Composition, light-shielding film, solid-state imaging device, image display device, and method for producing cured film

Abstract

To provide a composition from which a cured film having excellent light-shielding property and low reflection property can be obtained, a light-shielding film, a solid-state imaging element, an image display device, and a cured film production method.SOLUTION: A composition contains one or more selected from the group consisting of carbon black, barium sulfate, copper phthalocyanine and a copper phthalocyanine derivative, a resin, and a solvent, wherein the solvent contains a solvent A having a boiling point of 180°C or higher, a solvent B having a boiling point of 140°C or higher and lower than 180°C, and a solvent C having a boiling point of 100°C or higher and lower than 140°C.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition, a light-shielding film, a solid-state imaging device, an image display device, and a method for producing a cured film. [Background technology]

[0002] Compositions containing black powder have been used for a variety of purposes, including the preparation of light-shielding films to be placed in liquid crystal display devices and solid-state imaging devices such as CCD (Charge Coupled Device) image sensors and CMOS (Complementary Metal-Oxide Semiconductor) image sensors. For example, color filters used in liquid crystal display devices are provided with a light-shielding film called a black matrix for the purpose of blocking light between colored pixels to improve contrast. Furthermore, solid-state imaging devices are provided with light-shielding films at predetermined positions for the purposes of preventing noise generation and improving image quality.

[0003] For example, Patent Document 1 discloses a pigment dispersion resist composition for black matrices with good light-shielding properties and low reflectance, which is "a pigment dispersion composition for black matrices containing carbon black, precipitated barium sulfate, a basic group-containing pigment dispersant, a pigment derivative, an alkali-soluble resin, and a solvent, wherein the content ratio of carbon black to precipitated barium sulfate (carbon black / precipitated barium sulfate) is 95 / 5 to 65 / 35." In the examples section of Patent Document 1, only one solvent, PGMEA (propylene glycol monomethyl ether acetate), is used alone. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-082533 Summary of the Invention [Problem to be solved by the invention]

[0005] The present inventors have studied the composition described in Patent Document 1 and found that although the composition has good light-blocking properties, the reflectance may be higher than the currently required level. In other words, it has become clear that it is necessary to further reduce the reflectance while maintaining good light-blocking properties.

[0006] Therefore, an object of the present invention is to provide a composition that can be used to prepare a cured film having excellent light-blocking properties and low reflectivity. Another object of the present invention is to provide a method for producing a light-shielding film, a solid-state imaging device, an image display device, and a cured film. [Means for solving the problem]

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following configuration.

[0008] [1] A coating composition comprising carbon black, barium sulfate, one or more selected from the group consisting of copper phthalocyanine and copper phthalocyanine derivatives, a resin, and a solvent; The solvent is Solvent A having a boiling point of 180°C or higher; Solvent B having a boiling point of 140°C or higher but lower than 180°C; A composition comprising: a solvent C having a boiling point of 100°C or higher and lower than 140°C. [2] The composition according to [1], further comprising a compound containing an unsaturated double bond and a polymerization initiator. [3] The composition according to [2], wherein the polymerization initiator comprises a compound represented by formula (1) described below. [4] The solubility parameter of the solvent A is 11.0 to 14.0 (cal / cm 3 ) 1 / 2 The composition according to any one of [1] to [3], [5] The solubility parameter of the solvent A is 12.0 to 13.0 (cal / cm 3 ) 1 / 2The composition according to any one of [1] to [4], [6] The solvent A is at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, and benzyl alcohol; the solvent B is at least one selected from the group consisting of propylene glycol monomethyl ether acetate and cyclohexanone, The composition according to any one of [1] to [5], wherein the solvent C is at least one selected from the group consisting of butyl acetate and ethyl butyrate. [7] The composition according to any one of [1] to [6], wherein the copper phthalocyanine derivative is a salt composed of copper phthalocyanine having a sulfonic acid group and dimethyldioctadecylammonium. [8] The composition according to any one of [1] to [7], wherein the content of the carbon black is 15 to 40 mass % based on the total solid content of the composition. [9] The composition according to any one of [1] to [8], further comprising one or more types of metal-containing particles selected from the group consisting of metal nitrides and metal oxynitrides.

[10] The composition according to [9], wherein the metal-containing particles are nitrides or oxynitrides of one or more metals selected from the group consisting of titanium, zirconium, vanadium, and niobium.

[11] The composition according to any one of [1] to

[10] , further comprising a silicone surfactant.

[12] The composition according to

[11] , wherein the silicone surfactant is a surfactant having a phenyl group.

[13] The composition according to any one of [1] to

[12] , wherein the solid content is 10 to 40 mass %.

[14] The composition according to any one of [1] to

[13] , wherein the water content is 1.0 mass % or less based on the total mass of the composition.

[15] The content of the solvent A is 1.0 to 25.0 mass% based on the total content of the solvent A, the solvent B, and the solvent C; the content of the solvent B is 50.0 to 98.0 mass% with respect to the total content of the solvent A, the solvent B, and the solvent C; The composition according to any one of [1] to

[14] , wherein the content of the solvent C is 1.0 to 25.0 mass % with respect to the total content of the solvent A, the solvent B, and the solvent C.

[16] The composition according to any one of [1] to

[15] , which is a composition for forming a light-shielding film.

[17] A light-shielding film comprising a cured film formed from the composition according to any one of [1] to

[15] .

[18] A solid-state imaging device comprising a cured film formed from the composition according to any one of [1] to

[15] .

[19] An image display device comprising a cured film formed from the composition according to any one of [1] to

[15] .

[20] A composition layer forming step of forming a composition layer comprising the composition according to [2] on a support; an exposure step of exposing the composition layer to actinic rays or radiation; and a development step of performing a development treatment on the composition layer after the exposure. [Effects of the Invention]

[0009] According to the present invention, a composition can be provided that can form a cured film having excellent light-blocking properties and low reflectivity. Furthermore, the present invention can also provide a light-shielding film, a solid-state imaging device, an image display device, and a method for producing a cured film. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a schematic cross-sectional view showing an example of the configuration of a solid-state imaging device. [Figure 2] 2 is a schematic cross-sectional view showing an enlarged image pickup unit of FIG. 1. FIG. [Figure 3] FIG. 1 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0012] Furthermore, in the description of groups (atomic groups) in this specification, a description that does not specify whether they are substituted or unsubstituted encompasses both groups that contain a substituent and groups that do not contain a substituent. For example, the term "alkyl group" encompasses not only alkyl groups that do not contain a substituent (unsubstituted alkyl groups) but also alkyl groups that contain a substituent (substituted alkyl groups).

[0013] In addition, in this specification, "actinic rays" or "radiation" refers to, for example, far ultraviolet rays, extreme ultraviolet rays (EUV: Extreme ultraviolet lithography), X-rays, electron beams, etc. In addition, in this specification, light refers to actinic rays and radiation. Unless otherwise specified, in this specification, "exposure" includes not only exposure with far ultraviolet rays, X-rays, EUV light, etc., but also writing with particle beams such as electron beams and ion beams.

[0014] In addition, in this specification, "(meth)acrylate" refers to acrylate and methacrylate. In addition, in this specification, "(meth)acryl" refers to acryl and methacryl. In addition, in this specification, "(meth)acryloyl" refers to acryloyl and methacryloyl. In addition, in this specification, "(meth)acrylamide" refers to acrylamide and methacrylamide. In addition, in this specification, "monomer" and "monomer" are synonymous.

[0015] In this specification, the weight average molecular weight (Mw) is a value calculated as polystyrene by GPC (Gel Permeation Chromatography). The GPC method used herein is based on a method using HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, or TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm) as columns, and THF (tetrahydrofuran) as an eluent.

[0016] In this specification, the solid content of a composition means a composition layer formed using the composition, and when the composition contains a solvent, it means all components excluding the solvent. Furthermore, liquid components are also considered to be solids as long as they form a composition layer.

[0017] [Composition] The composition of the present invention contains carbon black, barium sulfate, one or more compounds selected from the group consisting of copper phthalocyanine and copper phthalocyanine derivatives (hereinafter also referred to as "copper phthalocyanines"), a resin, and a solvent, The solvent is A solvent A (hereinafter sometimes abbreviated as "solvent A") having a boiling point of 180°C or higher; Solvent B (hereinafter sometimes abbreviated as "solvent B") having a boiling point of 140°C or higher and lower than 180°C; and a solvent C (hereinafter sometimes abbreviated as "solvent C") having a boiling point of 100°C or higher and lower than 140°C.

[0018] Cured films prepared from the compositions of the present invention have excellent light-blocking properties (high minimum OD values ​​at wavelengths of 400 to 1000 nm) and low reflectivity (low maximum reflectivity at wavelengths of 400 to 700 nm). The mechanism by which the compositions of the present invention having such a configuration can solve the problems of the present invention is not entirely clear, but it is speculated that the inclusion of the above solvents A to C in the composition facilitates the induction of layer separation during film formation of the composition, which in turn facilitates the formation of surface irregularities and results in excellent low reflectivity. Furthermore, the compositions of the present invention also exhibit excellent light-blocking properties, primarily due to the inclusion of carbon black. In this specification, the term "cured film" refers to any film formed from a composition, and includes both films that have been subjected to a curing treatment such as exposure treatment and films that have not been subjected to a curing treatment such as exposure treatment.

[0019] Hereinafter, the term "better effects of the present invention" also refers to a cured film produced from the composition having better light-blocking properties (a higher minimum OD value at wavelengths of 400 to 1000 nm), better low reflectivity (a lower maximum reflectance at wavelengths of 400 to 700 nm), better undercut suppression performance of a cured film produced from the composition, better pencil hardness of a cured film produced from the composition, better peel suppression after humidity resistance and aging of a cured film produced from the composition, better viscosity stability over time of the composition, better solvent resistance of the composition (in other words, better removability by solvent), and / or better suppression of coating unevenness of the composition.

[0020] [Carbon black] The composition includes carbon black. The carbon black may be neutral, acidic, or basic, but is preferably acidic in that the effects of the present invention are more excellent. The acidic carbon black preferably has a pH of 2.0 to 4.0. Specific examples of acidic carbon black include Raven 1080 (average primary particle size 28 nm, pH 2.4) and Raven 1100 (average primary particle size 32 nm, pH 2.9) manufactured by Columbia Chemicals; and MA8 (average primary particle size 24 nm, pH 3.0), MA100 (average primary particle size 24 nm, pH 3.5), MA7 (average primary particle size 24 nm, pH 3.0), MA77 (average primary particle size 23 nm, pH 2.5), and MA220 (average primary particle size 55 nm, pH 3.0) manufactured by Mitsubishi Chemical. ), #2350 (average primary particle size 15 nm, pH 2.5, manufactured by Mitsubishi Chemical Corporation); Special Black 250 (average primary particle size 56 nm, pH 3.0), Special Black 350 (average primary particle size 31 nm, pH 3.0), Special Black 550 (average primary particle size 25 nm, pH 4), NEROX2500 (average primary particle size 56 nm, pH 3.0), and NEROX3500 (average primary particle size 31 nm, pH 3.0), manufactured by Orion Engineered Carbons;

[0021] Neutral and basic carbon blacks include, for example, those with a pH of 6.5 or higher. Specific examples of neutral and basic carbon black include Printex 25 (average primary particle size 56 nm, pH 9.5), Printex 35 (average primary particle size 31 nm, pH 9.5), and Printex 65 (average primary particle size 21 nm, pH 9.5) manufactured by Orion Engineered Carbons; #30 (average primary particle size 30 nm, pH 8.0) and #2600 (average primary particle size 13 nm, pH 6.5) manufactured by Mitsubishi Chemical Corporation; and the like.

[0022] The average primary particle size of the carbon black is preferably, for example, 10 to 60 nm, and more preferably 10 to 30 nm in terms of achieving better effects of the present invention.

[0023] The above pH of the carbon black is a catalog value, or if no catalog value is available, it is a value determined by the following measurement method. ≪pH measurement method≫ An aqueous suspension was prepared by adding 1 g of carbon black to 20 ml of decarbonated distilled water (pH 7.0) and mixing with a magnetic stirrer, and the value was measured at 25°C using a glass electrode (German Industrial Standard DIN ISO 787 / 9).

[0024] The average primary particle diameter of the carbon black is a catalog value, or if no catalog value is available, an arithmetic mean diameter value determined by observation with an electron microscope.

[0025] The carbon black content is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on the total solid content of the composition, and the upper limit is preferably 60% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less. The carbon black may be used alone or in combination of two or more types. When two or more types of carbon black are used in combination, the total content is preferably within the above range.

[0026] [Barium sulfate] The composition includes barium sulfate. The average primary particle size of barium sulfate is preferably 0.01 to 0.08 μm in terms of achieving better effects of the present invention and / or better dispersion stability. In order to obtain a more excellent effect of the present invention, the blending ratio by mass of carbon black and barium sulfate (carbon black / barium sulfate) is preferably 95 / 5 to 65 / 35, and more preferably 90 / 10 to 75 / 25. A preferred embodiment of barium sulfate is precipitated barium sulfate. Commercially available barium sulfate products include, for example, BF-20, BF-10, BF-21, BF-1, and BF-40 (all manufactured by Sakai Chemical Industry Co., Ltd.). The content of barium sulfate is preferably 1.0% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2.0% by mass or more, based on the total solid content of the composition, and the upper limit is preferably 10.0% by mass or less, more preferably 8.0% by mass or less, and even more preferably 6.0% by mass or less.

[0027] [Copper phthalocyanine and copper phthalocyanine derivatives (copper phthalocyanines)] The composition contains one or more members (copper phthalocyanines) selected from the group consisting of copper phthalocyanine and copper phthalocyanine derivatives. The copper phthalocyanine refers to a copper complex of phthalocyanine. The copper phthalocyanine derivative refers to a copper complex of phthalocyanine having a substituent (which may be in the form of a salt when the substituent contains a polar group such as an acid group or a basic group), and examples thereof include a copper complex of phthalocyanine having a substituent containing a polar group such as an acid group or a basic group, and salts thereof.

[0028] Examples of the acid group include a sulfonic acid group, a carboxylic acid group, and a phosphoric acid group, and the sulfonic acid group is preferred in that it provides a more excellent effect of the present invention. Examples of basic groups include primary amino groups, secondary amino groups, tertiary amino groups, heterocycles containing an N atom, and amide groups.

[0029] The salt is not particularly limited, and examples thereof include halide salts, alkali metal salts, and quaternary ammonium salts. Examples of halide ions that constitute halide salts include fluoride ions, chloride ions, bromide ions, and iodide ions. Examples of alkali metal ions that constitute alkali metal salts include lithium ions, sodium ions, and potassium ions. Examples of the quaternary ammonium ion that constitutes the quaternary ammonium salt include the quaternary ammonium ion represented by the following formula (NA). Formula (NA): N + (R A )(RB )(R C )(R D ) R A ~R D R each independently represents a hydrogen atom, or an alkyl group, an alkenyl group, or an alkynyl group, which may have a substituent. A ~R D Among them, alkyl groups which may have a substituent are preferred. The substituent is not particularly limited, and examples thereof include a hydroxyl group. The alkyl group, alkenyl group, and alkynyl group are preferably linear or branched. The alkyl group preferably has 1 to 30 carbon atoms, and more preferably 1 to 25 carbon atoms. The alkenyl group and alkynyl group preferably have 2 to 30 carbon atoms, and more preferably 2 to 25 carbon atoms. A preferred embodiment of the quaternary ammonium ion represented by formula (NA) is R A and R B If the long chain (e.g., R A and R B The number of carbon atoms in each of the groups independently is preferably 12 to 30, and more preferably 12 to 25, and R C and R C If the chain is short (e.g., R C and R C The number of carbon atoms of each of the groups independently is preferably 1 to 10, more preferably 1 to 6, and further preferably a methyl group. As the quaternary ammonium ion represented by formula (NA), dimethyldioctadecylammonium is preferred in terms of achieving better effects of the present invention.

[0030] As the copper phthalocyanines, in terms of achieving the effects of the present invention more excellently, a copper complex of a phthalocyanine having a substituent containing a sulfonic acid group or a salt thereof is preferred, a quaternary ammonium salt of a copper complex of a phthalocyanine having a substituent containing a sulfonic acid group is more preferred, and a salt composed of a copper complex of a phthalocyanine having a substituent containing a sulfonic acid group and dimethyldioctadecylammonium is even more preferred. The substituent containing a sulfonic acid group may be a sulfonic acid group or *-L A -sulfonic acid group (L A represents a divalent linking group, and * represents the bonding position. A The divalent linking group represented by the formula (I) is not particularly limited, and examples thereof include an alkylene group, an alkenylene group, an alkynylene group, -O-, -S-, -NR A -, -CO-, and combinations thereof. A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkylene group, the alkenylene group, and the alkynylene group may further have a substituent.

[0031] Examples of copper phthalocyanines include CI Pigment Blue 15:3. Commercially available copper phthalocyanines include, for example, "5000" from the "SOLSPERSE" series (manufactured by Lubrizol Nippon Co., Ltd.) and copper phthalocyanine-3,4',4'',4'''-tetrasulfonic acid tetrasodium salt sold by Sigma-Aldrich.

[0032] The content of copper phthalocyanines is preferably 1.0% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2.0% by mass or more, based on the total solid content of the composition, and the upper limit is preferably 10.0% by mass or less, more preferably 8.0% by mass or less, and even more preferably 6.0% by mass or less. The content ratio of barium sulfate to copper phthalocyanines (mass ratio: barium sulfate content / copper phthalocyanines content) is preferably, for example, 0.1 to 5.0, and more preferably 1.0 to 3.0 in terms of better effects of the present invention. The copper phthalocyanines may be used alone or in combination of two or more. When two or more copper phthalocyanines are used in combination, the total content is preferably within the above range.

[0033] 〔resin〕 The composition of the present invention contains a resin, for example, a dispersant and an alkali-soluble resin. The content of the resin in the composition is not particularly limited, but is preferably 3 to 60 mass %, more preferably 9 to 40 mass %, and even more preferably 9 to 35 mass %, based on the total solid content of the composition. One type of resin may be used alone, or two or more types may be used in combination. When two or more types of resins are used in combination, it is preferable that the total content is within the above range. The molecular weight of the resin is more than 2000. When the molecular weight of the resin is polydisperse, the weight average molecular weight is more than 2000.

[0034] <Dispersant> The composition preferably contains a dispersant. In this specification, the dispersant refers to a compound different from the alkali-soluble resin described below. The content of the dispersant in the composition is not particularly limited, but is preferably 2 to 40 mass % relative to the total solid content of the composition, more preferably 5 to 30 mass %, and even more preferably 10 to 25 mass %. The dispersant may be used alone or in combination of two or more. When two or more dispersants are used in combination, the total content is preferably within the above range. The mass ratio of the dispersant content to the carbon black content in the composition (dispersant content / carbon black content) is preferably 0.05 to 1.00, more preferably 0.1 to 0.80, and even more preferably 0.20 to 0.80.

[0035] As the dispersant, for example, known dispersants can be appropriately selected and used, and among them, polymer compounds are preferred. Examples of dispersants include polymer dispersants (e.g., polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (meth)acrylic copolymers, and naphthalenesulfonic acid-formalin condensates), polyoxyethylene alkyl phosphate esters, polyoxyethylene alkylamines, and pigment derivatives. Polymer compounds can be further classified into linear polymers, terminally modified polymers, graft polymers, and block polymers based on their structures.

[0036] ·Polymer compounds The polymer compound adsorbs to the surface of dispersed materials such as carbon black and other pigments used in combination as desired (hereinafter, carbon black and other pigments will be collectively referred to simply as "pigments") and acts to prevent reagglomeration of the dispersed materials. For this reason, a terminal-modified polymer, a graft-type (containing a polymer chain) polymer, or a block-type polymer containing an anchor site to the pigment surface is preferred.

[0037] The polymer compound may contain a curable group. Examples of the curable group include, but are not limited to, ethylenically unsaturated groups (e.g., (meth)acryloyl groups, vinyl groups, and styryl groups), and cyclic ether groups (e.g., epoxy groups and oxetanyl groups). Among these, the curable group is preferably an ethylenically unsaturated group because it allows polymerization control by a radical reaction, and the ethylenically unsaturated group is more preferably a (meth)acryloyl group.

[0038] The resin containing a curable group preferably contains one or more selected from the group consisting of a polyester structure and a polyether structure. In this case, the main chain may contain a polyester structure and / or a polyether structure, or, as described below, when the resin contains a structural unit containing a graft chain, the polymer chain may contain a polyester structure and / or a polyether structure. The polymer chain of the resin more preferably contains a polyester structure.

[0039] The polymer compound preferably contains a structural unit containing a graft chain. In this specification, the term "structural unit" has the same meaning as "repeating unit." A polymer compound containing such a structural unit having a graft chain has affinity with a solvent due to the graft chain, and therefore has excellent dispersibility of pigments, etc., and dispersion stability over time. Furthermore, due to the presence of the graft chain, the polymer compound containing the structural unit having a graft chain has affinity with polymerizable compounds or other resins that can be used in combination. As a result, residues are less likely to be generated by alkaline development. As the graft chain becomes longer, the steric repulsion effect increases, improving the dispersibility of pigments, etc. On the other hand, if the graft chain is too long, the adsorption force to pigments, etc. decreases, and the dispersibility of pigments, etc. tends to decrease. For this reason, the number of atoms excluding hydrogen atoms in the graft chain is preferably 40 to 10,000, more preferably 50 to 2,000, and even more preferably 60 to 500. Here, the graft chain refers to the chain from the base of the main chain of the copolymer (the atom bonded to the main chain in the group branching from the main chain) to the end of the group branching from the main chain.

[0040] The graft chain preferably contains a polymer structure, and examples of such polymer structures include a poly(meth)acrylate structure (e.g., a poly(meth)acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, and a polyether structure. In order to improve the interaction between the graft chain and the solvent and thereby enhance the dispersibility of the pigment or the like, the graft chain is preferably a graft chain containing one or more structures selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylate structure, and more preferably a graft chain containing at least one of a polyester structure and a polyether structure.

[0041] The macromonomer containing such a graft chain (a monomer having a polymer structure and binding to the main chain of the copolymer to form the graft chain) is not particularly limited, but a macromonomer containing a reactive double bond group can be preferably used.

[0042] Commercially available macromonomers that correspond to the structural unit containing the graft chain contained in the polymer compound and that can be suitably used for synthesizing 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 Co., Ltd.), AA-714 (trade name, manufactured by Toagosei Co., Ltd.), AY-707 (trade name, manufactured by Toagosei Co., Ltd.), AK-5 (trade name, manufactured by Toagosei Co., Ltd.), AK-30 ...AK-50 (trade name, manufactured by Toagosei Co., Ltd.), AK-30 (trade name, manufactured by Toagosei Co., Ltd.), AK-50 (trade name, manufactured by Toagosei Co., Ltd.), AK-50 (trade name, manufactured by Toagosei Co Examples of usable polymers include AK-32 (trade name, manufactured by Toagosei Co., Ltd.), AK-32 (trade name, manufactured by Toagosei Co., Ltd.), Blemmer PP-100 (trade name, manufactured by NOF Corporation), Blemmer PP-500 (trade name, manufactured by NOF Corporation), Blemmer PP-800 (trade 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), and Blemmer 43PAPE-600B (trade name, manufactured by NOF Corporation). Among these, AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AS-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), or Blenmar PME-4000 (trade name, manufactured by NOF Corporation) are preferred.

[0043] The dispersant preferably contains one or more structures selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or linear polyesters, more preferably one or more structures selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and linear polyesters, and even more preferably one or more structures selected from the group consisting of polymethyl acrylate structures, polymethyl methacrylate structures, polycaprolactone structures, and polyvalerolactone structures. The dispersant may contain only one of the above structures in a single dispersant, or may contain a plurality of these structures in a single dispersant. Here, the polycaprolactone structure refers to a structure containing a ring-opened ε-caprolactone structure as a repeating unit, and the polyvalerolactone structure refers to a structure containing a ring-opened δ-valerolactone structure as a repeating unit. Specific examples of dispersants containing a polycaprolactone structure include dispersants in which j and k in the following formulas (1) and (2) are 5. Specific examples of dispersants containing a polyvalerolactone structure include dispersants in which j and k in the following formulas (1) and (2) are 4. Specific examples of dispersants containing a polymethyl acrylate structure include those represented by the following formula (4): 5 is a hydrogen atom, and R 4 A specific example of a dispersant containing a polymethyl methacrylate structure is a dispersant represented by the following formula (4): 5 is a methyl group, and R 4 is a methyl group.

[0044] Structural units containing graft chains The polymer compound preferably contains a structural unit represented by any one of the following formulas (1) to (4) as a structural unit containing a graft chain, and more preferably contains a structural unit represented by any one of the following formulas (1A), (2A), (3A), (3B), and (4).

[0045] [ka]

[0046] In equations (1) to (4), W 1 , W 2 , W 3 , and W 4 Each independently represents an oxygen atom or NH. 1 , W 2 , W 3 , and W 4 is preferably an oxygen atom. In formulas (1) to (4), X 1 , X 2 , X3 , X 4 , and X 5 Each of X independently represents a hydrogen atom or a monovalent organic group. 1 , X 2 , X 3 , X 4 , and X 5 From the viewpoint of synthetic constraints, each of the groups is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group.

[0047] In formulas (1) to (4), Y 1 , Y 2 , Y 3 , and Y 4 each independently represents a divalent linking group, and the linking group is not particularly restricted in structure. 1 , Y 2 , Y 3 , and Y 4 Specific examples of the divalent linking group represented by the formula (I) include the following linking groups (Y-1) to (Y-21). In the structures shown below, A and B represent the bonding sites with the left and right terminal groups in formulas (1) to (4), respectively. Of the structures shown below, (Y-2) or (Y-13) is more preferred from the viewpoint of ease of synthesis.

[0048] [ka]

[0049] In formulas (1) to (4), Z 1 , Z 2 , Z 3 , and Z 4 Each of Z independently represents a monovalent organic group. The structure of the organic group is not particularly limited, but specific examples include 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. Among these, Z 1 , Z 2 , Z3 , and Z 4 As the organic group represented by the formula (I), a group having a steric repulsion effect is preferred, particularly from the viewpoint of improving dispersibility, and each independently an alkyl group or alkoxy group having 5 to 24 carbon atoms is more preferred, and among these, each independently 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 even more preferred. The alkyl group contained in the alkoxy group may be linear, branched, or cyclic.

[0050] In the formulas (1) to (4), n, m, p, and q each independently represent an integer of 1 to 500. In formulas (1) and (2), j and k each independently represent an integer of 2 to 8. In formulas (1) and (2), j and k are preferably integers of 4 to 6, more preferably 5, from the viewpoints of viscosity stability over time and developability of the composition. In formulas (1) and (2), n and m are preferably integers of 10 or greater, and more preferably integers of 20 or greater. When the dispersant contains a polycaprolactone structure and a polyvalerolactone structure, the sum of the repeating number of the polycaprolactone structure and the repeating number of the polyvalerolactone structure is preferably an integer of 10 or greater, and more preferably an integer of 20 or greater.

[0051] In formula (3), R 3 represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different from each other. In formula (4), R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. 4 R is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. 4When is an alkyl group, the alkyl group is preferably 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, more preferably a linear alkyl group having 1 to 20 carbon atoms, and even more preferably a linear alkyl group having 1 to 6 carbon atoms. In formula (4), when q is 2 to 500, the number of X present in the graft copolymer is 5 and R 4 may be the same or different from each other.

[0052] Furthermore, the polymer compound may contain structural units containing graft chains with two or more different structures. That is, the polymer compound molecule may contain structural units represented by formulas (1) to (4) with mutually different structures. When n, m, p, and q in formulas (1) to (4) each represent an integer of 2 or more, the side chains in formulas (1) and (2) may contain structures in which j and k are mutually different. In formulas (3) and (4), multiple R 3 , R 4 , and X 5 may be the same or different from each other.

[0053] The structural unit represented by formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of viscosity stability over time and developability of the composition. Furthermore, the structural unit represented by formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of viscosity stability over time and developability of the composition.

[0054] [ka]

[0055] In formula (1A), X 1 , Y 1 , Z 1 , and n is X in formula (1). 1 , Y 1 , Z 1 In formula (2A), X has the same meaning as n, and the preferred range is also the same. 2 , Y2 , Z 2 , and m is X in Equation (2). 2 , Y 2 , Z 2 , and m, and the preferred ranges are also the same.

[0056] Furthermore, the structural unit represented by formula (3) is more preferably a structural unit represented by formula (3A) or (3B) below, from the viewpoint of viscosity stability over time and developability of the composition.

[0057] [ka]

[0058] In formula (3A) or (3B), X 3 , Y 3 , Z 3 , and p is X in Equation (3). 3 , Y 3 , Z 3 , and p have the same meanings, and the preferred ranges are also the same.

[0059] The polymer compound more preferably contains a structural unit represented by formula (1A) as a structural unit containing a graft chain.

[0060] 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 preferably contained in a range of 2 to 90 mass % and more preferably in a range of 5 to 30 mass % relative to the total mass of the polymer compound. When the structural unit containing a graft chain is contained within this range, the dispersibility of the pigment is high and the developability of the cured film after exposure is good.

[0061] Hydrophobic structural unit Furthermore, the polymer compound preferably contains a hydrophobic structural unit different from the structural unit containing the graft chain (i.e., not corresponding to the structural unit containing the graft chain). However, in this specification, the hydrophobic structural unit is a structural unit that does not have an acid group (e.g., a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).

[0062] 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 more preferably a structural unit derived from a compound having a ClogP value of 1.2 to 8. This allows the effects of the present invention to be more reliably exhibited.

[0063] The ClogP values ​​are values ​​calculated using the program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides "calculated logP" values ​​calculated using the fragment approach of Hansch and Leo (see the literature below). The fragment approach is based on the chemical structure of a compound, and divides the chemical structure into substructures (fragments). The logP value of the compound is estimated by summing up the logP contributions assigned to the fragments. Details are described in the literature below. In this specification, the ClogP values ​​calculated using the program CLOGP v4.82 are used. AJ Leo, Comprehensive Medicinal Chemistry, Vol.4, C. Hansch, PG Sammnens, JB Taylor and CA Ramsden, Eds., p.295, Pergamon Press, 1990 C. Hansch & AJ Leo. SUbstituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. AJ Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993.

[0064] Log P is the common logarithm of the partition coefficient P, a physical property that quantitatively represents how an organic compound is distributed in equilibrium between a two-phase system of oil (generally 1-octanol) and water, and is expressed 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 water phase. As the logP value increases towards the positive side, including around 0, the oil solubility increases, and as the absolute value increases towards the negative side, the water solubility increases. It has a negative correlation with the water solubility of organic compounds, and is widely used as a parameter to estimate the hydrophilicity or hydrophobicity of organic compounds.

[0065] The polymer compound preferably contains, as a hydrophobic structural unit, one or more structural units selected from structural units derived from monomers represented by the following formulas (i) to (iii).

[0066] [ka]

[0067] In the above formulas (i) to (iii), R 1 , R 2 , and R 3 each independently represents 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.). R 1 , R 2 , and R 3 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. 2 and R 3 is more preferably a hydrogen atom. X represents an oxygen atom (-O-) or an imino group (-NH-), and is preferably an oxygen atom.

[0068] L is a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (e.g., an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (e.g., an arylene group and a substituted arylene group), a divalent heterocyclic group, an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), and a substituted imino group (—NR 31 -, where R 31 is an aliphatic group, an aromatic group, or a heterocyclic group), a carbonyl group (—CO—), and combinations thereof.

[0069] The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms in the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group.

[0070] The number of carbon atoms in the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and even 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.

[0071] The divalent heterocyclic group preferably contains a 5- or 6-membered ring as the heterocycle. The heterocycle may be condensed with another heterocycle, an aliphatic ring, or an aromatic ring. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (=O), a thioxo group (=S), an imino group (=NH), a substituted imino group (=NR 32 , where R 32 is an aliphatic group, an aromatic group, or a heterocyclic group), an aliphatic group, an aromatic group, and a heterocyclic group.

[0072] 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 also contain a polyoxyalkylene structure containing two or more repeating oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by -(OCH2CH2)n-, where n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.

[0073] Z may be an aliphatic group (e.g., an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (e.g., an aryl group, a substituted aryl group, an arylene group, a substituted arylene group), a heterocyclic group, or a combination thereof. These groups include an oxygen atom (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR 31 -, where R 31 may contain an aliphatic group, an aromatic group, or a heterocyclic group), or a carbonyl group (—CO—).

[0074] The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms in the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group further includes a ring-assembled hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring-assembled hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and a 4-cyclohexylphenyl group. Examples of the bridged cyclic hydrocarbon ring include bicyclic hydrocarbon rings such as pinane, bornane, norpinane, norbornane, and bicyclooctane rings (such as bicyclo[2.2.2]octane ring and bicyclo[3.2.1]octane ring), homobredane, adamantane, and tricyclo[5.2.1.0]octane ring. 2,6 ] decane, and tricyclo[4.3.1.1 2,5 ]undecane ring and the like, 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 also includes fused rings in which multiple 5- to 8-membered cycloalkane rings are fused, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenalene rings. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.

[0075] The number of carbon atoms in the aromatic group is preferably 6 to 20, more preferably 6 to 15, and even 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. However, the aromatic group does not have an acid group as a substituent.

[0076] The heterocyclic group preferably contains a 5- or 6-membered ring as the heterocycle. The heterocycle may be condensed with another heterocycle, an aliphatic ring, or an aromatic ring. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (=O), a thioxo group (=S), an imino group (=NH), a substituted imino group (=NR 32 , where R 32 is an aliphatic group, an aromatic group, or a heterocyclic group), an aliphatic group, an aromatic group, and a heterocyclic group, provided that the heterocyclic group does not have an acid group as a substituent.

[0077] In the above formula (iii), R 4 , R 5 , and R 6 R each independently represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, etc.), Z, or LZ, where L and Z have the same meanings as the groups defined above. 4 , R 5, and R 6 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

[0078] As the monomer represented by the above formula (i), R 1 , R 2 , and R 3 is a hydrogen atom or a methyl group, L is a single bond or a divalent linking group containing an alkylene group or an oxyalkylene structure, X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Furthermore, 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. 4 , R 5 , and R 6 is a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group.

[0079] Representative examples of the compounds represented by formulas (i) to (iii) include radical polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like. As representative examples of compounds represented by formulas (i) to (iii), reference can be made to the compounds described in paragraphs 0089 to 0093 of JP-A No. 2013-249417, the contents of which are incorporated herein by reference.

[0080] In the polymer compound, the hydrophobic structural unit is preferably contained in a range of 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the polymer compound. When the content is within the above range, sufficient pattern formation can be achieved.

[0081] Functional groups that can interact with pigments, etc. A functional group capable of forming an interaction with a pigment or the like (for example, a light-shielding pigment) can be introduced into the polymer compound. Here, it is preferable that the polymer compound further includes 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 or the like include an acid group, a basic group, a coordinating group, and a reactive functional group. When the polymer compound contains an acid group, a basic group, a coordinating group, or a reactive functional group, it preferably contains a structural unit containing an acid group, a structural unit containing a basic group, a structural unit containing a coordinating group, or a reactive structural unit, respectively. In particular, if the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as the acid group, the polymer compound can be endowed with developability for forming a pattern by alkali development. That is, by introducing an alkali-soluble group into a polymer compound, the polymer compound in the composition will have alkali solubility as a dispersant that contributes to the dispersion of pigments, etc. A composition containing such a polymer compound will have excellent light-blocking properties for a cured film formed by exposure, and will also have improved alkali developability in unexposed areas. Furthermore, if the polymer compound contains a structural unit containing an acid group, the polymer compound will have better compatibility with the solvent, and the coatability will also tend to improve. This is presumably because the acid groups in the structural units containing acid groups tend to interact with pigments, etc., allowing the polymer compound to stably disperse the pigments, etc., and also because the viscosity of the polymer compound that disperses the pigments, etc. is low, making it easier for the polymer compound itself to be stably dispersed.

[0082] However, the structural unit containing an alkali-soluble group as an acid group may be the same structural unit as or different from the structural unit containing the graft chain described above, but the structural unit containing an alkali-soluble group as an acid group is a structural unit different from the hydrophobic structural unit described above (i.e., does not correspond to the hydrophobic structural unit described above).

[0083] Examples of the acid group, which is a functional group capable of interacting with pigments, etc., include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and are preferably at least one selected from the group consisting of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, with a carboxylic acid group being more preferred. The carboxylic acid group has good adsorption power to pigments, etc., and high dispersibility. That is, it is preferable that the polymer compound further contains a structural unit containing one or more groups selected from the group consisting of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

[0084] The polymer compound may have one or more types of structural units containing an acid group. The polymer compound may or may not contain a structural unit containing an acid group. When the polymer compound contains the structural unit containing an acid group, the content of the structural unit containing an acid group is preferably 5 to 80 mass % relative to the total mass of the polymer compound, and more preferably 10 to 60 mass % from the viewpoint of suppressing damage to image strength due to alkali development.

[0085] Examples of basic groups, which are functional groups capable of forming interactions with pigments, etc., include primary amino groups, secondary amino groups, tertiary amino groups, heterocycles containing an N atom, and amide groups, and a preferred basic group is a tertiary amino group because of its good adsorption to pigments, etc. and high dispersibility. The polymer compound can contain one or more of these basic groups. The polymer compound may or may not contain a structural unit containing a basic group. When the polymer compound contains a structural unit containing a basic group, the content of the structural unit containing a basic group is preferably from 0.01 to 50 mass % relative to the total mass of the polymer compound, and from the viewpoint of suppressing development inhibition, more preferably from 0.01 to 30 mass %.

[0086] Examples of the coordinating group, which is a functional group capable of forming an interaction with a pigment or the like, and the reactive functional group include an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, and an acid chloride. A preferred functional group is the acetylacetoxy group, which has good adsorption power to a pigment or the like and high dispersibility of the pigment or 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. When the polymer compound contains such a structural unit, the content of the structural unit is preferably from 10 to 80 mass % relative to the total mass of the polymer compound, and from the viewpoint of suppressing development inhibition, more preferably from 20 to 60 mass %.

[0087] When the polymer compound contains, in addition to the graft chain, a functional group capable of forming an interaction with a pigment or the like, the polymer compound may contain a functional group capable of forming an interaction with the above-mentioned various pigments or the like, and there are no particular limitations on how these functional groups are introduced. However, it is preferable that the polymer compound contains one or more structural units selected from structural units derived from monomers represented by the following formulas (iv) to (vi):

[0088] [ka]

[0089] In formulas (iv) to (vi), R 11 , R 12 , and R 13 each independently represents 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.). 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 more preferably each independently a hydrogen atom or a methyl group. 12 and R 13More preferably, each of is a hydrogen atom.

[0090] X1 in formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), and is preferably an oxygen atom. In addition, Y in the formula (v) represents a methine group or a nitrogen atom.

[0091] Furthermore, L1 in formulas (iv) and (v) represents a single bond or a divalent linking group. The definition of the divalent linking group is the same as the definition of the divalent linking group represented by L in formula (i) above.

[0092] L1 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. L1 may also contain a polyoxyalkylene structure containing two or more repeating oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is preferably -(OCH2CH2) n -, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

[0093] In formulas (iv) to (vi), Z1 represents a functional group capable of forming an interaction with a pigment or the like other than the graft chain, and is preferably a carboxylic acid group or a tertiary amino group, more preferably a carboxylic acid group.

[0094] In formula (vi), R 14 , R 15 , and R 16 R each independently represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, etc.), -Z1, or L1-Z1. Here, L1 and Z1 have the same meanings as L1 and Z1 above, and preferred examples are also the same. R 14 , R 15 , and R 16are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

[0095] As the monomer represented by formula (iv), R 11 , R 12 , and R 13 are each independently a hydrogen atom or a methyl group, L1 is an alkylene group or a divalent linking group containing an oxyalkylene structure, X1 is an oxygen atom or an imino group, and Z1 is a carboxylic acid group. Furthermore, as the monomer represented by formula (v), R 11 is a hydrogen atom or a methyl group, L1 is an alkylene group, Z1 is a carboxylic acid group, and Y is a methine group. Further, as the monomer represented by formula (vi), R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group, L1 is a single bond or an alkylene group, and Z1 is a carboxylic acid group.

[0096] Representative examples of the monomers (compounds) represented by formulas (iv) to (vi) are shown below. Examples of the monomer include methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule (e.g., 2-hydroxyethyl methacrylate) with succinic anhydride, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with tetrahydroxyphthalic anhydride, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with trimellitic anhydride, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with pyromellitic anhydride, acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4-hydroxyphenyl methacrylamide.

[0097] The content of the structural unit containing a functional group capable of forming an interaction with a pigment or the like is preferably 0.05 to 90 mass %, more preferably 1.0 to 80 mass %, and even more preferably 10 to 70 mass %, relative to the total mass of the polymer compound, from the viewpoints of the interaction with the pigment or the like, viscosity stability over time, and permeability into a developer.

[0098] Other structural units Furthermore, for the purpose of improving various performances such as image strength, the polymer compound may further have other structural units having various functions (for example, structural units containing a functional group having affinity for a solvent, which will be described later) that are different from the structural unit containing a graft chain, the hydrophobic structural unit, and the structural unit containing a functional group capable of forming an interaction with a pigment or the like, as long as the effects of the present invention are not impaired. Examples of such other structural units include structural units derived from radical polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like. The polymer compound can use one or more of these other structural units, and the content thereof is preferably 0 to 80% by mass, more preferably 10 to 60% by mass, based on the total mass of the polymer compound. When the content is within the above range, sufficient pattern formability is maintained.

[0099] ·Physical properties of polymer compounds The acid value of the polymer compound is preferably from 0 to 250 mgKOH / g, more preferably from 10 to 200 mgKOH / g, and even more preferably from 30 to 180 mgKOH / g. When the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development of the cured film after exposure can be more effectively suppressed. When the acid value of the polymer compound is 10 mgKOH / g or more, alkaline developability is improved. When the acid value of the polymer compound is 20 mgKOH / g or more, sedimentation of pigments and the like can be more effectively suppressed, the number of coarse particles can be reduced, and the viscosity stability of the composition over time can be further improved.

[0100] In this specification, the acid value can be calculated, for example, from the average content of acid groups in the compound. Furthermore, a resin having a desired acid value can be obtained by changing the content of structural units containing acid groups, which are components of the resin.

[0101] The weight average molecular weight of the polymer compound is preferably 4,000 to 300,000, more preferably 5,000 to 200,000, even more preferably 6,000 to 100,000, and particularly preferably 10,000 to 50,000. The polymer compound can be synthesized based on a known method.

[0102] Specific examples of polymer compounds include "DA-7301" manufactured by Kusumoto Chemicals Co., Ltd., "Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing acid groups), 111 (phosphate-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 167, 170, 190 (polymer copolymer)" and "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)" manufactured by BYK Chemie, and "EFKA4047, 4050-4010-" manufactured by EFKA. 4165 (Polyurethane-based), EFKA4330-4340 (Block Copolymer), 4400-4402 (Modified Polyacrylate), 5010 (Polyesteramide), 5765 (High Molecular Weight Polycarboxylate), 6220 (Fatty Acid Polyester), 6750 (Azo Pigment Derivative), Ajinomoto Fine-Techno Co., Ltd.'s "Ajisper PB821, PB822, PB880, PB881", Kyoeisha Chemical Co., Ltd.'s "Florene TG-710 (Urethane Oligomer)", "Polyflow No. 50E, No. 300 (Acrylic Copolymer)" Kusumoto Chemicals' "Disparlon KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725"; Kao's "Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)", "Homogenol L-18 (polymeric polycarboxylic acid)", "Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)" ), "Acetamine 86 (Stearylamine Acetate)", Lubrizol Japan 22000 (Azo Pigment Derivative), 13240 (Polyesteramine), 3000, 12000, 17000, 20000, 27000 (Polymers with Functional Groups at the End), 24000, 28000, 32000, 38500 (Graft Copolymers), Nikko Chemical Co., Ltd. "Nikkol T106 (Polyoxyethylene Sorbitan Monooleate), MYS-IEX (Polyoxyethylene Monostearate)", Kawaken Fine ChemicalsHinoact T-8000E and other products manufactured by Shin-Etsu Chemical Co., Ltd., organosiloxane polymer KP341, Yusho's "W001: Cationic Surfactant", nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", and Morishita Sangyo's "EFKA-46" , EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450, San Nopco's Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100, and other polymer dispersants; ADEKA's ADEKA Pluronic (registered trademark) L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123; and Sanyo Chemical's IONET (trade name) S-20. Also usable are Acribase FFS-6752 and Acribase FFS-187.

[0103] It is also preferable to use an amphoteric resin containing an acid group and a basic group, and the amphoteric resin preferably has an acid value of 5 mg KOH / g or more and an amine value of 5 mg KOH / g or more. Commercially available amphoteric resins include, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2025, and BYK-9076 manufactured by BYK-Chemie Co., Ltd., and Ajisper PB821, Ajisper PB822, and Ajisper PB881 manufactured by Ajinomoto Fine-Techno Co., Ltd. These polymer compounds may be used alone or in combination of two or more.

[0104] As specific examples of the polymer compound, reference can be made to the polymer compounds described in paragraphs 0127 to 0129 of JP-A No. 2013-249417, the contents of which are incorporated herein by reference.

[0105] In addition to the above polymer compounds, the graft copolymers described in paragraphs 0037 to 0115 of JP 2010-106268 A (corresponding to paragraphs 0075 to 0133 of US 2011 / 0124824) can also be used as dispersants, the contents of which are incorporated herein by reference. In addition to the above, polymer compounds containing a component having a side chain structure in which an acid group is bonded via a linking group, as described in paragraphs 0028 to 0084 of JP 2011-153283 A (corresponding to paragraphs 0075 to 0133 of US 2011 / 0279759), can also be used, the contents of which are incorporated herein by reference.

[0106] Furthermore, as the dispersant, resins described in paragraphs 0033 to 0049 of JP 2016-109763 A can also be used, the contents of which are incorporated herein by reference.

[0107] Furthermore, a resin containing a repeating unit containing a polyalkyleneimine structure and a polyester structure (hereinafter also referred to as "resin X1") can also be suitably used as the dispersant. The repeating unit containing a polyalkyleneimine structure and a polyester structure preferably contains a polyalkyleneimine structure in the main chain and a polyester structure as a graft chain.

[0108] The polyalkyleneimine structure is a polymer structure containing two or more identical or different alkyleneimine chains. Specific examples of the alkyleneimine chain include alkyleneimine chains represented by the following formula (4A) and formula (4B).

[0109] [ka]

[0110] In formula (4A), R X1 and R X2 each independently represents a hydrogen atom or an alkyl group. 1 represents an integer greater than or equal to 2. 1 represents the bonding position to the polyester chain, the adjacent alkyleneimine chain, or the hydrogen atom or substituent.

[0111] [ka]

[0112] In formula (4B), R X3 and R X4 each independently represents a hydrogen atom or an alkyl group. 2 represents an integer of 2 or more. The alkyleneimine chain represented by formula (4B) is a polyester chain having an anionic group and a N + The anionic groups contained in the polyester chains form salt bridges, thereby bonding the polymer to the polymer.

[0113] * in formula (4A) and formula (4B), and * in formula (4B) 2 each independently represents a position at which the group is bonded to an adjacent alkyleneimine chain, a hydrogen atom, or a substituent. In particular, * in formula (4A) and formula (4B) preferably represents the position at which the alkyleneimine chain is bonded to the adjacent alkyleneimine chain.

[0114] R in formula (4A) X1 and R X2 , and R in formula (4B) X3 and R X4 each independently represents a hydrogen atom or an alkyl group. The alkyl group preferably has 1 to 6 carbon atoms, and more preferably has 1 to 3 carbon atoms. In formula (4A), R X1 and R X2 are preferably all hydrogen atoms. In formula (4B), R X3 and R X4are preferably all hydrogen atoms.

[0115] a in formula (4A) 1 and a in formula (4B) 2 is not particularly limited as long as it is an integer of 2 or more. The upper limit is preferably 10 or less, more preferably 6 or less, even more preferably 4 or less, still more preferably 2 or 3, and particularly preferably 2.

[0116] In formula (4A) and formula (4B), * represents the bonding position to the adjacent alkyleneimine chain, or to a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (e.g., an alkyl group having 1 to 6 carbon atoms) and —CO—R T Examples of the substituents include organic groups represented by the above R T Examples of the alkyl group include alkyl groups (for example, having 1 to 6 carbon atoms) or alkenyl groups (for example, having 2 to 6 carbon atoms) which may be substituted with an acid group (for example, a carboxy group, a sulfo group, a phosphate group, etc.). In addition, in formula (4A) and formula (4B), a polyester chain may be bonded as a substituent at the bonding position represented by *.

[0117] The alkyleneimine chain represented by formula (4A) is 1 Specifically, it is preferable that the carbonyl carbon in the polyester chain is linked to the polyester chain at the position 1 It is preferred that the bond is at the position The polyester chain may be represented by the following formula (5A).

[0118] [ka]

[0119] When the alkyleneimine chain is an alkyleneimine chain represented by formula (4B), the polyester chain is anionic (preferably oxygen anion O - ), and this anionic group and N in formula (4B) +It is preferred that the two form a salt bridge. Such a polyester chain includes a polyester chain represented by the following formula (5B).

[0120] [ka]

[0121] L in formula (5A) X1 , and L in formula (5B) X2 each independently represents a divalent linking group. The divalent linking group is preferably an alkylene group having 3 to 30 carbon atoms.

[0122] b in formula (5A) 11 , and b in formula (5B) 21 each independently represents an integer of 2 or more, preferably an integer of 6 or more, and the upper limit is, for example, 200 or less.

[0123] b in formula (5A) 12 , and b in formula (5B) 22 each independently represents 0 or 1.

[0124] X in formula (5A) A and X in formula (5B) B each independently represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a polyalkyleneoxyalkyl group, and an aryl group.

[0125] The number of carbon atoms in the alkyl group (which may be linear, branched, or cyclic) and the alkyl group contained in the alkoxy group (which may be linear, branched, or cyclic) can be 1 to 30, and preferably 1 to 10. The alkyl group can further have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom).

[0126] Polyalkyleneoxyalkyl groups are RX6 (OR X7 ) p (O) q R is a substituent represented by the formula X6 represents an alkyl group, and R X7 represents an alkylene group, p represents an integer of 2 or more, and q represents 0 or 1. R X6 The alkyl group represented by X A The alkyl group represented by R X7 The alkylene group represented by X A Examples of such alkyl groups include groups in which one hydrogen atom has been removed from an alkyl group represented by the following formula: p is an integer of 2 or more, and its upper limit is, for example, 10 or less, and preferably 5 or less.

[0127] The aryl group may be, for example, an aryl group having 6 to 24 carbon atoms (which may be either monocyclic or polycyclic). The aryl group may further have a substituent, and examples of the substituent include an alkyl group, a halogen atom, and a cyano group.

[0128] The polyester chain is preferably a structure obtained by ring-opening a lactone such as ε-caprolactone, δ-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, enantholactone, β-butyrolactone, γ-hexanolactone, γ-octanolactone, δ-hexalanolactone, δ-octanolactone, δ-dodecanolactone, α-methyl-γ-butyrolactone, or lactide (which may be either L- or D-isomer), and more preferably a structure obtained by ring-opening ε-caprolactone or δ-valerolactone.

[0129] The resin containing a repeating unit containing a polyalkyleneimine structure and a polyester structure can be synthesized according to the synthesis method described in Japanese Patent No. 5923557.

[0130] As examples of resins containing repeating units having a polyalkyleneimine structure and a polyester structure, reference can be made to the resins containing repeating units having a polyalkyleneimine structure and a polyester structure disclosed in Japanese Patent No. 5923557, the contents of which are incorporated herein by reference.

[0131] The acid value of Resin X1 is preferably 10 to 100 mgKOH / g, more preferably 20 to 80 mgKOH / g. The amine value of Resin X1 is preferably 5 mgKOH / g or more, more preferably 20 mgKOH / g or more, and even more preferably 30 mgKOH / g or more. The upper limit is preferably, for example, 100 mgKOH / g or less.

[0132] The weight-average molecular weight of Resin X1 is not particularly limited, but is, for example, preferably 3,000 or more, more preferably 4,000 or more, even more preferably 5,000 or more, and particularly preferably 6,000 or more.The upper limit is, for example, preferably 300,000 or less, more preferably 200,000 or less, even more preferably 100,000 or less, and particularly preferably 50,000 or less.

[0133] <Alkali-soluble resin> The composition preferably contains an alkali-soluble resin. In this specification, the alkali-soluble resin refers to a resin containing a group that promotes alkali solubility (an alkali-soluble group, for example, an acid group such as a carboxylic acid group), and is different from the dispersants already described. The content of the alkali-soluble resin in the composition is not particularly limited, but is preferably 1 to 30 mass %, more preferably 2 to 20 mass %, and even more preferably 5 to 15 mass %, based on the total solid content of the composition. The alkali-soluble resin may be used alone or in combination of two or more. When two or more alkali-soluble resins are used in combination, the total content is preferably within the above range.

[0134] Examples of alkali-soluble resins include resins containing at least one alkali-soluble group in the molecule, such as polyhydroxystyrene resins, polysiloxane resins, (meth)acrylic resins, (meth)acrylamide resins, (meth)acrylic / (meth)acrylamide copolymer resins, epoxy resins, and polyimide resins.

[0135] Specific examples of alkali-soluble resins include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds. The unsaturated carboxylic acid is not particularly limited, but examples thereof include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and vinylacetic acid; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, or acid anhydrides thereof; and polycarboxylic acid monoesters such as mono(2-(meth)acryloyloxyethyl)phthalate.

[0136] Examples of copolymerizable ethylenically unsaturated compounds include methyl (meth)acrylate, etc. Compounds described in paragraph 0027 of JP 2010-097210 A and paragraphs 0036 to 0037 of JP 2015-068893 A can also be used, and the contents of the above are incorporated herein by reference.

[0137] As the alkali-soluble resin, an alkali-soluble resin containing a curable group is also preferred in that the effects of the present invention are more excellent. The curable group may be contained in the polymer compound described above. The curable groups may be similarly exemplified, and the preferred ranges are also similar. An example of the alkali-soluble resin containing a curable group is an acrylic resin containing an ethylenically unsaturated group in a side chain. The acrylic resin containing an ethylenically unsaturated group in a side chain can be obtained, for example, by subjecting a carboxylic acid group of an acrylic resin containing a carboxylic acid group to an addition reaction with an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group. The alkali-soluble resin containing a curable group is preferably an alkali-soluble resin having a curable group in a side chain, etc. Examples of alkali-soluble resins containing a curable group include the Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (a COOH-containing polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.), Viscoat R-264, and KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Ltd.), the Cyclomer P series (e.g., ACA230AA), the Plaxel CF200 series (all manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel-Allnex Corporation), and Acricur RD-F8 (manufactured by Nippon Shokubai Co., Ltd.).

[0138] Examples of alkali-soluble resins include radical polymers containing carboxylic acid groups in the side chains described in JP-A-59-044615, JP-B-54-34327, JP-B-58-012577, JP-B-54-025957, JP-A-54-092723, JP-A-59-053836, and JP-A-59-071048; Examples of binder resins that can be used include acetal-modified polyvinyl alcohol binder resins containing alkali-soluble groups, as described in WO 2008 / 123097, WO 2008 / 123098, WO 2008 / 12309 ...

[0139] As the alkali-soluble resin, for example, compounds described in paragraphs 0225 to 0245 of JP-A No. 2016-075845 can also be used, the contents of which are incorporated herein by reference.

[0140] The alkali-soluble resin may also be a polyimide precursor, which is intended to be a resin obtained by subjecting a compound containing an acid anhydride group and a diamine compound to an addition polymerization reaction at 40 to 100°C. The polyimide precursor may be, for example, a resin containing a repeating unit represented by formula (1). The structure of the polyimide precursor may be, for example, a polyimide precursor containing an amic acid structure represented by formula (2) below, a polyimide precursor containing an imide structure represented by formula (3) below in which the amic acid structure is partially imide-ring-closed, and a polyimide precursor containing an imide structure represented by formula (4) below in which the amic acid structure is completely imide-ring-closed. In this specification, a polyimide precursor having an amic acid structure may be referred to as a polyamic acid.

[0141] [ka]

[0142] [ka]

[0143] [ka]

[0144] [ka]

[0145] In the above formulas (1) to (4), R1 represents a tetravalent organic group having 2 to 22 carbon atoms, R2 represents a divalent organic group having 1 to 22 carbon atoms, and n represents 1 or 2.

[0146] Specific examples of the polyimide precursor include the compounds described in paragraphs 0011 to 0031 of JP-A No. 2008-106250, the compounds described in paragraphs 0022 to 0039 of JP-A No. 2016-122101, and the compounds described in paragraphs 0061 to 0092 of JP-A No. 2016-068401, the contents of which are incorporated herein by reference.

[0147] The alkali-soluble resin preferably contains at least one selected from the group consisting of polyimide resins and polyimide precursors, since this results in a more excellent pattern shape of the cured film formed by exposure. The polyimide resin containing an alkali-soluble group is not particularly limited, and any known polyimide resin containing an alkali-soluble group can be used. Examples of the polyimide resin include the resins described in paragraph 0050 of JP 2014-137523 A, the resins described in paragraph 0058 of JP 2015-187676 A, and the resins described in paragraphs 0012 and 0013 of JP 2014-106326 A, the contents of which are incorporated herein by reference.

[0148] 〔solvent〕 The composition of the present invention includes a solvent. Examples of the solvent include water and organic solvents. The solvents include solvent A having a boiling point of 180°C or higher, solvent B having a boiling point of 140°C or higher and lower than 180°C, and solvent C having a boiling point of 100°C or higher and lower than 140°C. In this specification, the term "boiling point" means the boiling point under 1 atmosphere (760 mmHg).

[0149] <Solvent A> The boiling point of solvent A is not particularly limited as long as it is 180°C or higher, and the upper limit is preferably less than 235°C. The boiling point of solvent A is preferably 185 to 220°C, more preferably 189 to 215°C, in terms of achieving better effects of the present invention. The solubility parameter of the solvent A is not particularly limited, but may be, for example, 9.0 (cal / cm 3 ) 1 / 2 The above is preferable, and in terms of the effects of the present invention being more excellent, 11.0 (cal / cm 3 ) 1 / 2 More preferably, 12.0 (cal / cm 3 ) 1 / 2 The upper limit is, for example, 20.0 (cal / cm 3 ) 1 / 2 Preferably less than 17.0 (cal / cm3 ) 1 / 2 Less than 14.0 (cal / cm 3 ) 1 / 2 More preferably, 13.0 (cal / cm 3 ) 1 / 2 The following are particularly preferred: As used herein, the term "solubility parameter (cal / cm 3 ) 1 / 2 " is data obtained from Hansen, Charles (1967). The Three Dimensional Solubility Parameter and Solvent Diffusion Coefficient and Their Importance in Surface Coating Formulation. Copenhagen: Danish Technical Press or from known literature. The main representative examples of solvent A and their boiling points and solubility parameters are shown below.

[0150] [Table 1]

[0151] Other examples of the solvent A include diethylene glycol monomethyl ether (boiling point 194°C) and diethylene glycol diethyl ether (boiling point 188°C).

[0152] The solvent A is preferably at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, and benzyl alcohol, in that the effects of the present invention are more excellent.

[0153] <Solvent B> The boiling point of solvent B is not particularly limited as long as it is 140°C or higher and lower than 180°C, but is preferably 140 to 160°C, more preferably 145 to 160°C, in order to obtain better effects of the present invention. The solubility parameter of the solvent B is not particularly limited, but may be, for example, 8.0 (cal / cm3 ) 1 / 2 The above is preferable, and in terms of the effects of the present invention being more excellent, 9.0 (cal / cm 3 ) 1 / 2 More preferably, the upper limit is, for example, 11.0 (cal / cm 3 ) 1 / 2 Preferably less than 10.5 (cal / cm 3 ) 1 / 2 The following is more preferred: The main representative examples of solvent B and their boiling points and solubility parameters are shown below.

[0154] [Table 2]

[0155] Examples of solvent B other than those mentioned above include acetylacetone (boiling point 140°C), ethylene glycol monomethyl ether acetate (boiling point 145°C), ethylene glycol ethyl ether acetate (boiling point 145°C), ethylene glycol monoisopropyl ether (boiling point 144°C), ethylene glycol monobutyl ether acetate (boiling point 145°C), 3-methoxypropanol (boiling point 153°C), diethylene glycol dimethyl ether (boiling point 162°C), propylene glycol monoethyl ether acetate (boiling point 160°C), 3-methoxypropyl acetate (boiling point 146°C), N,N-dimethylformamide (boiling point 153°C), and methyl lactate (boiling point 144°C).

[0156] Solvent B is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate and cyclohexanone, as this will provide better effects for the present invention.

[0157] <Solvent C> The boiling point of solvent C is not particularly limited as long as it is 100°C or higher and lower than 140°C, but is preferably 100 to 135°C, more preferably 120 to 135°C, in order to obtain better effects of the present invention. The solubility parameter of the solvent C is not particularly limited, but may be, for example, 8.0 (cal / cm 3 ) 1 / 2 The above is preferable, and in terms of the effects of the present invention being more excellent, 8.5 (cal / cm 3 ) 1 / 2 More preferably, the upper limit is, for example, 11.0 (cal / cm 3 ) 1 / 2 Preferably less than 10.5 (cal / cm 3 ) 1 / 2 Less than 9.0 (cal / cm 3 ) 1 / 2 The following is even more preferred: Moreover, the solvent C is preferably an organic solvent.

[0158] The main representative examples of solvent C and their boiling points and solubility parameters are shown below.

[0159] [Table 3]

[0160] Examples of solvent C other than those mentioned above include toluene (boiling point 110°C), ethylene glycol monomethyl ether (boiling point 124°C), ethylene glycol monoethyl ether (boiling point 135°C), propylene glycol monomethyl ether (boiling point 121°C), and propylene glycol monoethyl ether (boiling point 133°C).

[0161] Solvent C is preferably at least one selected from the group consisting of butyl acetate and ethyl butyrate, as this provides better effects of the present invention.

[0162] <Other solvents> The solvent may optionally contain a solvent other than solvent A, solvent B, and solvent C (a solvent having a boiling point of less than 100°C).

[0163] <Content> The total content of solvents A, B, and C is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total mass of the solvents, and the upper limit is preferably 100% by mass or less, in order to obtain better effects of the present invention.

[0164] The content of solvent A is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, even more preferably 3.0% by mass or more, and particularly preferably 5.0% by mass or more, relative to the total content of solvents A, B, and C. In terms of providing better effects of the present invention, the content is preferably 30.0% by mass or less, and in terms of providing better effects of the present invention, the content is more preferably 25.0% by mass or less, even more preferably 20.0% by mass or less, and particularly preferably 15.0% by mass or less.

[0165] The content of solvent B is preferably 50.0% by mass or more, more preferably 55.0% by mass or more, even more preferably 60.0% by mass or more, and particularly preferably 70.0% by mass or more, relative to the total content of solvents A, B, and C. In terms of the effects of the present invention being more excellent, the content is preferably 98.0% by mass or less, and in terms of the effects of the present invention being more excellent, the content is more preferably 96.0% by mass or less, even more preferably 95.0% by mass or less, particularly preferably 90.0% by mass or less, and most preferably 85.0% by mass or less.

[0166] The content of solvent C is preferably 1.0% by mass or more relative to the total content of solvents A, B, and C. In terms of the effects of the present invention being more excellent, it is more preferably 2.0% by mass or more, even more preferably 3.0% by mass or more, particularly preferably 5.0% by mass or more, and most preferably 10.0% by mass or more. The upper limit is preferably 30.0% by mass or less, in terms of the effects of the present invention being more excellent, it is more preferably 25.0% by mass or less, even more preferably 20.0% by mass or less, and particularly preferably 15.0% by mass or less.

[0167] A suitable example of the contents of solvent A, solvent B, and solvent C is a combination in which the content of solvent A is 5.0 to 15.0 mass % relative to the total content of solvent A, solvent B, and solvent C, the content of solvent B is 70.0 to 90.0 mass % relative to the total content of solvent A, solvent B, and solvent C, and the content of solvent C is 5.0 to 15.0 mass % relative to the total content of solvent A, solvent B, and solvent C.

[0168] <Water> The composition may further contain water. The upper limit of the water content in the composition is, for example, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, relative to the total mass of the composition, and even more preferably 1.0% by mass or less, in terms of better viscosity stability over time of the composition. The lower limit of the water content in the composition is, for example, preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more, relative to the total mass of the composition.

[0169] [Polymerization initiator] The composition of the present invention preferably contains a polymerization initiator. The polymerization initiator is not particularly limited, and a known polymerization initiator can be used. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, and a photopolymerization initiator is preferred. Note that the polymerization initiator is preferably a so-called radical polymerization initiator. The content of the polymerization initiator in the composition is not particularly limited, but is preferably 0.5 to 20 mass % relative to the total solid content of the composition, more preferably 1.0 to 10 mass %, and even more preferably 1.5 to 8 mass %. One polymerization initiator may be used alone, or two or more polymerization initiators may be used in combination. When two or more polymerization initiators are used in combination, the total content is preferably within the above range.

[0170] <Thermal polymerization initiator> Examples of the thermal polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalenonitrile, and dimethyl-(2,2')-azobis(2-methylpropionate) [V-601], and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate. Specific examples of the polymerization initiator include those described on pages 65 to 148 of "Ultraviolet Curing System" by Kato Kiyomi (published by Sogo Gijutsu Center Co., Ltd., 1989).

[0171] <Photopolymerization initiator> The composition preferably contains a photoinitiator. The photopolymerization initiator is not particularly limited as long as it can initiate polymerization of the polymerizable compound, and known photopolymerization initiators can be used. As the photopolymerization initiator, for example, a photopolymerization initiator having photosensitivity to light in the ultraviolet to visible light range is preferred. In addition, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals, or an initiator that initiates cationic polymerization depending on the type of polymerizable compound. The photopolymerization initiator preferably contains one or more compounds having a molar absorption coefficient of at least 50 within a range of 300 to 800 nm (more preferably 330 to 500 nm).

[0172] The content of the photopolymerization initiator in the composition is not particularly limited, but is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, and even more preferably 1.5 to 8% by mass, based on the total solid content of the composition. One photopolymerization initiator may be used alone, or two or more may be used in combination. When two or more photopolymerization initiators are used in combination, the total content is preferably within the above range.

[0173] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds containing a triazine skeleton, compounds containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenone. Specific examples of photopolymerization initiators can be found in, for example, paragraphs 0265 to 0268 of JP-A No. 2013-029760, the contents of which are incorporated herein by reference.

[0174] More specifically, the photopolymerization initiator may be, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 or an acylphosphine-based initiator described in Japanese Patent No. 4225898. As the hydroxyacetophenone compound, for example, Omnirad-184, Omnirad-1173, Omnirad-500, Omnirad-2959, and Omnirad-127 (trade names: all manufactured by IGM RESINS BV) can be used. As the aminoacetophenone compound, for example, commercially available products such as Omnirad-907, Omnirad-369, and Omnirad-379EG (trade names: all manufactured by IGM RESINS BV) can be used. As the aminoacetophenone compound, compounds described in JP-A-2009-191179, which have an absorption wavelength matching a long-wavelength light source such as a wavelength of 365 nm or 405 nm, can also be used. As the acylphosphine compound, commercially available products such as Omnirad-819 or Omnirad-TPO (trade names: both manufactured by IGM RESINS BV) can be used.

[0175] (oxime compounds) As the photopolymerization initiator, an oxime ester-based polymerization initiator (oxime compound) is more preferred. In particular, an oxime compound is preferred because it has high sensitivity and high polymerization efficiency, and it is easy to design a high content of light-shielding pigment in the composition. Specific examples of the oxime compound that can be used include the compounds described in JP-A No. 2001-233842, JP-A No. 2000-080068, and JP-A No. 2006-342166. Examples of oxime compounds 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-ethoxycarbonyloxyimino-1-phenylpropan-1-one. Further examples include compounds described in J.C.S. Perkin II (1979) pp. 1653-1660, J.C.S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, JP-A No. 2000-066385, and compounds described in JP-A No. 2000-080068, JP-A No. 2004-534797, and JP-A No. 2006-342166. Commercially available products such as IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), and IRGACURE-OXE04 (manufactured by BASF) are also preferred. TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831, Adeka Arcles NCI-930 (manufactured by ADEKA), and N-1919 (a photoinitiator containing a carbazole oxime ester skeleton (manufactured by ADEKA)) can also be used.

[0176] Further, as oxime compounds other than those described above, the compound disclosed in JP-T-2009-519904 A in which an oxime is linked to the N-position of the carbazole; the compound disclosed in U.S. Pat. No. 7,626,957 A in which a heterosubstituent is introduced at the benzophenone moiety; the compounds disclosed in JP-A-2010-015025 A and U.S. Patent Publication No. 2009-292039 A in which a nitro group is introduced at the dye moiety; the ketoxime compound disclosed in WO-A-2009-131189 A; and the compound disclosed in U.S. Pat. No. 7,556,910 A which contains a triazine skeleton and an oxime skeleton in the same molecule; and the compound disclosed in JP-A-2009-221114 A which has an absorption maximum at 405 nm and has good sensitivity to a g-line light source. For example, see paragraphs 0274 to 0275 of Japanese Patent Application Laid-Open No. 2013-029760, the contents of which are incorporated herein by reference. Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1): The oxime compound may be an oxime compound in which the NO bond is an (E) form, an oxime compound in which the NO bond is an (Z) form, or a mixture of the (E) and (Z) forms.

[0177] [ka]

[0178] In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. In formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metallic 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. These groups may have one or more substituents. The aforementioned substituents may be further substituted with other substituents. Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group. In formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocycliccarbonyl group, and more preferably an aryl group or a heterocyclic group. These groups may have one or more substituents. Examples of the substituent include the substituents described above. In formula (OX-1), the divalent organic group represented by A is preferably an alkylene group, cycloalkylene group, or alkynylene group having 1 to 12 carbon atoms. These groups may have one or more substituents. Examples of the substituents include the substituents described above.

[0179] As the photopolymerization initiator, an oxime compound containing a fluorine atom can also be used. Specific examples of the oxime compound containing a fluorine atom include the compounds described in JP-A-2010-262028; compounds 24, 36 to 40 described in JP-A-2014-500852; and compound (C-3) described in JP-A-2013-164471. The contents of these compounds are incorporated herein by reference.

[0180] As the photopolymerization initiator, compounds represented by the following formulas (1) to (4) can also be used.

[0181] [ka]

[0182] [ka]

[0183] In formula (1), R 1 and R 2 each independently 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 arylalkyl group having 7 to 30 carbon atoms; R 1 and R 2When R is a phenyl group, the phenyl groups may be bonded to each other to form a fluorene group, and 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 heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.

[0184] In equation (2), R 1 , R 2 , R 3 , and R 4 is R in Equation (1). 1 , R 2 , R 3 , and R 4 is synonymous with R 5 -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 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.

[0185] In equation (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 arylalkyl group having 7 to 30 carbon atoms; R 3 and R 4each 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 a carbonyl group.

[0186] In equation (4), R 1 , R 3 , and R 4 is R in Equation (3). 1 , R 3 , and R 4 is synonymous with R 5 -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 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.

[0187] In the above formulas (1) and (2), R 1 and R 2 are each independently preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xylyl group. 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. 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 addition, in the above formulas (3) and (4), R 1are each independently preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xylyl group. 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. 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 the compounds described in paragraphs 0076 to 0079 of JP-A No. 2014-137466, the contents of which are incorporated herein by reference.

[0188] Furthermore, the oxime compound is preferably a compound represented by the following formula (1):

[0189] [ka]

[0190] In formula (1), R represents a group represented by the following formula (1a).

[0191] [ka]

[0192] In formula (1a), n represents an integer of 1 to 5. m represents an integer of 1 to 6. * represents a bonding position.

[0193] m is preferably 3 or 4. The compound represented by formula (1) can be synthesized, for example, according to the synthesis method described in JP-A-2012-519191.

[0194] Specific examples of oxime compounds that can be preferably used in the above composition are shown below. In addition, the compounds described in Table 1 of WO 2015-036910 can also be used as oxime compounds, the contents of which are incorporated herein by reference.

[0195] [ka] [ka]

[0196] [ka]

[0197] The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 to 500 nm, more preferably in the wavelength region of 360 to 480 nm, and even more preferably has high absorbance at wavelengths of 365 nm and 405 nm. From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, and even more preferably from 5,000 to 200,000. The molar absorption coefficient of a compound can be measured by a known method, but it is preferable to measure it, for example, using ethyl acetate at a concentration of 0.01 g / L with an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer). Two or more photopolymerization initiators may be used in combination as needed.

[0198] In addition, compounds described in paragraph 0052 of JP-A No. 2008-260927, paragraphs 0033 to 0037 of JP-A No. 2010-097210, and paragraph 0044 of JP-A No. 2015-068893 can also be used as the photopolymerization initiator, and the contents of the above are incorporated herein by reference.

[0199] The polymerization initiator is preferably an oxime ester polymerization initiator, and more preferably a compound represented by the above formula (1), in that the effects of the present invention are more excellent.

[0200] [Polymerizable compound] The composition of the present invention preferably contains a polymerizable compound. In this specification, the polymerizable compound refers to a compound that polymerizes under the action of a polymerization initiator, which will be described later, and refers to a component that is different from the dispersant and alkali-soluble resin described above. The polymerizable compound is intended to be a component different from the compound containing an epoxy group described below.

[0201] The content of the polymerizable compound in the composition is not particularly limited, but is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, and even more preferably 15 to 25% by mass, based on the total solid content of the composition. The polymerizable compound may be used alone or in combination of two or more. When two or more polymerizable compounds are used in combination, the total content is preferably within the above range. The polymerizable compound is preferably a low molecular weight compound, and the low molecular weight compound here means a compound having a molecular weight of 2000 or less.

[0202] The polymerizable compound is preferably a compound containing an unsaturated double bond. Specifically, the compound containing an unsaturated double bond is preferably a compound containing a group containing an ethylenically unsaturated bond (hereinafter also simply referred to as an "ethylenically unsaturated group"). The composition of the present invention preferably contains a low molecular weight compound containing an ethylenically unsaturated group as the polymerizable compound. The polymerizable compound is preferably a compound containing one or more ethylenically unsaturated bonds, more preferably a compound containing two or more (a compound containing two or more functional groups). In terms of the superior effects of the present invention, a compound containing three or more (a compound containing three or more functional groups) is even more preferred, a compound containing four or more (a compound containing four or more functional groups) is particularly preferred, and a compound containing six or more (a compound containing six or more functional groups) is most preferred. The upper limit is, for example, 15 or less (15 or less functional groups), preferably 10 or less (10 or less functional groups). Examples of ethylenically unsaturated groups include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group.

[0203] As the polymerizable compound, for example, the compounds described in paragraph 0050 of JP-A No. 2008-260927 and paragraph 0040 of JP-A No. 2015-068893 can be used, the contents of which are incorporated herein by reference.

[0204] The polymerizable compound may be in any chemical form, such as a monomer, a prepolymer, an oligomer, a mixture thereof, or a polymer thereof. The polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, and more preferably a 3- to 6-functional (meth)acrylate compound.

[0205] 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, see the compounds described in paragraph

[0227] of JP-A No. 2013-029760 and paragraphs

[0254] to

[0257] of JP-A No. 2008-292970, the contents of which are incorporated herein by reference.

[0206] Preferred polymerizable compounds include dipentaerythritol triacrylate (commercially available KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., and A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd.), and compounds having a structure in which the (meth)acryloyl group is connected via an ethylene glycol residue or a propylene glycol residue (e.g., SR454 and SR499, commercially available from Sartomer). Oligomeric types of these compounds can also be used. Additionally, NK Ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040, KAYARAD DPEA-12LT, KAYARAD DPHA LT, KAYARAD RP-3060, and KAYARAD DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.), etc. may also be used. Preferred embodiments of the polymerizable compound are shown below.

[0207] The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group. The polymerizable compound containing an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, more preferably a polymerizable compound in which an acid group is provided by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride, and even more preferably a compound in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-309, M-510, and M-520 manufactured by Toagosei Co., Ltd.

[0208] The acid value of the polymerizable compound containing an acid group is preferably 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development solubility is good, and if it is 40 mgKOH / g or less, it is advantageous in terms of production and / or handling. Furthermore, the photopolymerization performance is good and the curing property is excellent.

[0209] In a preferred embodiment, the polymerizable compound is 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, and examples thereof include ε-caprolactone-modified polyfunctional (meth)acrylates obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, or trimethylolmelamine with (meth)acrylic acid and ε-caprolactone. Among these, compounds containing a caprolactone structure represented by the following formula (Z-1) are preferred.

[0210] [ka]

[0211] In formula (Z-1), all six R's are groups represented by the following formula (Z-2), or 1 to 5 of the six R's are groups represented by the following formula (Z-2), and the remainder are groups represented by the following formula (Z-3).

[0212] [ka]

[0213] In formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents the number 1 or 2, and "*" represents a bond.

[0214] [ka]

[0215] In formula (Z-3), R 1 indicates a hydrogen atom or a methyl group, and "*" indicates a bond.)

[0216] Polymerizable compounds containing a caprolactone structure are, for example, KAYARAD It is commercially available as the DPCA series, and is DPCA-20 (in the above formulas (Z-1) to (Z-3), m=1, the number of groups represented by formula (Z-2)=2, R 1 are all hydrogen atoms), DPCA-30 (same formula, m=1, number of groups represented by formula (Z-2)=3, R 1 are all hydrogen atoms), DPCA-60 (same formula, m=1, number of groups represented by formula (Z-2)=6, R 1 are all hydrogen atoms), and DPCA-120 (in the formula, m=2, the number of groups represented by formula (Z-2)=6, R 1 are all hydrogen atoms).

[0217] The polymerizable compound may also be a compound represented by the following formula (Z-4) or (Z-5).

[0218] [ka]

[0219] In formulas (Z-4) and (Z-5), E is each independently -((CH2) y CH2O)- or ((CH2) y CH(CH3)O)-, each y independently represents an integer of 0 to 10, and each X independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxylic acid group. In formula (Z-4), the total number of (meth)acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the sum of all m's 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 sum of all n's is an integer of 0 to 60.

[0220] In formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. The sum of the m's is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 8. In formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. The sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and even more preferably an integer of 6 to 12. In addition, -((CH2) y CH2O)- or ((CH2) y In the case of CH(CH3)O)-, the terminal on the oxygen atom side is preferably bonded to X.

[0221] The compound 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), an embodiment in which all six Xs are acryloyl groups, and an embodiment in which all six Xs are acryloyl groups in formula (Z-5) are a mixture of a compound in which at least one of the six Xs is a hydrogen atom are preferred. Such a configuration can further improve developability.

[0222] The total content of the compound represented by formula (Z-4) or formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more. Among the compounds represented by formula (Z-4) or formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferred.

[0223] The polymerizable compound may also contain a cardo skeleton. As the polymerizable compound containing a cardo skeleton, a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferred. Examples of polymerizable compounds containing a cardo skeleton include, but are not limited to, Oncoat EX series (manufactured by Nagase & Co., Ltd.) and Oxol (manufactured by Osaka Gas Chemicals Co., Ltd.). The polymerizable compound is also preferably a compound containing an isocyanuric acid skeleton as a central core. An example of such a polymerizable compound is NK Ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.). The content of ethylenically unsaturated groups in the polymerizable compound (meaning the value obtained by dividing the number of ethylenically unsaturated groups in the polymerizable compound by the molecular weight (g / mol) of the polymerizable compound) is preferably 5.0 mmol / g or more. There is no particular upper limit, but it is generally 20.0 mmol / g or less. In addition, when the composition contains multiple types of polymerizable compounds and the double bond equivalents of the respective polymerizable compounds are not the same, it is preferable that the total value of the products of the mass ratios of the respective polymerizable compounds in all the polymerizable compounds and the double bond equivalents of the respective polymerizable compounds falls within the above range.

[0224] [Epoxy group-containing compound] The composition of the present invention may use a compound containing an epoxy group. The epoxy group-containing compound may be a compound having one or more epoxy groups in one molecule, and preferably a compound having two or more epoxy groups in one molecule. The epoxy group number in one molecule is preferably 1 to 100. The upper limit may be, for example, 10 or less, or 5 or less. The lower limit is preferably 2 or more. The compound containing an epoxy group is intended to be a component different from the dispersant, alkali-soluble resin, and polymerizable compound described above.

[0225] The epoxy group-containing compound preferably has an epoxy equivalent (= molecular weight of epoxy group-containing compound / number of epoxy groups) of 500 g / equivalent or less, more preferably 100 to 400 g / equivalent, and even more preferably 100 to 300 g / equivalent.

[0226] The compound containing an epoxy group may be either a low molecular weight compound (for example, a molecular weight of less than 2000) or a high molecular weight compound (macromolecule) (for example, a molecular weight of 2000 or more, and in the case of a polymer, a weight average molecular weight of 2000 or more). The weight average molecular weight of the compound containing an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is more preferably 10,000 or less, even more preferably 5,000 or less, and particularly preferably 3,000 or less.

[0227] The epoxy group-containing compound may be a commercially available product. Examples include EHPE3150 (manufactured by Daicel) and EPICLON N-695 (manufactured by DIC). The epoxy group-containing compound may be any of the compounds described in paragraphs 0034 to 0036 of JP 2013-011869 A, paragraphs 0147 to 0156 of JP 2014-043556 A, and paragraphs 0085 to 0092 of JP 2014-089408 A. The contents of these compounds are incorporated herein by reference.

[0228] When the composition contains a compound containing an epoxy group, the content of the compound containing an epoxy group in the composition is preferably 0.1 to 10 mass%, more preferably 0.5 to 8 mass%, and even more preferably 1.0 to 6 mass%, based on the total solid content of the composition. The epoxy group-containing compound may be used alone or in combination of two or more. When the composition contains two or more epoxy group-containing compounds, the total content thereof is preferably within the above range.

[0229] [Ultraviolet absorber] The composition may contain an ultraviolet absorber, which allows the pattern shape of the cured film formed by exposure to be more excellent (fine). The ultraviolet absorber may be a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based ultraviolet absorber. Specific examples of such an ultraviolet absorber include the compounds described in paragraphs 0137 to 0142 of JP 2012-068418 A (corresponding to paragraphs 0251 to 0254 of US 2012 / 0068292), the contents of which are incorporated herein by reference. Additionally, diethylamino-phenylsulfonyl ultraviolet absorbers (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) and the like are also preferably used. Examples of the ultraviolet absorber include the compounds exemplified in paragraphs 0134 to 0148 of JP-A No. 2012-032556. When the composition contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001 to 15 mass %, more preferably 0.01 to 10 mass %, and even more preferably 0.1 to 5 mass %, based on the total solid content of the composition.

[0230] [Silane coupling agent (adhesion agent)] The composition may also include a silane coupling agent. The silane coupling agent functions as an adhesive agent that improves adhesion between the substrate and the cured film when the cured film is formed on the substrate. A silane coupling agent is a compound containing a hydrolyzable group and other functional groups in the molecule, where the 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 through 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 carbon atoms, 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 preferred. Furthermore, when a cured film is formed on a substrate, the silane coupling agent preferably does not contain a fluorine atom or a silicon atom (excluding silicon atoms bonded to a hydrolyzable group) in order to improve adhesion between the substrate and the cured film, and more preferably does not contain a fluorine atom, a silicon atom (excluding silicon atoms bonded to a hydrolyzable group), an alkylene group substituted with a silicon atom, a linear alkyl group having 8 or more carbon atoms, or a branched alkyl group having 3 or more carbon atoms. The silane coupling agent may contain an ethylenically unsaturated group such as a (meth)acryloyl group. When the silane coupling agent contains an ethylenically unsaturated group, the number of the ethylenically unsaturated groups is preferably 1 to 10, more preferably 4 to 8. Note that a silane coupling agent containing an ethylenically unsaturated group (for example, a compound containing a hydrolyzable group and an ethylenically unsaturated group and having a molecular weight of 2000 or less) does not fall under the category of the above-mentioned polymerizable compound.

[0231] The content of the silane coupling agent in the composition is preferably 0.1 to 10 mass %, more preferably 0.5 to 8 mass %, and even more preferably 1.0 to 6 mass %, based on the total solid content in the composition. The composition may contain one silane coupling agent alone or two or more silane coupling agents. When the composition contains two or more silane coupling agents, the total amount thereof may be within the above range.

[0232] Examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

[0233] [Surfactant] The composition may contain a surfactant, which contributes to improving the applicability of the composition. When the composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 0.5 mass %, and even more preferably 0.01 to 0.1 mass %, based on the total solid content of the composition. The surfactant may be used alone or in combination of two or more. When two or more surfactants are used in combination, the total amount is preferably within the above range.

[0234] Examples of surfactants include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants. The surfactant preferably contains a silicone surfactant, as this provides a more excellent effect of the present invention.

[0235] Examples of silicone surfactants include linear polymers consisting of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains and / or terminals.

[0236] Specific examples of silicone surfactants include DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 from the DOWSIL (registered trademark) series (all manufactured by Dow Corning Toray Co., Ltd.); X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, and X-22 -6191, X-22-4515, KF-6000, KF-6004, KP-323, KP-341, KF-6001, and KF-6002 (all manufactured by Shin-Etsu Silicones Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials); BYK307, BYK323, and BYK330 (all manufactured by BYK-Chemie). As a preferred embodiment of the silicone surfactant, aromatic group-modified silicone surfactants (silicone surfactants having an aromatic group) are preferred, and phenyl-modified silicone surfactants (silicone surfactants having a phenyl group) are more preferred, in that the effects of the present invention are more excellent.

[0237] Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, and F780 (all manufactured by DIC Corporation); Fluorad FC430, FC431, and FC171 (all manufactured by DIC Corporation); (manufactured by Sumitomo 3M Limited); Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, and Surflon KH-40 (all manufactured by Asahi Glass Co., Ltd.); and PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA). A block polymer can also be used as the fluorine-based surfactant, and specific examples include the compounds described in JP-A-2011-89090.

[0238] <Pigments> The composition may further comprise pigments other than the carbon black and barium sulfate described above.

[0239] (black pigment) Examples of the pigment include black pigments other than carbon black. As the black pigment, various known black pigments can be used, and the black pigment may be an inorganic pigment or an organic pigment. Examples of black inorganic pigments include metal oxides, metal nitrides, and metal oxynitrides containing one or more metal elements selected from the group consisting of Group 4 metal elements such as titanium (Ti) and zirconium (Zr), Group 5 metal elements such as vanadium (V) and niobium (Nb), cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and silver (Ag). The inorganic pigment may be surface-modified. For example, inorganic particles that have been surface-modified with a surface treatment agent having both a silicone group and an alkyl group, such as the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., Ltd.), may be used as particles containing other atoms. For example, metal oxides, metal nitrides, and metal oxynitrides may be used as particles containing an atom (preferably a sulfur atom) selected from the group consisting of elements of Groups 13 to 17 of the Periodic Table.

[0240] In particular, it is preferable that the black pigment contains one or more types of metal-containing particles selected from the group consisting of metal nitrides and metal oxynitrides. The metal-containing particles are preferably nitrides or oxynitrides of Group 4 metal elements or nitrides or oxynitrides of Group 5 metal elements, and more preferably nitrides or oxynitrides of titanium, zirconium, vanadium, or niobium. Note that the nitride of titanium is titanium nitride, the nitride of zirconium is zirconium nitride, the nitride of vanadium is vanadium nitride, and the nitride of niobium is niobium nitride. Also, the oxynitride of titanium is titanium oxynitride, the oxynitride of zirconium is zirconium oxynitride, the oxynitride of vanadium is vanadium oxynitride, and the oxynitride of niobium is niobium oxynitride. When the composition contains, as a black pigment, one or more metal-containing particles selected from the group consisting of metal nitrides and metal oxynitrides, the content of the one or more metal-containing particles selected from the group consisting of metal nitrides and metal oxynitrides is preferably, for example, 0.1 to 30% by mass, more preferably 5 to 25% by mass, based on the total solid content of the composition.

[0241] The black pigment is preferably as fine as possible. Considering the handling property, the average primary particle diameter of the black pigment is preferably 0.01 to 0.1 μm, more preferably 0.01 to 0.05 μm.

[0242] In the present specification, titanium nitride is intended to mean TiN, and may contain oxygen atoms that are inevitable in production (for example, those in which the surface of TiN particles is oxidized unintentionally, etc.). In the present specification, titanium nitride is intended to mean a compound in which the diffraction angle 2θ of the peak derived from the (200) plane when CuKα rays are used as the X-ray source is 42.5° to 42.8°. In addition, in the present specification, titanium oxynitride is intended to mean a compound in which the diffraction angle 2θ of the peak derived from the (200) plane when CuKα rays are used as the X-ray source exceeds 42.8°. The upper limit value 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, etc. More specifically, for example, TiO2, Ti n O 2n-1 (1 ≤ n ≤ 20) low-order titanium oxides represented by, and / or TiN x O y A form containing titanium oxynitride represented by (0 < x < 2.0, 0.1 < y < 2.0) is included. In the following description, titanium nitride (the diffraction angle 2θ is 42.5° to 42.8°) and titanium oxynitride (the diffraction angle 2θ exceeds 42.8°) are collectively referred to as titanium nitride, and the form thereof will be described. Titanium nitride may also be used as particles further containing other atoms. For example, titanium nitride may be used as titanium nitride-containing particles further containing an atom (preferably, a sulfur atom) selected from the group consisting of elements of Groups 13 to 17 of the periodic table. The same applies to other metal nitrides; metal nitrides, which collectively refer to metal nitrides and metal oxynitrides, may also be used as particles further containing other atoms. For example, metal nitrides may be used as metal nitrides further containing an atom (preferably, a sulfur atom) selected from the group consisting of elements of Groups 13 to 17 of the periodic table.

[0243] When measuring the X-ray diffraction spectrum of titanium nitride using CuKα radiation as an X-ray source, the most intense peaks observed for TiN are those derived from the (200) plane at around 2θ = 42.5°, and for TiO, the most intense peaks are those derived from the (200) plane at around 2θ = 43.4°. On the other hand, although not the most intense peaks, the peaks derived from the (200) plane of anatase TiO2 are observed at around 2θ = 48.1°, and the peaks derived from the (200) plane of rutile TiO2 are observed at around 2θ = 39.2°. Therefore, the more oxygen atoms a titanium oxynitride contains, the higher the peak position shifts toward higher angles relative to 42.5°.

[0244] When the titanium nitride contains titanium oxide (TiO2), the most intense peaks are those attributable to anatase TiO2 (101) at around 2θ = 25.3° and those attributable to rutile TiO2 (110) at around 2θ = 27.4°. However, TiO2 is white and can reduce the light-shielding properties of the light-shielding film formed from the composition, so it is preferable that these peaks are reduced to the extent that they are not observable.

[0245] The crystallite size of 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 the Scherrer equation.

[0246] The crystallite size of 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 transmittance of ultraviolet light (particularly i-line (wavelength 365 nm)) tends to be higher, and a composition with higher photosensitivity can be obtained.

[0247] 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 ​​titanium nitride is 5 to 100 m 2 / g is preferred, and 10 to 60m 2 / g is more preferred.

[0248] The method for producing the black pigment is not particularly limited, and known production methods can be used, for example, a gas phase reaction method. Examples of the gas phase reaction method include an electric furnace method and a thermal plasma method, but the thermal plasma method is preferred in terms of reducing the amount of impurities mixed in, facilitating uniform particle diameters, and providing high productivity. In the thermal plasma method, the method for generating the thermal plasma is not particularly limited, and examples thereof include direct current arc discharge, multilayer arc discharge, radio frequency (RF) plasma, and hybrid plasma, with radio frequency plasma being more preferred as it involves less impurities from the electrodes. Specific methods for producing black pigments using thermal plasma methods are not particularly limited, but examples thereof include a method for producing titanium nitride by reacting titanium tetrachloride with ammonia gas in a plasma flame (Japanese Patent Laid-Open Publication No. 2-022110), a method for evaporating titanium powder using high-frequency thermal plasma, introducing nitrogen as a carrier gas, and nitriding the titanium powder during the cooling process (Japanese Patent Laid-Open Publication No. 61-011140), and a method for blowing ammonia gas into the peripheral portion of the plasma (Japanese Patent Laid-Open Publication No. 63-085007). However, the method for producing the black pigment is not limited to the above, and there are no limitations on the production method as long as a black pigment having the desired physical properties can be obtained.

[0249] The black pigment may have a layer of a compound containing silicon (hereinafter referred to as a "silicon-containing compound") on its surface. That is, the (oxy)nitride of the above metal atom may be coated with a silicon-containing compound to form the black pigment. The method for coating with a metal atom (oxy)nitride is not particularly limited, and known methods can be used, such as the method described in JP-A-53-033228, page 2, bottom right to page 4, top right (using a metal atom (oxy)nitride instead of titanium oxide), the method described in JP-A-2008-069193, paragraphs 0015 to 0043 (using a metal atom (oxy)nitride instead of fine titanium dioxide particles), and the method described in JP-A-2016-074870, paragraphs 0020 and 0124 to 0138 (using a metal atom (oxy)nitride instead of fine metal oxide particles), the contents of which are incorporated herein by reference. The black pigment may be used alone or in combination of two or more kinds.

[0250] (Other pigments) The pigment may be any pigment other than the black pigment, and the other pigment may be an inorganic pigment or an organic pigment, provided that the pigment is a pigment other than the above-mentioned barium sulfate.

[0251] Inorganic pigments The inorganic pigment is not particularly limited, and any known inorganic pigment can be used. Examples of inorganic pigments include zinc oxide, white lead, lithopone, titanium oxide, chromium oxide, iron oxide, red lead, iron oxide red, yellow lead, zinc yellow (zinc yellow type 1, zinc yellow type 2), ultramarine blue, Prussian blue (potassium iron ferrocyanide), zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, Victoria green, iron blue (unrelated to Prussian blue), vanadium zirconium blue, chrome tin pink, ceramic red, and salmon pink. The inorganic pigment may be surface-modified, for example, with a surface treatment agent having both a silicone group and an alkyl group, such as the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0252] Pigments having infrared absorbing properties can also be used. As the pigment having infrared absorption properties, tungsten compounds and metal borides are preferred. Among them, tungsten compounds are preferred from the viewpoint of excellent light-shielding properties in the infrared wavelength region. In particular, tungsten compounds are preferred from the viewpoint of excellent light transmittance in the visible light region and in the light absorption wavelength region of oxime ester polymerization initiators, which are involved in the curing efficiency by exposure.

[0253] Two or more of these pigments may be used in combination, or may be used in combination with a dye described below. In order to adjust the color and to enhance the light-shielding property in a desired wavelength region, for example, a black pigment or a pigment having infrared-shielding properties may be mixed with a chromatic pigment such as red, green, yellow, orange, purple, or blue, or a dye described below. It is preferable to mix a red pigment or dye, or a purple pigment or dye, with a pigment having infrared-shielding properties, and it is more preferable to mix a red pigment with a pigment having infrared-shielding properties. Furthermore, an infrared absorbing agent, which will be described later, may be added.

[0254] Organic pigments Examples of organic pigments include 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, 162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc. CI 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. CI 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, 146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,19 0,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279 etc; CI Pigment Green 10, 37, 58, 59 etc.; CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc.; Examples include CI Pigment Blue 1, 2, 16, 22, 60, 64, 66, 79, and 80. The pigments may be used alone or in combination of two or more.

[0255] <dye> As the coloring dye, for example, chromatic dyes such as R (red), G (green), and B (blue) can be used, as well as the colorants described in paragraphs 0027 to 0200 of JP-A 2014-042375. Also, a black dye can be used. As the dye, for example, coloring matter disclosed in JP-A Nos. 64-090403, 64-091102, 1-094301, 6-011614, JP-A No. 2592207, U.S. Pat. Nos. 4,808,501, 5,667,920, 505,950, 5,667,920, 5-333207, 6-035183, 6-051115, and 6-194828 can be used. In terms of chemical structure, pyrazole azo compounds, pyrromethene compounds, anilino azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, or pyrrolopyrazole azomethine compounds can be used. Furthermore, dye multimers can be used as dyes. Examples of dye multimers include the compounds described in JP-A-2011-213925 and JP-A-2013-041097. Furthermore, polymerizable dyes having a polymerizable group in the molecule can also be used. Commercially available products include, for example, the RDW series manufactured by Wako Pure Chemical Industries, Ltd.

[0256] <Infrared absorber> The colorant may further contain an infrared absorbing agent. The infrared absorber refers to a compound that has absorption in the infrared region (preferably, wavelengths of 650 to 1300 nm). The infrared absorber is preferably a compound that has a maximum absorption wavelength in the wavelength region of 675 to 900 nm. Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds (provided that these are phthalocyanine compounds other than copper phthalocyanine and copper phthalocyanine derivatives), iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quattarylene compounds, dithiol metal complex compounds, and croconium compounds. The phthalocyanine compounds (provided that they are phthalocyanine compounds other than copper phthalocyanine and copper phthalocyanine derivatives), naphthalocyanine compounds, iminium compounds, cyanine compounds, squarium compounds, and croconium compounds may be those disclosed in paragraphs 0010 to 0081 of JP 2010-111750 A, the contents of which are incorporated herein by reference. For cyanine compounds, see, for example, "Functional Dyes, by Makoto Okawara, Masaru Matsuoka, Teijiro Kitao, and Kosuke Hirashima, published by Kodansha Scientific, the contents of which are incorporated herein by reference.

[0257] As the colorant having the above-described spectral properties, there may be used compounds disclosed in paragraphs

[0004] to

[0016] of JP-A No. 07-164729 and / or compounds disclosed in paragraphs

[0027] to

[0062] of JP-A No. 2002-146254, and near-infrared absorbing particles comprising crystallites of an oxide containing Cu and / or P and having a number average agglomerated particle size of 5 to 200 nm, as disclosed in paragraphs

[0034] to

[0067] of JP-A No. 2011-164583.

[0258] The compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm is preferably at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds (provided that the phthalocyanine compounds are phthalocyanine compounds other than copper phthalocyanine and copper phthalocyanine derivatives), and naphthalocyanine compounds. The infrared absorber is preferably a compound that dissolves at 1% by mass or more in water at 25° C., and more preferably a compound that dissolves at 10% by mass or more in water at 25° C. Use of such a compound improves solvent resistance. Regarding pyrrolopyrrole compounds, see paragraphs

[0049] to

[0062] of JP 2010-222557 A, the contents of which are incorporated herein by reference. Regarding cyanine compounds and squarylium compounds, see paragraphs

[0022] to

[0063] of WO 2014 / 088063 A, paragraphs

[0053] to

[0118] of WO 2014 / 030628 A, paragraphs

[0028] to

[0074] of JP 2014-059550 A, paragraphs

[0013] to

[0091] of WO 2012 / 169447 A, Paragraphs 0019 to 0033 of JP 2015-176046 A, paragraphs 0053 to 0099 of JP 2014-063144 A, paragraphs 0085 to 0150 of JP 2014-052431 A, paragraphs 0076 to 0124 of JP 2014-044301 A, paragraphs 0045 to 0078 of JP 2012-008532 A , paragraphs 0027 to 0067 of JP 2015-172102 A, paragraphs 0029 to 0067 of JP 2015-172004 A, paragraphs 0029 to 0085 of JP 2015-040895 A, paragraphs 0022 to 0036 of JP 2014-126642 A, paragraphs 0011 to 00 17, paragraphs 0010 to 0025 of JP 2015-157893 A, paragraphs 0013 to 0026 of JP 2014-095007 A, paragraphs 0013 to 0047 of JP 2014-080487 A, and paragraphs 0007 to 0028 of JP 2013-227403 A, etc., the contents of which are incorporated herein by reference.

[0259] [Other optional ingredients] The composition may further contain optional components other than the above-mentioned components, such as a polymerization inhibitor, a sensitizer, a co-sensitizer, a crosslinking agent, a curing accelerator, a filler, a heat curing accelerator, a plasticizer, a diluent, and an oil sensitizer, and further, known additives such as an adhesion promoter for the substrate surface and other auxiliary agents (e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, antioxidants, fragrances, surface tension modifiers, and chain transfer agents) may be added as needed. For details of these components, please refer to, for example, paragraphs

[0183] to

[0228] of JP 2012-003225 A (corresponding paragraphs

[0237] to

[0309] of U.S. Patent Application Publication No. 2013 / 0034812), paragraphs

[0101] to

[0102] ,

[0103] to

[0104] , and

[0107] to

[0109] of JP 2008-250074 A, and paragraphs

[0159] to

[0184] of JP 2013-195480 A, the contents of which are incorporated herein by reference.

[0260] [Solid content of composition] The solid content of the composition is preferably 10 to 40 mass %, more preferably 15 to 30 mass %, relative to the total mass of the composition. That is, the content of the solvent in the composition is not particularly limited, but it is preferable that the solid content of the composition is adjusted to the above content.

[0261] [Method for producing the composition] It is preferable to first prepare a dispersion composition by dispersing carbon black, and then mix the dispersion composition obtained with other components to prepare the composition. The dispersion composition is preferably prepared by mixing carbon black, barium sulfate, copper phthalocyanines, a resin (preferably a dispersant), any metal-containing particles (e.g., metal nitrides and metal oxynitrides), and a solvent. It is also preferable to incorporate a polymerization inhibitor into the dispersion composition. The solvent used in preparing the dispersion composition may be one or more of Solvents A to C, or a solvent other than Solvents A to C.

[0262] 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 grinder, or a wet disperser).

[0263] After preparing the dispersion composition, the dispersion composition, a resin (alkali-soluble resin), a polymerizable compound, a polymerization initiator, and solvents (solvent A, solvent B, solvent C) can be mixed together to prepare a new dispersion composition. When preparing the composition, the components may be mixed all at once, or each component may be dissolved or dispersed in a solvent and then mixed successively. The order of addition and working conditions for mixing are not particularly limited.

[0264] The composition is preferably filtered through a filter for the purpose of removing foreign matter and reducing defects. Any filter that has been conventionally used for filtration purposes can be used without any particular limitation. Examples include filters made of fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins (including high density and ultra-high molecular weight) such as polyethylene and polypropylene (PP). Among these materials, polypropylene (including high density polypropylene) and nylon are preferred. The pore size of the filter is preferably 0.1 to 7.0 μm, more preferably 0.2 to 2.5 μm, even more preferably 0.2 to 1.5 μm, and particularly preferably 0.3 to 0.7 μm. Within this range, it is possible to reliably remove minute foreign matter such as impurities and aggregates contained in the pigment while suppressing filtration clogging of the pigment (including the light-blocking pigment). When using filters, different filters may be combined. In this case, filtering with the first filter may be performed only once or two or more times. When different filters are combined and filtering is performed two or more times, it is preferable that the pore size of the second and subsequent filters be the same as or larger than the pore size of the first filter. Furthermore, first filters with different pore sizes within the above-mentioned range may be combined. The pore size here can refer to the nominal value of the filter manufacturer. Commercially available filters can be selected from various filters provided by, for example, Nippon Pall Corporation, Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), and Kitz Microfilter Co., Ltd. The second filter can be made of the same material as the first filter, etc. The pore size of the second filter is preferably 0.2 to 10.0 μm, more preferably 0.2 to 7.0 μm, and even more preferably 0.3 to 6.0 μm. The composition preferably does not contain impurities such as metals, metal salts containing halogens, acids, alkalis, etc. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, even more preferably 100 ppt or less, particularly preferably 10 ppt or less, and most preferably substantially free (below the detection limit of the measuring device). The above impurities can be measured using an inductively coupled plasma mass spectrometer (Agilent 7500cs model, manufactured by Yokogawa Analytical Systems).

[0265] [Method for producing cured film] When the composition contains a polymerization initiator and a polymerizable compound, the method for producing a cured film preferably includes the following steps: By going through the following steps, for example, a patterned cured film can be formed. ·Composition layer formation process Exposure process ·Development process Each step will be described below.

[0266] <Composition layer formation process> In the composition layer forming step, prior to exposure, a composition is applied onto a support or the like to form a layer (composition layer) made of the composition. The support may be, for example, a substrate for a solid-state imaging device, in which an imaging device (light-receiving device) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (e.g., a silicon substrate). If necessary, a primer layer may be provided on the support to improve adhesion with upper layers, prevent diffusion of substances, and flatten the substrate surface.

[0267] The composition can be applied to a substrate by various coating methods such as slit coating, ink jet coating, spin coating, casting coating, roll coating, or screen printing. The thickness of the composition layer is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and even more preferably 0.2 to 3 μm. The composition layer coated on the substrate can be dried (prebaked) at a temperature of 50 to 140° C. for 10 to 300 seconds using a hot plate, oven, or the like.

[0268] [Exposure process] The exposure step is a step of irradiating the composition layer formed in the composition layer-forming step with actinic rays or radiation to expose it. Specifically, the exposure step is a step of irradiating the composition layer formed in the composition layer-forming step with actinic rays or radiation to expose it, thereby curing the light-irradiated region of the composition layer. The method of light irradiation is not particularly limited, but it is preferable to irradiate with light through a photomask having patterned openings. The exposure is preferably carried out by irradiation with radiation, and the radiation that can be used for exposure is preferably ultraviolet light such as g-ray, h-ray, and i-ray, and the light source is preferably a high-pressure mercury lamp. The irradiation intensity is 5 to 1500 mJ / cm. 2 is preferred, and 10 to 1000 mJ / cm 2 is more preferred. When the composition contains a thermal polymerization initiator, it is also preferable to heat the composition layer in the exposure step. 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, when the composition layer is heated in the exposure step, this may also serve as a post-heating step described later. In other words, when the composition layer is heated in the exposure step, the method for producing a cured film does not need to include a post-heating step.

[0269] [Development process] The development step is a step of carrying out a development treatment on the composition layer after exposure. This step dissolves the composition layer in the light-exposed region in the exposure step, leaving only the photocured portion. For example, when the light irradiation is carried out through a photomask having a patterned opening in the exposure step, a patterned cured film is obtained. The type of developer used in the development step is not particularly limited, but an alkaline developer that does not damage the underlying image pickup element and circuits is preferred. The development temperature is, for example, 20 to 30°C. The developing time is, for example, 20 to 90 seconds. In recent years, the developing time may be extended to 120 to 180 seconds to further remove residues. Furthermore, to further improve residue removal, the developer may be shaken off every 60 seconds and new developer may be supplied, and this process may be repeated several times.

[0270] The alkaline developer is preferably an alkaline aqueous solution prepared by dissolving an alkaline compound in water to a concentration of 0.001 to 10% by mass (preferably 0.01 to 5% by mass). Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene (among these, organic alkalis are preferred). When an alkaline developer is used, a washing treatment with water is generally carried out after development.

[0271] [Post-bake] After the exposure step, it is preferable to carry out a heat treatment (post-baking). Post-baking is a heat treatment after development to complete curing. The heating temperature is preferably 240°C or less, more preferably 220°C or less. There is no particular lower limit, but in consideration of efficient and effective processing, it is preferably 50°C or more, more preferably 100°C or more. Post-baking can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater.

[0272] The post-baking is preferably carried out in an atmosphere with a low oxygen concentration. The oxygen concentration is preferably 19% by volume or less, more preferably 15% by volume or less, even more preferably 10% by volume or less, particularly preferably 7% by volume or less, and most preferably 3% by volume or less. There is no particular lower limit, but a concentration of 10 ppm by volume or more is practical.

[0273] Further, instead of the post-baking by heating, the curing may be completed by UV (ultraviolet) irradiation. In this case, the composition preferably further contains a UV curing agent. The UV curing agent is preferably a UV curing agent that can be cured at a wavelength shorter than 365 nm, which is the exposure wavelength of the polymerization initiator added for a typical i-line lithography process. Examples of UV curing agents include Chiba Ilgacure 2959 (trade name). When UV irradiation is performed, the composition layer is preferably a material that cures at a wavelength of 340 nm or less. While there is no particular lower limit for the wavelength, it is generally 220 nm or more. The exposure dose of UV irradiation is preferably 100 to 5,000 mJ, more preferably 300 to 4,000 mJ, and even more preferably 800 to 3,500 mJ. This UV curing process is preferably performed after the lithography process to more effectively perform low-temperature curing. An ozone-free mercury lamp is preferably used as the exposure light source.

[0274] [Physical properties and uses of cured films] [Physical properties of cured film] The cured film obtained using the composition of the present invention has excellent light-shielding properties, and therefore preferably has an optical density (OD) per 1.5 μm film thickness in the wavelength range of 400 to 1000 nm of 2.5 or more, more preferably 3.5 or more. There is no particular upper limit, but generally, 10 or less is preferred. The cured film can be preferably used as a light-shielding film. In this specification, an optical density of 3.5 or more per 1.5 μm film thickness in the wavelength region of 400 to 1000 nm means that the optical density is 3.5 or more per 1.5 μm film thickness over the entire wavelength region of 400 to 1000 nm. In this specification, the optical density of a cured film is measured by first forming a cured film on a glass substrate and measuring the optical density using a spectrophotometer (for example, U-4100 manufactured by Hitachi High-Technologies Corporation). The thickness of the cured film is, for example, preferably 0.1 to 4.0 μm, more preferably 1.0 to 2.5 μm, and may be thinner or thicker than this range depending on the application. Furthermore, in order to have excellent low reflectivity, the cured film obtained using the composition of the present invention preferably has a maximum reflectance (incident angle 5°) per 1.5 μm film thickness in the wavelength range of 400 to 700 nm of less than 4%, more preferably less than 2%, and even more preferably less than 1%. The lower limit is not particularly limited, but is generally 0% or more. In this specification, the maximum reflectance of a cured film is measured by first forming a cured film on a glass substrate, obtaining a reflectance spectrum at an incident angle of 5° using a spectrometer (for example, the VAR unit of a spectrometer V7200 manufactured by JASCO Corporation), and determining the reflectance of light at a wavelength that exhibits the maximum reflectance in the wavelength region of 400 to 700 nm.

[0275] The cured film is also suitable for light-shielding members and light-shielding films, as well as anti-reflection members and anti-reflection films, of optical filters and modules used in portable devices such as personal computers, tablets, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as printer / multifunction devices and scanners; industrial devices such as surveillance cameras, barcode readers, automated teller machines (ATMs), high-speed cameras, and devices with identity authentication functions using facial image recognition; in-vehicle camera devices; medical camera devices such as endoscopes, capsule endoscopes, and catheters; and space equipment such as biosensors, military reconnaissance cameras, 3D map cameras, meteorological and marine observation cameras, land resource exploration cameras, and space astronomy and deep space target exploration cameras.

[0276] The cured film can also be used in applications such as micro LEDs (Light Emitting Diodes) and micro OLEDs (Organic Light Emitting Diodes).The cured film is suitable for optical filters and optical films used in micro LEDs and micro OLEDs, as well as for components that provide a light-blocking function or an anti-reflection function. Examples of micro LEDs and micro OLEDs include those described in JP-A-2015-500562 and JP-A-2014-533890.

[0277] The cured film is also suitable as an optical film for use in quantum dot sensors and quantum dot solid-state imaging devices. It is also suitable as a component for imparting light-shielding and anti-reflection functions. Examples of quantum dot sensors and quantum dot solid-state imaging devices include those described in U.S. Patent Application Publication No. 2012 / 37789 and WO 2008 / 131313.

[0278] [Light-shielding film, solid-state imaging element, and solid-state imaging device] The cured film obtained using the composition of the present invention is preferably used as a so-called light-shielding film, and such a light-shielding film is also preferably used in a solid-state imaging device. A light-shielding film is one of the preferred applications of the cured film obtained using the composition of the present invention, and the light-shielding film can be produced in the same manner as described above for producing the cured film. Specifically, the light-shielding film can be produced by applying the composition to a substrate to form a composition layer, exposing it to light, and developing it. The solid-state imaging device of the present invention is a solid-state imaging device having a cured film (light-shielding film) obtained using the above-mentioned composition of the present invention. As described above, the solid-state imaging device according to the present invention includes the above-mentioned cured film (light-shielding film). The form in which the solid-state imaging device includes the cured film (light-shielding film) is not particularly limited, and examples thereof include a form in which a substrate has a plurality of photodiodes constituting a light-receiving area of ​​a solid-state imaging device (such as a CCD image sensor or a CMOS image sensor) and light-receiving elements made of polysilicon or the like, and the cured film is provided 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, etc.) or on the opposite side of the forming surface. Furthermore, when a cured film (light-shielding film) is used as a light-attenuating film, the dynamic range of the solid-state imaging element can be improved by, for example, positioning the light-attenuating film so that some light passes through the light-attenuating film before entering the light-receiving element. The solid-state imaging device includes the solid-state imaging element.

[0279] An example of the configuration of a solid-state imaging device and a solid-state imaging element will be described with reference to Figures 1 and 2. In Figures 1 and 2, in order to clarify each part, the thickness and / or width ratios of the parts are ignored and some parts are exaggerated. As shown in FIG. 1 , a 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. Furthermore, a lens layer 111 is provided on the cover glass 103 via a spacer 104. The lens layer 111 is composed of a support 113 and a lens material 112. The lens layer 111 may be configured such that the support 113 and the lens material 112 are integrally molded. Stray light entering the peripheral region of the lens layer 111 reduces the light-collecting effect of the lens material 112 due to light diffusion, thereby reducing the amount of light reaching the imaging unit 102. Stray light also generates noise. Therefore, a light-shielding film 114 is provided on the peripheral region of the lens layer 111 to shield it from light. A cured film obtained using the composition of the present invention can also be used as the light-shielding film 114.

[0280] Solid-state imaging element 101 photoelectrically converts an optical image formed on imaging section 102, which serves as its light-receiving surface, and outputs the converted image signal. Solid-state imaging element 101 includes laminated substrate 105, which is made up of two laminated substrates. Laminated substrate 105 is made up of rectangular chip substrate 106 and circuit substrate 107, both of the same size, with circuit substrate 107 laminated on the back surface of chip substrate 106.

[0281] The material of the substrate used as the chip substrate 106 is not particularly limited, and known materials can be used.

[0282] An imaging unit 102 is provided in the center of the surface of the chip substrate 106. Furthermore, if stray light enters the peripheral region of the imaging unit 102, a dark current (noise) will be generated from the circuitry in this peripheral region, and therefore this peripheral region is provided with a light-shielding film 115 to shield it from light. A cured film obtained using the composition of the present invention is preferably used as the light-shielding film 115.

[0283] A plurality of electrode pads 108 are provided on the edge of the surface of the chip substrate 106. The electrode pads 108 are electrically connected to the imaging unit 102 via signal lines (not shown) (which may be bonding wires) provided on the surface of the chip substrate 106.

[0284] External connection terminals 109 are provided on the rear surface of the circuit board 107 at positions approximately below the electrode pads 108. Each external connection terminal 109 is connected to each electrode pad 108 via a through electrode 110 that vertically penetrates the laminated substrate 105. Each external connection terminal 109 is also connected via wiring (not shown) to a control circuit that controls the driving of the solid-state imaging element 101, an image processing circuit that performs image processing on an imaging signal output from the solid-state imaging element 101, and the like.

[0285] 2, the imaging unit 102 is composed of various components, such as a light receiving element 201, a color filter 202, and a microlens 203, which are provided on a substrate 204. The color filter 202 has blue pixels 205b, red pixels 205r, green pixels 205g, and a black matrix 205bm. A cured film obtained using the composition of the present invention may be used as the black matrix 205bm.

[0286] The substrate 204 can be made of the same material as the aforementioned chip substrate 106. A p-well layer 206 is formed on the surface of the substrate 204. In this p-well layer 206, light-receiving elements 201, which are made of n-type layers and generate and store signal charges by photoelectric conversion, are arranged in a square lattice pattern.

[0287] 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 in the surface layer of the p-well layer 206. On the other side of the light-receiving element 201, a vertical transfer path 208 belonging to an adjacent pixel is formed via an element isolation region 209 made of a p-type layer. The readout gate portion 207 is a channel region for reading out signal charges accumulated in the light-receiving element 201 to the vertical transfer path 208.

[0288] A gate insulating film 210 made of an ONO (Oxide-Nitride-Oxide) film is formed on the surface of the substrate 204. On this gate insulating film 210, vertical transfer electrodes 211 made of polysilicon or amorphous silicon are formed so as to cover the vertical transfer paths 208, the readout gate sections 207, and the device isolation regions 209 substantially directly above them. The vertical transfer electrodes 211 function as drive electrodes that drive the vertical transfer paths 208 to transfer charges, and as readout electrodes that drive the readout gate sections 207 to read out signal charges. The signal charges are transferred from the vertical transfer paths 208 to horizontal transfer paths and an output section (floating diffusion amplifier), not shown, in that order, and then output as a voltage signal.

[0289] 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 directly above the light-receiving element 201 and shields the other regions from light. A cured film obtained using the composition of the present invention may be used as the light-shielding film 212. A transparent intermediate layer is provided on the light-shielding film 212. The intermediate layer is made of an insulating film 213 made of BPSG (borophospho silicate glass), an insulating film (passivation film) 214 made of P-SiN, and a planarization film 215 made of transparent resin or the like. The color filter 202 is formed on the intermediate layer.

[0290] [Image display device] The cured film obtained using the composition of the present invention is also preferably applied to image display devices. The image display device of the present invention includes a cured film obtained using the composition of the present invention. An example of an image display device having a cured film is one in which the cured film is contained in a black matrix, and a color filter including such a black matrix is ​​used in the image display device. Next, a black matrix and a color filter including a black matrix will be described, and further, as a specific example of an image display device, a liquid crystal display device including such a color filter will be described.

[0291] <Black matrix> The cured film obtained using the composition of the present invention is also preferably contained in a black matrix, which may be contained in a color filter, a solid-state imaging device, or an image display device such as a liquid crystal display device. Examples of black matrices include those already described above, black edges provided on the periphery of image display devices such as liquid crystal display devices, grid-like and / or stripe-like black portions between red, blue, and green pixels, and dot-like and / or line-like black patterns for shading TFTs (thin film transistors). The definition of this black matrix is ​​found, for example, in Taihei Kanno's "Liquid Crystal Display Manufacturing Equipment Terminology Dictionary," Second Edition, Nikkan Kogyo Shimbun, 1996, p. 64. It is preferable that the black matrix has high light-blocking properties (optical density OD of 3 or more) in order to improve display contrast and, in the case of an active matrix driven liquid crystal display device using thin film transistors (TFTs), to prevent degradation of image quality due to light current leakage.

[0292] The method for producing the black matrix is ​​not particularly limited, but it can be produced by the same method as the method for producing the cured film described above. Specifically, a composition is applied to a substrate to form a composition layer, which is then exposed to light 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.

[0293] The material of the substrate is not particularly limited, but preferably has a transmittance of 80% or more for 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; and plastics such as polyester resins and polyolefin resins. From the viewpoints of chemical resistance and heat resistance, alkali-free glass or quartz glass is preferred.

[0294] <Color filter> The cured film obtained using the composition of the present invention is also preferably contained in a color filter. The form of the color filter including the cured film is not particularly limited, but may be a color filter including a substrate and the black matrix, i.e., a color filter including red, green, and blue colored pixels formed in openings of the black matrix formed on the substrate.

[0295] A color filter including a black matrix (cured film) can be produced, for example, by the following method. First, a coating film (composition layer) of a composition containing a pigment corresponding to each color pixel of the color filter is formed in the openings of the patterned black matrix formed on the substrate. Note that the composition for each color is not particularly limited and any known composition can be used, but it is preferable to use a composition in which the light-blocking pigment in the composition described in this specification is replaced with a colorant corresponding to each pixel. Next, the composition layer is exposed to light through a photomask having a pattern corresponding to the openings of the black matrix. The unexposed areas are then removed by development, and the resulting layer is baked to form colored pixels in the openings of the black matrix. By performing this series of operations using compositions for each color containing, for example, red, green, and blue pigments, a color filter having red, green, and blue pixels can be produced.

[0296] <Liquid crystal display device> The cured film obtained using the composition of the present invention is also preferably contained in a liquid crystal display device. The liquid crystal display device may include a color filter including the black matrix (cured film) as described above, although the embodiment is not particularly limited.

[0297] The liquid crystal display device may have, for example, a pair of substrates arranged opposite to each other and a liquid crystal compound sealed between the substrates. The substrates are as already described as the substrates for the black matrix.

[0298] A specific example of the liquid crystal display device is a laminate including, from the user's side, a polarizing plate / substrate / color filter / transparent electrode layer / alignment film / liquid crystal layer / alignment film / transparent electrode layer / TFT (Thin Film Transistor) element / substrate / polarizing plate / backlight unit in this order.

[0299] The liquid crystal display device is not limited to the above, and examples thereof include the liquid crystal display devices described in "Electronic Display Devices" (written by Akio Sasaki, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd. in 1989). Further examples thereof include the liquid crystal display devices described in "Next Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994).

[0300] [Infrared sensor] The cured film obtained using the composition of the present invention is also preferably contained in an infrared sensor. The infrared sensor according to the above embodiment will be described with reference to Fig. 3. In the infrared sensor 300 shown in Fig. 3, reference numeral 310 denotes a solid-state imaging element. The imaging region provided on the solid-state imaging element 310 is configured by combining an infrared absorbing filter 311 and a color filter 312 according to an embodiment of the present invention. The infrared absorbing filter 311 is a film that transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared region (for example, light with a wavelength of 800 to 1300 nm, preferably light with a wavelength of 900 to 1200 nm, more preferably light with a wavelength of 900 to 1000 nm), and a cured film containing an infrared absorber (the form of the infrared absorber is as already explained) as a colorant can be used. The color filter 312 is a color filter formed with pixels that transmit and absorb light of specific wavelengths in the visible light range, and for example, a color filter formed with red (R), green (G), and blue (B) pixels is used, and its form is as already explained. Between the infrared transmission filter 313 and the solid-state imaging element 310, a resin film 314 (for example, a transparent resin film) that allows light of the wavelength that has passed through the infrared transmission filter 313 to pass therethrough is disposed. The infrared transmission filter 313 is a filter that has visible light blocking properties and transmits infrared rays of a specific wavelength, and can be a cured film obtained using the composition of the present invention, which contains a colorant that absorbs light in the visible light region (e.g., a perylene compound and / or a bisbenzofuranone compound) and an infrared absorber (e.g., a pyrrolopyrrole compound, a phthalocyanine compound (but a phthalocyanine compound other than copper phthalocyanine and copper phthalocyanine derivatives), a naphthalocyanine compound, and a polymethine compound).The infrared transmission filter 313 preferably blocks light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1300 nm, for example. A microlens 315 is disposed on the incident light hν side of the color filter 312 and the infrared transmission filter 313. A planarization film 316 is formed so as to cover the microlens 315. 3, the resin film 314 is disposed, but an infrared transmission filter 313 may be formed in place of the resin film 314. That is, the infrared transmission filter 313 may be formed on the solid-state imaging element 310. In the embodiment shown in FIG. 3, the color filter 312 and the infrared transmission filter 313 have the same thickness, but the thicknesses of the two may be different. In addition, in the embodiment shown in FIG. 3, the color filter 312 is provided closer to the incident light hν side than the infrared absorbing filter 311. However, the order of the infrared absorbing filter 311 and the color filter 312 may be reversed, and the infrared absorbing filter 311 may be provided closer to the incident light hν side than the color filter 312. 3, the infrared absorbing filter 311 and the color filter 312 are laminated adjacent to each other, but the two filters do not necessarily have to be adjacent to each other, and another layer may be provided between them. A cured film obtained using the composition of the present invention can be used as a light-shielding film on the edge and / or side of the surface of the infrared absorbing filter 311, and when used on the inner wall of an infrared sensor, it can prevent internal reflection and / or unintended incidence of light on the light-receiving part, thereby improving sensitivity. This infrared sensor can simultaneously capture image information, enabling motion sensing that recognizes the movement of an object. Furthermore, because it can acquire distance information, it can also capture images that include 3D information.

[0301] Next, a solid-state imaging device to which the above-described infrared sensor is applied will be described. The solid-state imaging device includes a lens optical system, a solid-state imaging element, an infrared light emitting diode, etc. Note that for each configuration of the solid-state imaging device, paragraphs 0032 to 0036 of JP 2011-233983 A can be referred to, the contents of which are incorporated herein by reference. [Example]

[0302] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0303] [Preparation of pigment dispersion] A pigment dispersion was prepared using the following raw materials.

[0304] [Raw materials for pigment dispersion] <Carbon black> The carbon blacks used were CB-1 to CB-5 shown below. CB-1: #2350 (average primary particle size 15 nm, pH 2.5, manufactured by Mitsubishi Chemical Corporation) CB-2: MA77 (average primary particle size 23 nm, pH 2.5, manufactured by Mitsubishi Chemical Corporation) CB-3: Raven 1080 (average primary particle size 28 nm, pH 2.4, manufactured by Columbia Chemicals) CB-4: MA220 (average primary particle size 55 nm, pH 3.0, manufactured by Mitsubishi Chemical Corporation) CB-5: #2600 (average primary particle size 13 nm, pH 6.5, manufactured by Mitsubishi Chemical Corporation)

[0305] <Nitride particles or oxynitride particles> The nitride particles or oxynitride particles P-1 to P-3 shown below were used. P-1:13M-T (titanium oxynitride, manufactured by Mitsubishi Materials Corporation) P-2: Titanium nitride particles (titanium nitride, manufactured by Hefei Kai'er Co., Ltd.) P-3: Zirconium oxynitride particles (zirconium oxynitride, manufactured by Mitsubishi Materials Corporation)

[0306] <Barium sulfate> BS-1: BF-20 (Sakai Chemical Industry Co., Ltd.) (average particle size: 0.03 μm, pH: 10)

[0307] <Copper phthalocyanine or copper phthalocyanine derivative> CP-1: Pigment Blue 15 (copper phthalocyanine, manufactured by Tokyo Chemical Industry Co., Ltd.) CP-2: Copper phthalocyanine-3,4',4'',4'''-tetrasulfonic acid tetrasodium salt (copper phthalocyanine derivative, manufactured by Sigma-Aldrich) CP-3: Solsperse 5000 (copper phthalocyanine derivative, manufactured by Lubrizol) "CP-3 (Solsperse 5000)" corresponds to a salt composed of copper phthalocyanine having a sulfonic acid group and dimethyldioctadecylammonium.

[0308] <Dispersant> Dispersants H-1 to H-4 having the following structures were used as dispersants. The numerical value for each structural unit contained in the main chain indicates the mole percentage of each structural unit relative to all structural units. The numerical value for each structural unit contained in the side chain indicates the number of repetitions. H-1: Dispersant with the following structure (acid value = 103 mg KOH / g, amine value = 103 mg KOH / g, weight average molecular weight = 13,000)

[0309] [ka]

[0310] H-2: Dispersant with the following structure (acid value = 52 mg KOH / g, weight average molecular weight = 13,000)

[0311] [ka]

[0312] H-3: Dispersant with the following structure (acid value = 33 mg KOH / g, amine value = 44 mg KOH / g, weight average molecular weight = 23,000)

[0313] [ka]

[0314] H-4: Disperbyk167 (BYK)

[0315] <Solvent> PGMEA (Propylene glycol monomethyl ether acetate, solvent B) Butyl acetate (corresponding to solvent C) Cyclopentanone (corresponding to solvent C)

[0316] [Preparation of pigment dispersion] First, a mixture was obtained by mixing carbon black, barium sulfate, copper phthalocyanines (one or more selected from copper phthalocyanine and copper phthalocyanine derivatives), dispersant, solvent, and optionally added nitride and oxynitride in the compositions and amounts shown in Table 4 using a mixer (EUROSTAR manufactured by IKA Corporation). Next, the mixture was subjected to a dispersion treatment under the following conditions using an NPM-Pilot manufactured by Shinmaru Enterprises, to obtain a pigment dispersion.

[0317] <Dispersion conditions> Bead diameter: φ0.05mm (Nikkato zirconia beads, YTZ) Bead filling rate: 65% by volume Mill peripheral speed: 10m / sec Separator peripheral speed: 13m / s Amount of mixed liquid to be dispersed: 15 kg ·Circulation flow rate (pump supply amount): 90kg / hour Treatment liquid temperature: 19~21℃ ·Cooling water: water Processing time: Approximately 22 hours

[0318] The composition of the pigment dispersion is shown in the table below.

[0319] [Table 4]

[0320] [Preparation of Composition] The compositions were prepared using the following raw materials.

[0321] [Raw materials for the composition] <Pigment dispersion> As the pigment dispersions, the pigment dispersions prepared in the upper section (dispersions 1 to 18, comparative dispersions 1 and 2) were used.

[0322] <Alkali-soluble resin> The following resins C-1 to C-2 were used as alkali-soluble resins. The structures of resins C-1 to C-2 are shown below. The numerical values ​​shown for each structural unit indicate the mole percentage of each structural unit relative to all structural units.

[0323] C-1: Resin with the following structure (acid value = 110 mg KOH / g weight average molecular weight = 33,000)

[0324] [ka]

[0325] C-2: Resin with the following structure (acid value = 70 mg KOH / g weight average molecular weight = 11,000)

[0326] [ka]

[0327] <Polymerizable compound> As the polymerizable compounds, the following D-1 to D-3 were used. D-1: KAYARAD DPHA (Nippon Kayaku, hexafunctional monomer) D-2: NK Ester A-TMMT (Shinnakamura Chemical Co., Ltd., tetrafunctional monomer) D-3: Aronix M-309 (Toagosei, trifunctional monomer)

[0328] <Photopolymerization initiator> As the photopolymerization initiators, the following E-1 to E-8 were used. E-1: IRGACURE OXE01 (BASF, oxime ester polymerization initiator) E-2: IRGACURE OXE02 (BASF, oxime ester polymerization initiator) E-3: Compound with the following structure (oxime ester polymerization initiator)

[0329] [ka]

[0330] E-4: Compound with the following structure (oxime ester polymerization initiator)

[0331] [ka]

[0332] E-5: NCI-831 (ADEKA, oxime ester polymerization initiator) E-6: Compound having the following structure (corresponding to the compound represented by formula (1) above; oxime ester polymerization initiator)

[0333] [ka]

[0334] E-7: Omnirad 369 (IGM Resins BV, non-oxime ester polymerization initiator) E-8: Omnirad 379 (IGM Resins BV, non-oxime ester polymerization initiator)

[0335] <Solvent> As the solvents, the following solvents S-1 to S-19 were used.

[0336] [Table 5]

[0337] <Other ingredients> As other components, the following G-1 to G-8 were used. G-1: EHPE 3150 (manufactured by Daicel) (compound containing epoxy groups) G-2: EPICLON N-695 (DIC) (compound containing epoxy groups) G-3: Compound with the following structure (ultraviolet absorber (diethylamino-phenylsulfonyl ultraviolet absorber))

[0338] [ka]

[0339] G-4: Compound with the following structure (adhesion agent)

[0340] [ka]

[0341] W-1: Compound having the following structure (fluorine-based surfactant. Weight-average molecular weight = 15,000. In the following formula, the contents of the left-hand structural unit and the right-hand structural unit are 62% by mass and 38% by mass, respectively.)

[0342] [ka]

[0343] W-2: KF-6000 (silicone surfactant (carbinol-modified silicone; dimethyl type), manufactured by Shin-Etsu Chemical Co., Ltd.) W-3: Dowsil SH-8400 Fluid (silicone surfactant (EO-modified silicone; dimethyl type), manufactured by Dow) W-4: KP323 (silicone surfactant (phenyl-modified silicone), manufactured by Shin-Etsu Chemical Co., Ltd.)

[0344] [Preparation of Composition] The components shown in Tables 6 to 10 below were mixed with the pigment dispersion in the proportions shown in Tables 6 to 10 to obtain compositions of the examples and comparative examples. The compositions obtained are shown in Tables 6 to 10.

[0345] [Table 6]

[0346] [Table 7]

[0347] [Table 8]

[0348] [Table 9]

[0349] [Table 10]

[0350] [evaluation] The resulting compositions were subjected to the following tests and evaluations.

[0351] <Minimum OD value between 400-1000nm> The compositions of the examples and comparative examples obtained above were used to form films on a 0.7 mm thick, 10 cm square glass plate (EagleXG, Corning) by spin coating, adjusting the rotation speed so that the film thickness was 1.5 μm. The formed films were then dried by heat treatment at 100°C for 2 minutes on a hot plate, and then exposed to 1000 mJ / cm using an exposure device (light source: ultra-high pressure mercury lamp) manufactured by Ushio Lighting Inc. 2 After exposure to light at an exposure dose of 1000 ppm, the substrate was post-heated on a hot plate at 220°C for 5 minutes to obtain a cured film. The optical density (OD value) of the substrate containing the obtained cured film was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies). The higher the OD value, the better the light-blocking properties of the cured film. Evaluation was based on the following criteria. The lowest OD value in the wavelength range of 400 to 1000 nm was taken as the minimum OD value. In the following evaluation criteria, A to C are levels that present no practical problems. (Judgment criteria) A: The minimum OD value between 400 and 1000 nm is 3.5 or more. B: The minimum OD value between 400 and 1000 nm is 3.0 or more and less than 3.5 C: The minimum OD value between 400 and 1000 nm is 2.5 or more and less than 3.0 D: The minimum OD value between 400 and 1000 nm is less than 2.5.

[0352] <Highest reflectance from 400-700nm> The compositions of the examples and comparative examples obtained above were used to form films on a 0.7 mm thick, 10 cm square glass plate (EagleXG, Corning) by spin coating, adjusting the rotation speed so that the film thickness was 1.5 μm. The formed films were then dried by heat treatment at 100°C for 2 minutes on a hot plate, and then exposed to 1000 mJ / cm using an exposure device (light source: ultra-high pressure mercury lamp) manufactured by Ushio Lighting Inc. 2 After exposure at an exposure dose of 100 ppm, the substrate was post-heated on a hot plate at 220°C for 5 minutes to obtain a cured film. Light with a wavelength of 400 to 700 nm was incident on the substrate containing the obtained cured film at an incident angle of 5° using a VAR unit of a V7200 (trade name) spectrometer manufactured by JASCO Corporation, and the reflectance was determined from the resulting reflectance spectrum. Specifically, the reflectance of the light with the wavelength that showed the maximum reflectance in the wavelength range of 400 to 700 nm was taken as the reflectance of the cured film. In the following evaluation criteria, A to C are levels that present no practical problems.

[0353] (Judgment criteria) A: Maximum reflectance of less than 1% from 400 to 700 nm B: Maximum reflectance of 400-700nm is 1% or more and less than 2% C: Maximum reflectance of 400-700nm is 2% or more and less than 4% D: Maximum reflectance of 400-700nm is 4% or more and less than 6% E: Maximum reflectance of 6% or more from 400 to 700 nm

[0354] <Viscosity stability over time (rate of viscosity change over time after one year of refrigeration)> The composition obtained above was left to stand for one year in an environment at a temperature of 7°C, after which the change in viscosity was evaluated. The viscosity was measured using an E-type rotational viscometer RE85L manufactured by Toki Sangyo Co., Ltd., with a standard cone rotor (1°34' x R24), with the rotation speed set to 50 rpm and the sample cup temperature adjusted to 23±0.2°C. The viscosity was evaluated according to the following criteria. In the following evaluation criteria, A to C are levels that present no practical problems.

[0355] (Judgment criteria) A: The change in viscosity before and after the aging test is 0.0% or more and less than 3.0%. B: The change in viscosity before and after the aging test is 3.0% or more and less than 5.0%. C: The change in viscosity before and after the aging test is 5.0% or more and less than 10.0%. D: The change in viscosity before and after the aging test is 10.0% or more and less than 15.0%. E: The change in viscosity before and after the aging test is 15.0% or more.

[0356] <Minimum transmittance of glass substrate after development (solvent resistance)> Each of the compositions obtained above was applied using a spin coater onto an 8-inch glass wafer with an undercoat layer (CT-4000L, manufactured by Fujifilm Electronic Materials Co., Ltd.) so that the film thickness after drying would be 1.5 μm, and the coating was then heat-treated (pre-baked) for 120 seconds using a hot plate at 110°C. Next, a mask aligner exposure system EVG6200 (manufactured by EVG) was used to irradiate the wafer with 365 nm wavelength light at 1000 mJ / cm. 2 The film was exposed to light at 1000 kJ / cm through a mask having a 2 cm x 2 cm pattern. The glass wafer with the exposed coating film was then placed on the horizontal rotating table of a spin-shower developer (DW-30 model, manufactured by Chemitronics Corporation), and puddle development was performed using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23°C for 60 seconds, forming a 2 cm x 2 cm pattern on the glass wafer. A glass wafer with a 2 cm × 2 cm pattern formed on it was fixed to the horizontal rotating table using a vacuum chuck, and while rotating the glass wafer at 50 rpm using a rotating device, pure water was sprayed from a nozzle above the center of rotation to rinse the wafer, followed by spray drying. This was followed by a 5-minute heat treatment (post-bake: 220°C / 5 minutes) using a hot plate at 220°C. The minimum transmittance of the non-image area after the creation of the 2 cm x 2 cm pattern formed above at wavelengths of 400 to 1000 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies) and used as an evaluation of the minimum transmittance of the glass substrate after development. The smaller the fluctuation, the better the solvent resistance, which is more desirable. In the following evaluation criteria, A to C are levels that present no practical problems.

[0357] (Judgment criteria) A: Minimum transmittance is 99% or more and 100% or less B: Minimum transmittance is 98% or more and less than 99% C: Minimum transmittance is 97% or more and less than 98% D: Minimum transmittance is 95% or more and less than 97% E: Minimum transmittance is less than 95%

[0358] <Undercut> The compositions of the examples and comparative examples obtained above were prepared. Each composition was applied by spin coating onto an 8-inch silicon wafer with an undercoat layer (CT-4000L, manufactured by Fujifilm Electronic Materials Co., Ltd.) so that the film thickness after application was 1.5 μm, and then heated on a hot plate at 110° C. for 2 minutes to obtain a composition layer. Next, the resulting composition layer was exposed (exposure dose 500 mJ / cm ) through a mask to form a 300 μm line and space pattern using a mask aligner exposure system EVG6200 (manufactured by EVG). 2 )did. Next, development was performed using a developing device (Act-8, manufactured by Tokyo Electron). A 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) was used as the developer, and shower development was performed at 23°C for 60 seconds. After that, rinsing was performed with a spin shower using pure water, resulting in a 300 μm line and space pattern. The cross section of the resulting pattern was observed with a scanning electron microscope (SEM) (S-4800, manufactured by Hitachi High-Technologies Corporation) to measure the undercut width and evaluate it according to the following criteria. In the following evaluation criteria, A to C are levels that present no practical problems.

[0359] (Judgment criteria) A: 0.0 μm or more and less than 3.0 μm B: 3.0 μm or more and less than 6.0 μm C: 6.0 μm or more and less than 10.0 μm D: 10.0 μm or more and less than 25.0 μm E:25.0μm or more

[0360] <Uneven coating (coating properties)> The resulting composition was applied to a silicon wafer using a spin coater so that the film thickness after drying would be 1.5 μm, and then heat-treated (pre-baked) for 120 seconds using a hot plate at 110° C. The surface of the resulting film was observed under an optical microscope (at unit magnification) to check for the presence or absence of wavy coating unevenness, and evaluated according to the following criteria. In the following evaluation criteria, a grade of A to B is considered to be at a level that presents no practical problems.

[0361] (Judgment criteria) A: No streaky coating unevenness B: Very slight streaky coating unevenness was observed C: Many streaky coating irregularities were observed

[0362] <Evaluation of pencil hardness> Each of the compositions obtained above was applied using a spin coater onto an 8-inch silicon wafer with an undercoat layer (CT-4000L, manufactured by Fujifilm Electronic Materials Co., Ltd.) so that the film thickness after drying would be 1.5 μm, and the wafer was then heat-treated (pre-baked) for 120 seconds using a hot plate at 110°C. Next, a mask aligner exposure system EVG6200 (manufactured by EVG) was used to irradiate the wafer with 365 nm wavelength light at 1000 mJ / cm. 2 The film was exposed to light at 1000 kJ / cm through a mask having a 5 cm x 5 cm pattern. The silicon wafer with the exposed coating film was then placed on the horizontal rotating table of a spin-shower developer (DW-30 model, manufactured by Chemitronics Corporation), and puddle development was performed using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23°C for 60 seconds, forming a 5 cm x 5 cm pattern on the silicon wafer. A glass wafer with a 5 cm × 5 cm pattern formed on it was fixed to the horizontal rotating table using a vacuum chuck, and while rotating the glass wafer at 50 rpm using a rotating device, pure water was showered from a nozzle above the center of rotation to rinse the wafer, followed by spray drying. This was followed by a 5-minute heat treatment (post-bake: 220°C / 5 minutes) using a hot plate at 220°C. The pencil hardness of the 5 cm x 5 cm pattern formed above was evaluated using a continuous load scratch resistance tester TYPE: 18 (manufactured by Shinto Scientific) according to the method described in JIS K5600-5-4. In the following evaluation criteria, A to C are levels that present no practical problems.

[0363] (Judgment criteria) A: Pencil hardness 4H or higher B: Pencil hardness 3H C: Pencil hardness 2H D: Pencil hardness 1H or less

[0364] <Evaluation of peeling after humidity resistance test> The compositions of the examples and comparative examples obtained above were prepared. Each composition was applied by spin coating onto an 8-inch silicon wafer with an undercoat layer (CT-4000L, manufactured by Fujifilm Electronic Materials Co., Ltd.) so that the film thickness after application was 1.5 μm, and then heated on a hot plate at 110° C. for 2 minutes to obtain a composition layer. Next, the resulting composition layer was exposed (exposure dose 500 mJ / cm ) through a mask to form a 300 μm line and space pattern using a mask aligner exposure system EVG6200 (manufactured by EVG). 2 )did. Next, development was performed using a Tokyo Electron Act-8 developing device. A 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) was used as the developer, and shower development was performed at 23°C for 60 seconds. After that, the substrate was rinsed with a spin shower using pure water, resulting in a 300 μm line and space pattern. The resulting patterned substrate was left standing in an atmosphere of 85° C. temperature and 85% relative humidity for 750 hours, 1000 hours, and 1500 hours using a thermo-hygrostat (EHS-221M) manufactured by Yamato Scientific Co., Ltd. After the moisture resistance test, the cross section of each pattern was observed using a scanning electron microscope (SEM) (S-4800, manufactured by Hitachi High-Technologies Corporation) to check for peeling. In the following evaluation criteria, a grade of A to B is considered to be at a level that presents no practical problems.

[0365] (Judgment criteria) A: No peeling after 1500 hours of standing B: Peeling observed after leaving for 1500 hours C: Peeling observed after leaving for 1000 hours D: Peeling observed after leaving for 750 hours

[0366] [result] The test results for the compositions used in the tests are shown in Tables 11 and 12 below.

[0367] [Table 11]

[0368] [Table 12]

[0369] The results in Tables 11 and 12 clearly show that the cured films prepared using the compositions of the examples have excellent light-blocking properties (high minimum OD values ​​in the wavelength range of 400 to 1000 nm) and also have excellent low reflectivity (low maximum reflectance in the wavelength range of 400 to 700 nm). Furthermore, by comparing Examples 1 to 7, it was found that the composition had a solubility parameter of 11.0 to 14.0 (cal / cm 3 ) 1 / 2 It was confirmed that when the composition contains a solvent having a solubility parameter of 12.0 to 13.0 (cal / cm) as solvent A, the maximum reflectance at wavelengths of 400 to 700 nm is lower and the viscosity stability over time is more excellent. 3 ) 1 / 2 It was also confirmed that when the solvent contained the composition, the coating properties were also more excellent.

[0370] Furthermore, a comparison of Example 2 with Examples 8 to 12 confirmed that the viscosity stability over time was superior when solvent B in the composition was a solvent with a boiling point of 140 to 160° C. In particular, it was confirmed that the coatability was also superior when solvent B in the composition contained cyclohexanone.

[0371] Furthermore, a comparison between Example 2 and Examples 13 to 16 confirmed that the viscosity stability over time was superior when solvent C in the composition was a solvent having a boiling point of 100 to 135° C. In particular, it was confirmed that the coatability was also superior when solvent C in the composition was a solvent having a boiling point of 120 to 135° C. (preferably butyl acetate or cyclopentanone).

[0372] Comparing Example 2 with Example 17, it was confirmed that when the alkali-soluble resin has a double bond in the side chain (preferably when the side chain contains an ethylenically unsaturated group), the undercut suppression, pencil hardness, and peel suppression after humidity aging are better.

[0373] Comparison of Examples 17 to 19 confirmed that when the polymerizable compound was a tetrafunctional or higher ethylenically unsaturated compound, the undercut suppression property was superior. In particular, when the polymerizable compound was a hexafunctional or higher ethylenically unsaturated compound, it was confirmed that in addition to the undercut suppression property, the pencil hardness and the peel suppression property after humidity aging were also superior.

[0374] Comparison of Example 17 with Examples 20 to 26 confirmed that when the polymerization initiator was an oxime ester polymerization initiator, the undercut suppression property and pencil hardness were more excellent. In particular, when the polymerization initiator was a compound represented by the above formula (1), it was confirmed that in addition to the undercut suppression property and pencil hardness, the peel suppression property after humidity aging was also more excellent.

[0375] Comparing Example 17 with Examples 27 and 28, it was confirmed that the pencil hardness was further improved when a compound having an epoxy group was added.

[0376] Comparing Example 24 with Example 30, it was confirmed that when an adhesion agent was added, the undercut suppression property was superior.

[0377] Comparing Example 24 with Examples 31 to 33, it was confirmed that when the composition contained a silicone surfactant, the maximum reflectance in the wavelength range of 400 to 700 nm became lower.

[0378] Comparing Example 24 with Examples 35 and 36, it was confirmed that when the composition contains a salt composed of copper phthalocyanine having a sulfonic acid group and dimethyldioctadecylammonium as a compound selected from copper phthalocyanine and copper phthalocyanine derivatives, the minimum transmittance of the glass substrate after development becomes lower.

[0379] Comparison of Example 24 with Examples 37 to 39 confirmed that when the composition contained the above-mentioned resin X1 as a dispersant, various properties such as viscosity stability over time were more excellent.

[0380] Comparing Example 24 with Examples 40 and 41, it was confirmed that when the content ratio of barium sulfate to copper phthalocyanines in the composition (mass ratio: barium sulfate content / copper phthalocyanines content) was 1.0 to 3.0, the viscosity stability over time was better and the maximum reflectance at a wavelength of 400 to 700 nm was lower (when the content ratio was less than 1.0, the viscosity stability over time was excellent, but the maximum reflectance at a wavelength of 400 to 700 nm may be high. On the other hand, when the content ratio exceeded 3.0, the maximum reflectance at a wavelength of 400 to 700 nm was low, but the viscosity stability over time was poor).

[0381] Comparing Example 39 with Examples 42 to 45, it was confirmed that when the average primary particle diameter of the carbon black was 10 to 30 nm, the minimum OD value in the wavelength range of 400 to 1000 nm was higher. It was also confirmed that when the carbon black was acidic, the viscosity stability over time was better.

[0382] Comparing Example 24 with Examples 49 to 52, it was confirmed that when the content of solvent A was 5.0 to 15.0 mass% relative to the total mass of the solvents (total content of solvents A, B, and C), the maximum reflectance in the wavelength range of 400 to 700 nm was lower. Comparing Example 33 with Examples 46 to 49 and Examples 53 to 56, it was confirmed that coating unevenness is further suppressed when the content of solvent C is 5.0 to 15.0 mass% relative to the total mass of the solvents (total content of solvents A, B, and C).

[0383] Comparing Example 24 with Examples 57 to 59, it was confirmed that when the composition further contains one or more selected from the group consisting of metal nitrides and metal oxynitrides, the minimum OD value in the wavelength range of 400 to 1000 nm is high, the maximum reflectance in the wavelength range of 400 to 700 nm is low, and all other performances are excellent.

[0384] Examples 61 to 63 When the water concentration of Example Composition 2 (Example 2) was measured, the water content was 0.1% by mass relative to the total mass of the composition. Next, an appropriate amount of water was added to this Example Composition 2, and the water content relative to the total mass of the composition was 0.5%, 1.0%, and 1.5% by mass, respectively (water content 0.5% by mass: Example Composition 2-1 (Example 61), water content 1.0% by mass: Example Composition 2-2 (Example 62), water content 1.5% by mass: Example Composition 2-3 (Example 63)). The viscosity stability over time was evaluated in the same manner as Example Composition 2 (Example 2). The viscosity stability over time of Example Composition 2-1 (Example 61), Example Composition 2-2 (Example 62), and Example Composition 2-3 (Example 63) was A, A, and B, respectively. [Explanation of symbols]

[0385] 100 Solid-state imaging device 101 Solid-state image sensor 102 Imaging unit 103···Cover glass 104···Spacer 105...Laminated substrate 106 Chip substrate 107 Circuit board 108 Electrode pad 109 External connection terminal 110...Through electrode 111 Lens layer 112 Lens material 113...Support 114, 115...cured film 201....Photodetector 202···Color filter 201....Photodetector 202···Color filter 203 Microlens 204... Substrate 205b Blue pixel 205r...Red pixel 205g Green pixel 205bm Black Matrix 206···p-well layer 207 Read gate section 208 Vertical transfer path 209: Element isolation region 210 Gate insulating film 211 Vertical transfer electrode 212...cured film 213, 214....insulating film 215...Planarization film 300···Infrared sensor 310 Solid-state image sensor 311···Infrared absorbing filter 312···Color filter 313 Infrared transmission filter 314...Resin film 315···Microlens 316...Planarization film

Claims

1. The ink composition includes carbon black, barium sulfate, one or more selected from the group consisting of copper phthalocyanine and copper phthalocyanine derivatives, a resin, and a solvent, The solvent is a solvent A having a boiling point of 180°C or higher; Solvent B having a boiling point of 140°C or higher but lower than 180°C; A composition comprising: a solvent C having a boiling point of 100°C or higher and lower than 140°C, wherein the solvent A is dimethyl sulfoxide.

2. The composition according to claim 1 , further comprising a compound containing an unsaturated double bond and a polymerization initiator.

3. The composition according to claim 2 , wherein the polymerization initiator comprises a compound represented by the following formula (1): 【Chemistry 1】 In formula (1), R represents a group represented by the following formula (1a): 【Chemistry 2】 In formula (1a), n represents an integer of 1 to 5. m represents an integer of 1 to 6. * represents a bonding position.

4. the solvent A is dimethyl sulfoxide, the solvent B is at least one selected from the group consisting of propylene glycol monomethyl ether acetate and cyclohexanone, The composition according to any one of claims 1 to 3, wherein the solvent C is at least one selected from the group consisting of butyl acetate and ethyl butyrate.

5. 5. The composition according to claim 1, wherein the copper phthalocyanine derivative is a salt formed from copper phthalocyanine having a sulfonic acid group and dimethyldioctadecylammonium.

6. The composition according to any one of claims 1 to 5, wherein the content of the carbon black is 15 to 40 mass% based on the total solid content of the composition.

7. The composition according to any one of claims 1 to 6, further comprising one or more metal-containing particles selected from the group consisting of metal nitrides and metal oxynitrides.

8. 8. The composition of claim 7, wherein the metal-containing particles are nitrides or oxynitrides of one or more metals selected from the group consisting of titanium, zirconium, vanadium, and niobium.

9. The composition according to any one of claims 1 to 8, further comprising a silicone surfactant.

10. The composition according to claim 9, wherein the silicone surfactant is a surfactant having a phenyl group.

11. The composition according to any one of claims 1 to 10, wherein the solid content is 10 to 40 mass%.

12. The composition according to any one of claims 1 to 11, wherein the water content is 1.0 mass% or less, based on the total mass of the composition.

13. the content of the solvent A is 5.0 to 15.0 mass% with respect to the total content of the solvent A, the solvent B, and the solvent C; the content of the solvent B is 70.0 to 90.0 mass% with respect to the total content of the solvent A, the solvent B, and the solvent C; The composition according to any one of claims 1 to 12, wherein the content of the solvent C is 5.0 to 15.0 mass% with respect to the total content of the solvent A, the solvent B, and the solvent C.

14. The composition according to any one of claims 1 to 13, which is a composition for forming a light-shielding film.

15. A light-shielding film comprising a cured film formed from the composition according to any one of claims 1 to 13.

16. A solid-state imaging device comprising a cured film formed from the composition according to any one of claims 1 to 13.

17. An image display device comprising a cured film formed from the composition according to any one of claims 1 to 13.

18. a composition layer forming step of forming a composition layer comprising the composition according to claim 2 on a support; an exposure step of exposing the composition layer to actinic rays or radiation; and a development step of performing a development treatment on the composition layer after the exposure.

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