：φ０．０５ｍｍ
・ビーズ充填率：６５体積％
・ミル周速：１０ｍ／ｓｅｃ
・セパレーター周速：１１ｍ／ｓ
・分散処理する混合液量：１５．０ｇ
・循環流量（ポンプ供給量）：６０ｋｇ／ｈｏｕｒ
・処理液温度：２０～２５℃
・冷却水：水道水　５℃
・ビーズミル環状通路内容積：２．２Ｌ
・パス回数：８４パス (Distribution condition)
・ Bead diameter: φ0.05mm
・ Bead filling rate: 65% by volume
・ Mill peripheral speed: 10m / sec
・ Separator peripheral speed: 11m / s
・ Amount of liquid mixture for dispersion treatment: 15.0 g
・ Circulating flow rate (pump supply amount): 60 kg / hour
・ Processing liquid temperature: 20-25 ℃
・ Cooling water: tap water 5 ℃
・ Bead mill annular passage internal volume: 2.2L
・ Number of passes: 84 passes
・チタンブラック（ａ－１）の作製
　平均粒径１５ｎｍの酸化チタンＭＴ－１５０Ａ（商品名、テイカ製）（１００ｇ）、ＢＥＴ表面積３００ｍ２／ｇのシリカ粒子ＡＥＲＯＳＩＬ（登録商標）３００／３０（エボニック製）（２５ｇ）、及び、分散剤ＤＩＳＰＥＲＢＹＫ－１９０（商品名、ＢＹＫ社製）（１００ｇ）秤量し、イオン電気交換水（７１ｇ）を加えてＫＵＲＡＢＯ製ＭＡＺＥＲＳＴＡＲ　ＫＫ－４００Ｗを使用して、公転回転数１３６０ｒｐｍ、自転回転数１０４７ｒｐｍにて２０分間処理することにより均一な混合物水溶液を得た。この水溶液を石英容器に充填し、小型ロータリーキルン（株式会社モトヤマ製）を用いて酸素雰囲気中で９２０℃に加熱した後、窒素で雰囲気を置換し、同温度でアンモニアガスを１００ｍＬ／ｍｉｎで５時間流すことにより窒化還元処理を実施した。終了後回収した粉末を乳鉢で粉砕し、Ｓｉ原子を含有し、粉末状の比表面積７３ｍ２／ｇのチタンブラック（ａ－１）を得た。 Preparation of titanium black (a-1) Titanium oxide MT-150A (trade name, manufactured by Teika) (100 g) having an average particle diameter of 15 nm, silica particles AEROSIL (registered trademark) 300/30 (Evonik) having a BET surface area of 300 m 2 / g ) (25 g) and dispersant DISPERBYK-190 (trade name, manufactured by BYK) (100 g), weighed, added ion-exchange water (71 g), and revolved using KURABO MAZERSTAR KK-400W. A uniform mixture aqueous solution was obtained by treatment at several 1360 rpm and a rotational speed of 1047 rpm for 20 minutes. This aqueous solution is filled in a quartz container, heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.), then the atmosphere is replaced with nitrogen, and ammonia gas is kept at 100 mL / min for 5 hours at the same temperature. The nitriding reduction treatment was carried out by flowing. After the completion, the recovered powder was pulverized in a mortar to obtain titanium black (a-1) containing Si atoms and having a powdery specific surface area of 73 m 2 / g.
（Ａ－２：カーボンブラック分散液（Ａ－２））
　下記に示す原料を使用してカーボンブラック分散液（Ａ－２）を得た。
・被覆カーボンブラック（詳細は後述する）
・樹脂（Ｘ－１）（樹脂Ｂに相当、チタンブラック分散液（Ａ－１）の調製に使用したものと同じ）
・ソルスパース１２０００（顔料誘導体、ルーブリゾール社製）
・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） (A-2: Carbon black dispersion (A-2))
A carbon black dispersion (A-2) was obtained using the raw materials shown below.
・ Coated carbon black (details will be described later)
Resin (X-1) (equivalent to Resin B, the same as that used for the preparation of titanium black dispersion (A-1))
Solsperse 12000 (pigment derivative, manufactured by Lubrizol)
・ PGMEA (propylene glycol monomethyl ether acetate)
　被覆カーボンブラック（２０質量部）に対し、樹脂（Ｘ－１）（４．５質量部）、及び、ソルスパース１２０００（１質量部）を加え、更に、固形分濃度が３５質量％となるようにＰＧＭＥＡを加えた。
　得られた混合液を攪拌機により十分に攪拌し、プレミキシングを行った。更に、分散物に対し、寿工業（株）製のウルトラアペックスミルＵＡＭ０１５を使用して下記分散条件にて分散処理を行い、分散組成物を得た。分散終了後、フィルタによりビーズと分散液を分離して、カーボンブラック分散液（Ａ－２）を調製した。 Resin (X-1) (4.5 parts by mass) and Solsperse 12000 (1 part by mass) are added to the coated carbon black (20 parts by mass), and the solid content concentration is further 35% by mass. PGMEA was added.
The obtained mixed liquid was sufficiently stirred with a stirrer and premixed. Furthermore, the dispersion was subjected to a dispersion treatment under the following dispersion conditions using an Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. to obtain a dispersion composition. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a carbon black dispersion (A-2).
（分散条件）
・ビーズ径：φ０．０５ｍｍ
・ビーズ充填率：７５体積％
・ミル周速：８ｍ／ｓｅｃ
・分散処理する混合液量：５００ｇ
・循環流量（ポンプ供給量）：１３ｋｇ／ｈｏｕｒ
・処理液温度：２５～３０℃
・冷却水：水道水
・ビーズミル環状通路内容積：０．１５Ｌ
・パス回数：９０パス (Distribution condition)
・ Bead diameter: φ0.05mm
・ Bead filling rate: 75% by volume
・ Mill peripheral speed: 8m / sec
・ Amount of liquid mixture to be dispersed: 500 g
・ Circulation flow rate (pump supply amount): 13 kg / hour
・ Processing liquid temperature: 25-30 ℃
・ Cooling water: Tap water ・ Bead mill annular passage volume: 0.15L
・ Number of passes: 90 passes
・被覆カーボンブラックの作製
　通常のオイルファーネス法で、カーボンブラックを製造した。ただし、原料油としては、Ｎａ分量、Ｃａ分量、及び、Ｓ分量の少ないエチレンボトム油を用い、ガス燃料を用いて燃焼を行った。更に、反応停止水としては、イオン交換樹脂で処理した純水を用いた。
　ホモミキサーを用いて、得られたカーボンブラック（５４０ｇ）を純水（１４５００ｇ）と共に５，０００～６，０００ｒｐｍで３０分撹拌し、スラリーを得た。このスラリーをスクリュー型撹拌機付容器に移して、約１，０００ｒｐｍで混合しながらエポキシ樹脂「エピコート８２８」（ジャパンエポキシレジン製）（６０ｇ）を溶解したトルエン（６００ｇ）を少量ずつ添加した。約１５分で、水に分散していたカーボンブラックは全量トルエン側に移行し、約１ｍｍの粒子となった。
　次に、６０メッシュ金網で水切りを行った後、分離された粒を真空乾燥機に入れ、７０℃で７時間乾燥し、トルエン及び水を除去した。得られた被覆カーボンブラックの樹脂被覆量は、カーボンブラックと樹脂の合計量に対して１０質量％であった。 -Production of coated carbon black Carbon black was produced by a normal oil furnace method. However, as the raw material oil, an ethylene bottom oil having a small Na content, Ca content, and S content was used, and combustion was performed using gas fuel. Furthermore, pure water treated with an ion exchange resin was used as the reaction stop water.
Using a homomixer, the obtained carbon black (540 g) was stirred with pure water (14500 g) at 5,000 to 6,000 rpm for 30 minutes to obtain a slurry. The slurry was transferred to a container with a screw type stirrer, and toluene (600 g) in which an epoxy resin “Epicoat 828” (manufactured by Japan Epoxy Resin) (60 g) was dissolved was added little by little while mixing at about 1,000 rpm. In about 15 minutes, the entire amount of carbon black dispersed in water moved to the toluene side and became particles of about 1 mm.
Next, after draining with a 60 mesh wire net, the separated particles were put into a vacuum dryer and dried at 70 ° C. for 7 hours to remove toluene and water. The resin coating amount of the obtained coated carbon black was 10% by mass with respect to the total amount of carbon black and resin.
（Ａ－３：黒色染料溶液（Ａ－３））
　下記に示す原料を使用して黒色染料溶液（Ａ－３）を得た。
・ＶＡＬＩＦＡＳＴ　ＢＬＡＣＫ　３８０４（黒色染料、オリエント化学工業製）
・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） (A-3: Black dye solution (A-3))
A black dye solution (A-3) was obtained using the following raw materials.
・ VALIFAST BLACK 3804 (black dye, manufactured by Orient Chemical Industries)
・ PGMEA (propylene glycol monomethyl ether acetate)
　ＶＡＬＩＦＡＳＴ　ＢＬＡＣＫ　３８０４（オリエント化学工業製）（２６．８質量部）に、ＰＧＭＥＡ（７３．２質量部）を加え、溶解させることにより黒色染料溶液（Ａ－３）を調製した。 A black dye solution (A-3) was prepared by adding PGMEA (73.2 parts by mass) to VALIFAST BLACK 3804 (manufactured by Orient Chemical Industries) (26.8 parts by mass) and dissolving it.
＜樹脂（樹脂溶液）＞
　下記構造１又は構造２で表される樹脂を含有する樹脂溶液（Ｂ－１）～（Ｂ－９）を、硬化性組成物の調製に用いた。
　構造式において、各繰り返し単位に付された数字（Ｘ及びＹも数字とする）は、各繰り返し単位の樹脂中における含有量（モル比）を意図する。
　構造１の樹脂においては、それぞれの樹脂の酸価が表１に示す値となるように、Ｘ及びＹの比を適宜変更させた。 <Resin (resin solution)>
Resin solutions (B-1) to (B-9) containing a resin represented by the following structure 1 or structure 2 were used for the preparation of the curable composition.
In the structural formula, the numbers given to each repeating unit (X and Y are also numbers) intend the content (molar ratio) in the resin of each repeating unit.
In the resin of structure 1, the ratio of X and Y was appropriately changed so that the acid value of each resin would be the value shown in Table 1.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　樹脂溶液（Ｂ－１）～（Ｂ－９）に含まれる樹脂の構造、並びに、その分子量及び酸価を下記表に示す。
　また、樹脂溶液に含まれる樹脂と溶剤（ＰＧＭＥＡ）との含有量の割合（質量比）も下記表に示す。
　樹脂溶液（Ｂ－１）～（Ｂ－５）が含有する樹脂が、樹脂Ａに相当する。 The structures of the resins contained in the resin solutions (B-1) to (B-9), their molecular weights and acid values are shown in the following table.
Moreover, the ratio (mass ratio) of content of resin and solvent (PGMEA) contained in the resin solution is also shown in the following table.
Resins contained in the resin solutions (B-1) to (B-5) correspond to the resin A.
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023
＜光重合開始剤＞
　以下の光重合開始剤を、硬化性組成物の調製に用いた。
・Ｃ－１：ＩＲＧＡＣＵＲＥ　ＯＸＥ－０３（ＢＡＳＦ製）
・Ｃ－２：ＩＲＧＡＣＵＲＥ　ＯＸＥ－０２（ＢＡＳＦ製）
・Ｃ－３：ＩＲＧＡＣＵＲＥ　３６９（ＢＡＳＦ製）
　なお、上記光重合性化合物の内、Ｃ－１及びＣ－２は、オキシムエステル系重合開始剤である。
　また、Ｃ－１は、以下に示す構造を有する。 <Photopolymerization initiator>
The following photoinitiators were used for the preparation of the curable composition.
・ C-1: IRGACURE OXE-03 (manufactured by BASF)
・ C-2: IRGACURE OXE-02 (BASF)
・ C-3: IRGACURE 369 (BASF)
Of the photopolymerizable compounds, C-1 and C-2 are oxime ester polymerization initiators.
C-1 has the following structure.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
＜重合性化合物＞
　以下の重合性化合物を、硬化性組成物の調製に用いた。
・Ｄ－１：「Ｃ－（ＣＨ２ＯＯＣ－ＣＨ＝ＣＨ２）４」で表される化合物。（４官能、二重結合当量１１．３ｍｍｏｌ／ｇ）
・Ｄ－２：下記化合物（５～６官能、二重結合当量１０．１ｍｍｏｌ／ｇ）
・Ｄ－３：下記化合物（４官能、二重結合当量７．６ｍｍｏｌ／ｇ）
　上記「官能」の値は、重合性化合物１分子が有するエチレン性不飽和基の数を示す。
　なお、Ｄ－２は、５官能の重合性化合物と６官能の重合性化合物とが混在しており、その混合比は、５官能の重合性化合物／６官能の重合性化合物＝３０／７０（質量比）である。Ｄ－２全体としての二重結合当量（６官能の重合性化合物及び５官能の重合性化合物の、二重結合当量の加重平均の値）が１０．１ｍｍｏｌ／ｇである。 <Polymerizable compound>
The following polymerizable compounds were used in the preparation of the curable composition.
D-1: a compound represented by “C— (CH 2 OOC—CH═CH 2 ) 4 ”. (Tetrafunctional, double bond equivalent 11.3 mmol / g)
D-2: the following compound (5-6 functional, double bond equivalent 10.1 mmol / g)
D-3: The following compound (tetrafunctional, double bond equivalent 7.6 mmol / g)
The value of the above “functionality” indicates the number of ethylenically unsaturated groups that one molecule of the polymerizable compound has.
Note that D-2 is a mixture of a pentafunctional polymerizable compound and a hexafunctional polymerizable compound, and the mixing ratio thereof is pentafunctional polymerizable compound / 6 hexafunctional polymerizable compound = 30/70 ( Mass ratio). The double bond equivalent (the weighted average value of the double bond equivalents of the hexafunctional polymerizable compound and the pentafunctional polymerizable compound) as a whole of D-2 is 10.1 mmol / g.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
＜界面活性剤＞
　以下の界面活性剤を、硬化性組成物の調製に用いた。
・Ｅ－１：下記構造式で表される界面活性剤
　なお、下記構造式中の各繰り返し単位に付された数字は、各繰り返し単位のモル比を示す。また、構造式中、ｍ１＝１７、ｍ２＝１７、ｌ１＋ｎ１＝１４、ｌ２＋ｎ２＝１４である。重量平均分子量は１５０００である。 <Surfactant>
The following surfactants were used in the preparation of the curable composition.
E-1: Surfactant represented by the following structural formula The numbers given to each repeating unit in the following structural formula indicate the molar ratio of each repeating unit. In the structural formula, m 1 = 17, m 2 = 17, l 1 + n 1 = 14, and l 2 + n 2 = 14. The weight average molecular weight is 15000.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
＜重合禁止剤＞
　以下の重合禁止剤を、硬化性組成物の調製に用いた。
・ｐ－メトキシフェノール <Polymerization inhibitor>
The following polymerization inhibitors were used in the preparation of the curable composition.
・ P-Methoxyphenol
＜溶剤＞
　以下の溶剤を、硬化性組成物の調製に用いた。
・シクロヘキサノン <Solvent>
The following solvents were used in the preparation of the curable composition.
・ Cyclohexanone
　上述の成分を混合して、各実施例又は各比較例で使用する、硬化性組成物を調製した。 The above components were mixed to prepare a curable composition to be used in each example or each comparative example.
〔試験〕
＜線幅の測定（線幅安定性）＞
　調製直後の硬化性組成物を、ガラス基板上にスピンコート法により塗布して、露光後の膜厚が１．７μｍになるような塗膜を形成した。１００℃で１２０秒のプリベークを行った後、得られた硬化性組成物層に対して、ＵＸ－１０００ＳＭ－ＥＨ０４（ウシオ電機（株）製）を用いて、高圧水銀ランプ（ランプパワー５０ｍＷ／ｃｍ２）で、開口線幅５０μｍのラインアンドスペースパターンのマスクを介したプロキシミティ方式による露光（プロキシミティ露光）を行った。
　この際、露光量は、現像後に得られるパターンのライン部の幅（線幅）の平均値（１００点の平均値）が５０μｍになるように調整した。
　露光後、現像装置（ＡＤ－１２００、ミカサ製）を使用して、現像液（ＣＤ－２０６０、富士フイルムエレクトロニクスマテリアルズ社製）で１５秒間、パドル法による現像を行った。更に、シャワーノズルを用いて純水で３０秒洗浄し、基板上にパターン状の硬化膜（単に「パターン」ともいう）を形成した。
　光学顕微鏡を用いてパターンの線幅を測定（１００点）し、線幅のバラつき（３σ）を、以下の観点により評価した。 〔test〕
<Measurement of line width (stability of line width)>
The curable composition immediately after the preparation was applied on a glass substrate by a spin coating method to form a coating film having a film thickness after exposure of 1.7 μm. After pre-baking at 100 ° C. for 120 seconds, the resulting curable composition layer was subjected to high pressure mercury lamp (lamp power 50 mW / cm) using UX-1000SM-EH04 (USHIO INC.). In 2 ), exposure by proximity method (proximity exposure) through a mask of a line and space pattern with an opening line width of 50 μm was performed.
At this time, the exposure amount was adjusted so that the average value (the average value of 100 points) of the width (line width) of the line portion of the pattern obtained after development was 50 μm.
After the exposure, using a developing device (AD-1200, manufactured by Mikasa), development was performed by a paddle method for 15 seconds with a developer (CD-2060, manufactured by FUJIFILM Electronics Materials). Further, it was washed with pure water for 30 seconds using a shower nozzle to form a patterned cured film (also simply referred to as “pattern”) on the substrate.
The line width of the pattern was measured using an optical microscope (100 points), and the line width variation (3σ) was evaluated from the following viewpoints.
Ａ：線幅のバラつきが、４μｍ以下
Ｂ：線幅のバラつきが、４μｍ超８μｍ以下
Ｃ：線幅のバラつきが、８μｍ超 A: Line width variation is 4 μm or less B: Line width variation is more than 4 μm and 8 μm or less C: Line width variation is more than 8 μm
＜アンダーカット幅の測定（アンダーカット抑制性）＞
　線幅の測定の試験と同様にして、基板上にパターンを形成した。
　走査型電子顕微鏡（ＳＥＭ、Ｓ－４８００（日立ハイテクノロジーズ（株）））を用いてパターンの断面ＳＥＭ像を観察し、アンダーカット幅を測定し、以下の観点により、評価した。 <Measurement of undercut width (undercut suppression)>
A pattern was formed on the substrate in the same manner as in the line width measurement test.
The cross-sectional SEM image of the pattern was observed using a scanning electron microscope (SEM, S-4800 (Hitachi High-Technologies Corporation)), the undercut width was measured, and evaluated from the following viewpoints.
Ａ：アンダーカット幅が、１．２μｍ未満で問題ないレベル
Ｂ：アンダーカット幅が、１．２μｍ以上１．８μｍ未満で実用上問題ないレベル
Ｃ：アンダーカット幅が、１．８μｍ以上で実用上問題あるレベル A: There is no problem when the undercut width is less than 1.2 μm B: Practically no problem when the undercut width is 1.2 μm or more and less than 1.8 μm C: Practical when the undercut width is 1.8 μm or more Problem level
＜剥がれの測定（剥がれ抑制性）＞
　線幅の測定の試験と同様にして、基板上にパターンを形成した。
　光学顕微鏡を用いてパターンの表面の顕微鏡画像を観察し、パターン剥がれの有無に関して以下の観点により、評価した。 <Measurement of peeling (peeling suppression)>
A pattern was formed on the substrate in the same manner as in the line width measurement test.
A microscopic image of the surface of the pattern was observed using an optical microscope, and the presence or absence of pattern peeling was evaluated from the following viewpoints.
Ａ：パターン全体で剥がれが見られず問題ないレベル
Ｂ：一部パターンで剥がれが見られるが実用上問題ないレベル
Ｃ：パターンの大部分が剥がれており実用上問題あるレベル A: There is no problem in that peeling is not observed in the entire pattern. B: Peeling is observed in a part of the pattern, but there is no problem in practical use. C: A level in which most of the pattern is peeled off and practically problematic.
＜残渣の測定（残渣抑制性）＞
　線幅の測定の試験と同様にして、基板上にパターンを形成した。
　走査型電子顕微鏡（Ｓ－４８００（日立ハイテクノロジーズ（株）））を用いて、基板上の、現像工程で硬化性組成物層が除去された箇所を観察し、以下の観点により、評価した。 <Measurement of residue (residue suppression)>
A pattern was formed on the substrate in the same manner as in the line width measurement test.
Using a scanning electron microscope (S-4800 (Hitachi High-Technologies Corporation)), the portion of the substrate where the curable composition layer was removed in the development process was observed and evaluated from the following viewpoints.
Ａ：残渣が全く見られず問題ないレベル
Ｂ：一部残渣が見られるが実用上問題ないレベル
Ｃ：残渣が多く見られ実用上問題あるレベル A: Level where no residue is observed and no problem B: Partial residue is observed but there is no problem in practical use C: Level in which a large amount of residue is observed and practical problem
＜反射率の評価＞
　露光の際にマスクを用いずに光を照射したこと以外は、線幅の測定の試験と同様にして、基板上に硬化膜を有する、硬化膜形成基板を作製した。
　作製した硬化膜形成基板に対し、日本分光株式会社製分光器（製品名：Ｖ７２００、絶対反射率測定ユニットを併用）を用いて、角度５°の入射角で波長５００ｎｍの光を入射して測定した反射率から、以下の観点により評価した。反射率は、小さい方が好ましい。 <Evaluation of reflectance>
A cured film-formed substrate having a cured film on the substrate was produced in the same manner as in the line width measurement test except that light was irradiated without using a mask during exposure.
Measured by using a spectroscope manufactured by JASCO Corporation (product name: V7200, combined with an absolute reflectance measurement unit) and incident light with a wavelength of 500 nm on an incident angle of 5 ° on the produced cured film forming substrate. The reflectance was evaluated from the following viewpoints. A smaller reflectance is preferable.
Ａ：反射率が３％未満で問題ないレベル
Ｂ：反射率が３％以上５％未満で実用上問題ないレベル
Ｃ：反射率が５％以上７％未満で実用上問題ないレベル
Ｄ：反射率が７％以上で実用上問題あるレベル A: No problem when the reflectivity is less than 3% B: No problem for practical use with a reflectivity of 3% or more and less than 5% C: No problem for practical use when the reflectivity is 5% or more but less than 7% D: Reflectance Is more than 7% and is a practically problematic level
＜反射率の変化率の評価（反射率の経時安定性）＞
　調製後の硬化性組成物を、２３℃において１０日間保存した後、更に、７℃において９０日間保存した。このような保存処理後の硬化性組成物を使用した点以外は上述したのと同様にして反射率の評価を行い、得られた結果から反射率の変化率を下記式に従って算出し、以下の基準で反射率の経時安定性を評価した。反射率の変化率は、小さい方が好ましい。
（式）（反射率の変化率）＝（（（保存処理後の硬化性組成物を用いて形成された硬化膜の反射率）－（保存処理前の硬化性組成物を用いて形成された硬化膜の反射率））／（保存処理前の硬化性組成物を用いて形成された硬化膜の反射率））×１００（％） <Evaluation of reflectance change rate (stability of reflectance over time)>
The curable composition after preparation was stored at 23 ° C. for 10 days, and further stored at 7 ° C. for 90 days. Except for using such a curable composition after storage treatment, the reflectance is evaluated in the same manner as described above, and the change rate of the reflectance is calculated according to the following formula from the obtained results. The stability of reflectance over time was evaluated based on the standard. A smaller change rate of reflectance is preferable.
(Formula) (Change rate of reflectance) = (((Reflectance of cured film formed using curable composition after storage treatment) − (Formed using curable composition before storage treatment) Reflectivity of cured film)) / (Reflectivity of cured film formed using curable composition before storage treatment)) × 100 (%)
Ａ：反射率の変化率が５％未満で問題ないレベル。
Ｂ：反射率の変化率が５％以上で問題あるレベル。 A: The rate of change in reflectivity is less than 5%, and there is no problem.
B: A problem level when the reflectance change rate is 5% or more.
＜線幅の変化率の評価（線幅の経時安定性）＞
　調製後の硬化性組成物を、２３℃において１０日間保存した後、更に、７℃において９０日間保存した。
　このような保存処理後の硬化性組成物を使用して、線幅の測定の試験と同様にパターンを形成した。ただしここでは、保存処理前の硬化性組成物を使用して線幅５０μｍのパターンを形成した際の露光量と同一の露光量で露光した。
　得られたパターンの線幅を１００点測定した平均値を、保存処理後の硬化性組成物を用いて形成されたパターンの線幅とした。
　得られた結果から線幅の変化率を下記式に従って算出し、以下の基準で線幅の経時安定性を評価した。線幅の変化率は、小さい方が好ましい。
（式）（線幅の変化率）＝（（（保存処理後の硬化性組成物を用いて形成されたパターンの線幅）－（保存処理前の硬化性組成物を用いて形成されたパターンの線幅））／（保存処理前の硬化性組成物を用いて形成されたラインパターンの線幅））×１００（％） <Evaluation of change rate of line width (stability of line width over time)>
The curable composition after preparation was stored at 23 ° C. for 10 days, and further stored at 7 ° C. for 90 days.
Using such a curable composition after storage treatment, a pattern was formed in the same manner as in the line width measurement test. However, here, the exposure was performed at the same exposure amount as that when a pattern having a line width of 50 μm was formed using the curable composition before the storage treatment.
The average value obtained by measuring the line width of the obtained pattern at 100 points was defined as the line width of the pattern formed using the curable composition after the storage treatment.
From the obtained results, the rate of change of the line width was calculated according to the following formula, and the temporal stability of the line width was evaluated according to the following criteria. A smaller change rate of the line width is preferable.
(Formula) (Line width change rate) = (((Line width of pattern formed using curable composition after storage treatment)-(Pattern formed using curable composition before storage treatment) Line width)) / (line width of line pattern formed using curable composition before storage treatment)) × 100 (%)
Ａ：線幅の変化率が５％未満で問題ないレベル。
Ｂ：線幅の変化率が５％以上で問題あるレベル。 A: The change rate of the line width is less than 5% and no problem.
B: A problem level when the change rate of the line width is 5% or more.
〔結果〕
　下記表に、各実施例及び比較例で使用した硬化性組成物の配合、並びに、試験結果を示す。
　なお、比較例１及び４の化合物においては、パターンを形成できなかった。
　表中、「含有量」の欄は、各硬化性組成物中における各成分の含有量（質量％）を示す。溶剤の含有量としての「残部」の記載は、表に記載の各成分の含有量の合計が１００になるように必要な量の溶剤を添加したことを示す。
　例えば、実施例１の硬化性組成物は、チタンブラック分散液（Ａ－１）を、６３質量％含有することを示す。
　「樹脂の酸価」の欄は、硬化性組成物に使用した樹脂溶液が含有する樹脂の酸価を示す。
　「樹脂の分子量」の欄は、硬化性組成物に使用した樹脂溶液が含有する樹脂の重量平均分子量を示す。
　「樹脂Ｂ」の欄は、硬化性組成物が樹脂Ｂを含有するか否かを示す。上記要件を満たす場合をＡとし、満たさない場合をＢとした。
　「オキシム系光重合開始剤」の欄は、硬化性組成物が含有する光重合開始剤がオキシムエステル系重合開始剤であるか否かを示す。上記要件を満たす場合をＡとし、満たさない場合をＢとした。
　「特定光重合開始剤」の欄は、硬化性組成物が含有する光重合開始剤が特定重合開始剤であるか否かを示す。上記要件を満たす場合をＡとし、満たさない場合をＢとした。
　「黒色色材の種類」の欄は、硬化性組成物が含有する黒色色材の種類を示す。ＴＢは、チタンブラック（窒化チタン）を意図し、ＣＢはカーボンブラックを意図し、黒染料は黒色染料を意図する。
　「重合性化合物の官能基数」の欄は、硬化性組成物が含有する重合性化合物が有するエチレン性不飽和基の数を示す。 〔result〕
The following table shows the composition of the curable compositions used in each Example and Comparative Example, and the test results.
In addition, in the compounds of Comparative Examples 1 and 4, a pattern could not be formed.
In the table, the “content” column indicates the content (% by mass) of each component in each curable composition. The description of “balance” as the content of the solvent indicates that a necessary amount of the solvent was added so that the total content of each component described in the table was 100.
For example, it shows that the curable composition of Example 1 contains 63% by mass of the titanium black dispersion (A-1).
The column “Resin acid value” indicates the acid value of the resin contained in the resin solution used in the curable composition.
The column of “molecular weight of resin” indicates the weight average molecular weight of the resin contained in the resin solution used in the curable composition.
The column “Resin B” indicates whether or not the curable composition contains the resin B. The case where the above requirements were satisfied was designated as A, and the case where the above requirements were not satisfied was designated as B.
The column of “oxime photopolymerization initiator” indicates whether or not the photopolymerization initiator contained in the curable composition is an oxime ester polymerization initiator. The case where the above requirements were satisfied was designated as A, and the case where the above requirements were not satisfied was designated as B.
The column of “specific photopolymerization initiator” indicates whether or not the photopolymerization initiator contained in the curable composition is a specific polymerization initiator. The case where the above requirements were satisfied was designated as A, and the case where the above requirements were not satisfied was designated as B.
The column “type of black color material” indicates the type of black color material contained in the curable composition. TB is intended for titanium black (titanium nitride), CB is intended for carbon black, and black dye is intended for black dye.
The column “number of functional groups of polymerizable compound” indicates the number of ethylenically unsaturated groups that the polymerizable compound contained in the curable composition has.
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
　本発明の硬化性組成物を使用すれば、線幅安定性に優れる硬化膜（パターン状硬化膜を含有する）を形成できることが確認された。
　また、重合禁止剤を含有しない比較例５の硬化性組成物では、得られる硬化膜の線幅の経時安定性については問題がない一方で、反射率の経時安定性には問題があった。対して、重合禁止剤を含有する本発明の硬化性組成物は、得られる硬化膜の反射率の経時安定性も良好であった。
　硬化性組成物が樹脂Ｂを含有する場合、硬化膜の反射率がより優れることが確認された（実施例５と６との比較）。
　黒色色材として黒色顔料を使用する場合、硬化膜の反射率がより優れ（実施例５と６との比較）、更に、黒色顔料がチタンブラック（チタン窒化物）である場合、硬化膜の剥がれ抑制性がより優れることが確認された（実施例１と５との比較）。
　要件１を満たす樹脂Ａの酸価が、１７０～３００ｍｇＫＯＨ／ｇである場合、硬化膜の線幅安定性、アンダーカット抑制性、及び、反射率がより優れることが確認された（実施例１と８との比較）。
　要件２を満たす樹脂Ａの重量平均分子量が、６５００以下である場合、硬化膜の残渣抑制性がより優れ（実施例９と１０との比較）、３０００～５０００である場合、硬化膜の線幅安定性、アンダーカット抑制性、及び、反射率がより優れることが確認された（実施例１と９との比較）。
　光重合性化合物が、オキシム系光重合開始剤である場合、硬化膜の線幅安定性及びアンダーカット抑制性がより優れ（実施例３と１２との比較）、特定光重合開始剤である場合、硬化膜の剥がれ抑制性がより優れることが確認された（実施例１と３との比較）。
　重合性化合物が有するエチレン性不飽和基の数が４個である場合、硬化膜の反射率がより優れ（実施例７とその他の実施例との比較）、更に、重合性化合物の二重結合当量が１１．０ｍｍｏｌ／ｇ以上である場合、硬化膜の線幅安定性、アンダーカット抑制性、剥がれ抑制性、及び、反射率がより優れることが確認された（実施例１と１１との比較）。 It was confirmed that if the curable composition of the present invention is used, a cured film (containing a patterned cured film) having excellent line width stability can be formed.
Moreover, in the curable composition of Comparative Example 5 containing no polymerization inhibitor, there was no problem with the temporal stability of the line width of the resulting cured film, but there was a problem with the temporal stability of the reflectance. On the other hand, the curable composition of the present invention containing a polymerization inhibitor also had good stability over time of the reflectance of the resulting cured film.
When the curable composition contained the resin B, it was confirmed that the reflectance of the cured film was more excellent (comparison between Examples 5 and 6).
When a black pigment is used as the black color material, the reflectance of the cured film is more excellent (comparison with Examples 5 and 6). Further, when the black pigment is titanium black (titanium nitride), the cured film is peeled off. It was confirmed that the inhibitory properties were more excellent (comparison between Examples 1 and 5).
When the acid value of the resin A satisfying the requirement 1 is 170 to 300 mgKOH / g, it was confirmed that the cured film had more excellent line width stability, undercut suppression, and reflectance (Example 1 and Comparison with 8).
When the weight average molecular weight of the resin A satisfying Requirement 2 is 6500 or less, the residual suppression of the cured film is more excellent (comparison with Examples 9 and 10). When the weight average molecular weight is 3000 to 5000, the line width of the cured film It was confirmed that the stability, the undercut suppressing property, and the reflectance were more excellent (comparison between Examples 1 and 9).
When the photopolymerizable compound is an oxime photopolymerization initiator, the cured film has more excellent line width stability and undercut suppression (comparison with Examples 3 and 12), and is a specific photopolymerization initiator. Further, it was confirmed that the cured film was more excellent in inhibition of peeling (comparison between Examples 1 and 3).
When the number of ethylenically unsaturated groups contained in the polymerizable compound is 4, the cured film has more excellent reflectivity (comparison between Example 7 and other examples), and further the double bond of the polymerizable compound When the equivalent was 11.0 mmol / g or more, it was confirmed that the line width stability, the undercut suppressing property, the peeling suppressing property, and the reflectance of the cured film were more excellent (Comparison with Examples 1 and 11). ).
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

  DESCRIPTION OF SYMBOLS 100 ... Solid-state imaging device 101 ... Solid-state image sensor 102 ... Imaging part 103 ... Cover glass 104 ... Spacer 105 ... Laminated substrate 106 ... Chip substrate 107 ... Circuit board 108 ... Electrode pad 109 ... External connection terminal 110 ... Penetration electrode 111 ... Lens layer 112 ... Lens material 113 ... Supports 114, 115 ... Curing film 201 ... Light receiving element 202 ... Color filter 201 ... Light receiving element 202 ... Color filter 203 ... Micro lens 204 ... Substrate 205b ... Blue pixel 205r ... Red pixel 205g ... Green pixel 205bm ... Black matrix 206... P well layer 207... Readout gate portion 208... Vertical transfer path 209. Over gate insulating film 211 ... vertical transfer electrodes 212 ... cured film 213 ... insulating film 215 ... flattening film

Claims (17)

  1. 　黒色色材、重合性化合物、樹脂Ａ、光重合開始剤、及び、重合禁止剤を含有し、
    　前記樹脂Ａが、酸価が１２０～３５０ｍｇＫＯＨ／ｇであること、及び、重量平均分子量が３０００～７５００であることのいずれか一方の要件を満たす、硬化性組成物。     Contains black color material, polymerizable compound, resin A, photopolymerization initiator, and polymerization inhibitor,
    A curable composition, wherein the resin A satisfies any one of an acid value of 120 to 350 mgKOH / g and a weight average molecular weight of 3000 to 7500.
  2. 　前記重合性化合物の含有量に対する、前記重合禁止剤の含有量の質量比が、０．０００５超である、請求項１に記載の硬化性組成物。 The curable composition according to claim 1, wherein a mass ratio of the content of the polymerization inhibitor to the content of the polymerizable compound is more than 0.0005.
  3. 　更に、前記樹脂Ａとは異なる樹脂であって、オキシアルキレン基及びオキシアルキレンカルボニル基からなる群から選択される１種以上の基を有する樹脂である樹脂Ｂを含有する、請求項１又は２に記載の硬化性組成物。 Furthermore, the resin B is a resin different from the resin A, and the resin B is a resin having one or more groups selected from the group consisting of oxyalkylene groups and oxyalkylenecarbonyl groups. The curable composition as described.
  4. 　前記重合性化合物が、４個のエチレン性不飽和基を有する、請求項１～３のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 3, wherein the polymerizable compound has four ethylenically unsaturated groups.
  5. 　前記樹脂Ａの酸価が１７０～３００ｍｇＫＯＨ／ｇである、請求項１～４のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 4, wherein the acid value of the resin A is 170 to 300 mgKOH / g.
  6. 　前記樹脂Ａの重量平均分子量が３０００～５０００である、請求項１～５のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 5, wherein the resin A has a weight average molecular weight of 3,000 to 5,000.
  7. 　前記樹脂Ａの全繰り返し単位中、（メタ）アクリル系単量体由来の繰り返し単位の含有量が５０モル％以上である、請求項１～６のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 6, wherein the content of repeating units derived from (meth) acrylic monomers is 50 mol% or more in all repeating units of the resin A.
  8. 　前記樹脂Ａが、ベンジル（メタ）アクリレート及び（メタ）アクリル酸の共重合体である、請求項１～７のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 7, wherein the resin A is a copolymer of benzyl (meth) acrylate and (meth) acrylic acid.
  9. 　前記重合性化合物の二重結合当量が、１１．０ｍｍｏｌ／ｇ以上である、請求項１～８のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 8, wherein the double bond equivalent of the polymerizable compound is 11.0 mmol / g or more.
  10. 　前記光重合開始剤が、オキシムエステル系重合開始剤である、請求項１～９のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 9, wherein the photopolymerization initiator is an oxime ester polymerization initiator.
  11. 　前記光重合開始剤が、下記一般式（Ａ）で表される化合物である、請求項１～１０のいずれか１項に記載の硬化性組成物。
    Figure JPOXMLDOC01-appb-C000001
         The curable composition according to any one of claims 1 to 10, wherein the photopolymerization initiator is a compound represented by the following general formula (A).
    Figure JPOXMLDOC01-appb-C000001
  12. 　前記黒色色材が、黒色顔料である、請求項１～１１のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 11, wherein the black color material is a black pigment.
  13. 　請求項１～１２のいずれか１項に記載の硬化性組成物を用いて形成される、硬化膜。 A cured film formed using the curable composition according to any one of claims 1 to 12.
  14. 　遮光膜である、請求項１３に記載の硬化膜。 The cured film according to claim 13, which is a light shielding film.
  15. 　請求項１３又は１４に記載の硬化膜を有する、光学素子。 An optical element having the cured film according to claim 13 or 14.
  16. 　請求項１３又は１４に記載の硬化膜を有する、固体撮像素子。 A solid-state imaging device having the cured film according to claim 13 or 14.
  17. 　請求項１３又は１４に記載の硬化膜を有する、カラーフィルタ。

          A color filter comprising the cured film according to claim 13 or 14.

PCT/JP2019/005476 2018-03-08 2019-02-15 Curable composition, cured film, optical element, solid-state imaging element and color filter WO2019171902A1 (en)

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