JP2010160380A - Photosensitive resin composition for near-infrared absorbent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for a near-IR absorbent which absorbs near-IR rays with wavelengths of 800 to 1,000 nm, and can form a fine pattern. <P>SOLUTION: The photosensitive resin composition for the near-IR absorbent contains: a colorant (A) containing a phthalocyanine compound having an absorption maximum wavelength in a near-IR region; a binder resin (B); a photopolymerizable compound (C); a photopolymerization initiator (D); and a solvent (E). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition for a near infrared absorber.

In recent years, plasma display panels that are thin and applicable to large screens have attracted attention. The plasma display panel generates near-infrared light having wavelengths of around 825, 880, 920, and 980 nm during plasma discharge. The near-infrared light acts on electronic devices in the vicinity such as a cordless phone, a video deck using a near-infrared remote controller, and the like, causing a problem of malfunction. Therefore, a filter for a plasma display panel and a material thereof that can efficiently absorb near infrared rays having the above-described wavelengths (825, 880, 920, and 980 nm) are desired.
For example, Patent Document 1 describes a near-infrared absorbing material that is made of a phthalocyanine compound that is a near-infrared absorbing dye and a resin and absorbs near-infrared light having a wavelength of 800 to 1000 nm. It is described that the near-infrared absorbing material can be molded into a desired shape by extrusion molding, injection molding, cast polymerization, press molding, calendar molding, cast film forming method, or the like.

JP 2007-56105 A

  In the conventional near-infrared absorbing material, it may be difficult to obtain a fine pattern.

As a result of intensive studies, the present inventors have reached the present invention.
That is, the present invention relates to a colorant (A) containing a phthalocyanine compound having an absorption maximum wavelength in the near infrared region, a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E ) Containing a photosensitive resin composition for near infrared absorbers.

  Moreover, this invention is the said photosensitive resin composition for near-infrared absorbers whose said phthalocyanine compound is a compound represented by Formula (1).

[In the formula (1), any one of 3 to 5 groups selected from the group consisting of Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ and Z ¹⁶ are independently OR ^1. 3 or 4 groups independently of each other represent NHR ³ and the remainder represents a fluorine atom.
Z ² , Z ³ , Z ⁶ , Z ⁷ , Z ¹⁰ , Z ¹¹ , Z ¹⁴ and Z ¹⁵ each independently represent OR ¹ or SR ² .
R ¹ and R ² each independently represent an aryl group having 6 to 20 carbon atoms. The hydrogen atom contained in the aryl group is a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, or a carbon number of 3 It may be substituted with -20 cycloalkyl groups or cyano groups.
R ³ represents a linear or branched alkyl group having 1 to 20 carbon atoms. The hydrogen atom contained in the alkyl group is a halogen atom, a linear or branched alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or cyano. It may be substituted with a group.
M represents a metal atom, a metal oxide, or a metal halide.
n represents 0 or 1. ]

In the present invention, any one of 3 to 5 groups selected from the group consisting of Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ and Z ¹⁶ may independently form OR ¹ . It represents the remainder being the near infrared absorbing material for a photosensitive resin composition representing the NHR ^3.

In the present invention, any one of four groups selected from the group consisting of Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ and Z ¹⁶ independently represents OR ¹ , The rest is the above-mentioned photosensitive resin composition for near-infrared absorbers that represents NHR ² independently of each other.

The present ^{invention, Z 2, Z 3, Z} 6, Z 7, Z 10, Z 11, Z 14 and ^{Z 15} are, in the near-infrared absorbing material for a photosensitive resin composition that represents the SR ² independently of one another is there.

In the present invention, R ¹ and R ² are phenyl optionally substituted by a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms. It is the said photosensitive resin composition for near-infrared absorbers which represents group.

  Moreover, this invention is the said photosensitive resin composition for near-infrared absorbers in which n represents 1 and M represents copper or vanadyl.

  Moreover, this invention is an optical filter formed using the said photosensitive resin composition for near-infrared absorbers.

Moreover, this invention is a manufacturing method of the optical filter which has the following processes.
(1) The process of apply | coating the said photosensitive resin composition for near infrared absorbers on a board | substrate (2) The process of removing a solvent from the apply | coated photosensitive resin composition layer for near infrared absorbers (3) Solvent Step of exposing the photosensitive resin composition layer for near infrared absorber after removal through a mask (4) Step of developing the photosensitive resin composition layer for near infrared absorber after exposure with an alkali developer ( 5) The process of obtaining the optical filter by heating the photosensitive resin composition layer for near-infrared absorbers after image development

  Moreover, this invention is a liquid crystal display element which has the said optical filter.

  According to the present invention, it is possible to absorb near infrared rays having a wavelength of 800 to 1000 nm and to form a fine pattern.

The photosensitive resin composition for near-infrared absorbing material of the present invention (hereinafter sometimes referred to as “photosensitive resin composition”) includes a colorant (A) and a binder containing a phthalocyanine compound having an absorption maximum wavelength in the near-infrared region. A resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E) are included. The near infrared region refers to a wavelength region of 800 to 1000 nm.
The phthalocyanine compound having an absorption maximum wavelength in the near infrared region is preferably a compound represented by the formula (1) (hereinafter sometimes referred to as “compound (1)”).

[In the formula (1), any one of 3 to 5 groups selected from the group consisting of Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ and Z ¹⁶ are independently OR ^1. 3 or 4 groups independently of each other represent NHR ³ and the remainder represents a fluorine atom.
Z ² , Z ³ , Z ⁶ , Z ⁷ , Z ¹⁰ , Z ¹¹ , Z ¹⁴ and Z ¹⁵ each independently represent OR ¹ or SR ² .
R ¹ and R ² each independently represent an aryl group having 6 to 20 carbon atoms. The hydrogen atom contained in the aryl group is a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, or a carbon number of 3 It may be substituted with -20 cycloalkyl groups or cyano groups.
R ³ represents a linear or branched alkyl group having 1 to 20 carbon atoms. The hydrogen atom contained in the alkyl group is a halogen atom, a linear or branched alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or cyano. It may be substituted with a group.
M represents a metal atom, a metal oxide, or a metal halide.
n represents 0 or 1. ]

Any 3 to 5 selected from the group consisting of Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ and Z ¹⁶ (substituents substituted at eight α positions of the phthalocyanine nucleus) It is preferred that each group independently represents OR ¹ and the rest represent NHR ³ . Furthermore, any four groups selected from the group consisting of Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ and Z ¹⁶ independently represent OR ¹ and the rest More preferably it represents NHR ² independently.

Z ² , Z ³ , Z ⁶ , Z ⁷ , Z ¹⁰ , Z ¹¹ , Z ¹⁴ and Z ¹⁵ (substituents substituting at eight β-positions of the phthalocyanine nucleus) are independently of each other OR ¹ or SR ² To express. By such substitution, it is possible to achieve a longer absorption wavelength, excellent control of the substitution position when substituted with an amino compound after substitution with OR ¹ or SR ² in the manufacturing stage, and excellent compatibility with the resin. Is played.
Z ² , Z ³ , Z ⁶ , Z ⁷ , Z ¹⁰ , Z ¹¹ , Z ¹⁴ and Z ¹⁵ preferably represent SR ² independently of each other.

  Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, phenethyl group, o-, m- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl. Group, biphenylyl group, benzhydryl group, trityl group, pyrenyl group and the like, and phenyl group is particularly preferable.

  The halogen atom is a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom.

  Specific examples of the linear or branched alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. Tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2 -Dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl -1-isopropylbutyl group, 2-methyl-1-isopropyl group, 1-t-butyl-2-methylpropyl group, n-nonyl group, 3,5,5 Trimethyl hexyl group, n- decyl and n- dodecyl and the like. Among these, a linear or branched alkyl group having 2 to 12 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 8 carbon atoms is more preferable. An n-hexyl group and a 2-ethylhexyl group are particularly preferable.

  The linear or branched alkoxy group having 1 to 20 carbon atoms is preferably a linear or branched alkoxy group having 1 to 8 carbon atoms. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, neo Examples include pentyloxy group, 1,2-dimethyl-propoxy group, n-hexyloxy group, cyclohexyloxy group, 1,3-dimethylbutoxy group, 1-isopropylpropoxy group and the like. Of these, methoxy and ethoxy groups are preferred.

  Specific examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Among these, a C3-C12 cycloalkyl group is preferable and a C3-C8 cycloalkyl group is more preferable.

Examples of the metal atom in M include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin.
Examples of the metal oxide in M include titanyl and vanadyl.
Examples of the metal halide in M include aluminum chloride, indium chloride, germanium chloride, tin (II) chloride, tin (IV) chloride, and silicon chloride.
M is preferably copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride, tin (II) chloride, more preferably copper, vanadyl or zinc, and copper or vanadyl. Particularly preferred.
n is preferably 1.
When n is 0, a covalent bond from a nitrogen atom bonded to M is bonded to a hydrogen atom and there is no coordination bond.

Examples of the compound (1) include the following. Further, in the following compounds, the 3rd and 6th positions are substituted with the α position of the phthalocyanine nucleus (substitution positions of Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ , Z ¹⁶ ). The 4th and 5th positions are substituted at the β position of the phthalocyanine nucleus (substitution positions of Z ² , Z ³ , Z ⁶ , Z ⁷ , Z ¹⁰ , Z ¹¹ , Z ¹⁴ , Z ¹⁵ ). In the abbreviations of the following compounds, Pc represents a phthalocyanine nucleus, Cu represents a central metal copper, 8 substituents substituted at the β position immediately after Pc, and after the substituents substituted at the β position Eight substituents substituted at the α-position are represented.

-4,5-octakis (phenylthio) -3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (n-hexylamino)} copper phthalocyanine Abbreviation: CuPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (CH ₃ (CH ₂ ) ₅ NH) ₄
-4,5-octakis (phenylthio) -3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (2-ethylhexylamino)} copper phthalocyanine Abbreviation; CuPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CH ₂ NH) ₄
-4,5-octakis (4-chlorophenylthio) -3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (n-hexylamino)} copper phthalocyanine Abbreviation: CuPc (4-Cl-PhS) ₈ { 2,6- (CH ₃ ) ₂ PhO} ₄ (CH ₃ (CH ₂ ) ₅ NH) ₄
・ 4,5-octakis (2-methylphenylthio) -3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (n-hexylamino)} copper phthalocyanine Abbreviation: CuPc (2-CH ₃ -PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (CH ₃ (CH ₂ ) ₅ NH) ₄
・ 4,5-octakis (4-methoxyphenylthio) -3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (n-hexylamino)} copper phthalocyanine Abbreviation: CuPc (4-CH ₃ OPhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (CH ₃ (CH ₂ ) ₅ NH) ₄
-4,5-octakis (phenylthio) -3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (3-ethoxypropylamino)} copper phthalocyanine Abbreviation; CuPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (CH ₃ CH ₂ O (CH ₂ ) ₃ NH) ₄
-4,5-octakis (5-tert-butyl-2-methylphenylthio) -3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (n-hexylamino)} copper phthalocyanine Abbreviation: CuPc {5 _{-t-Bu-2- (CH 3} ) PhS} 8 {2,6- (CH3) 2 PhO} 4 (CH 3 (CH 2) 5 NH) 4
• 4,5-octakis (2,5-dichlorophenoxy) -3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (DL-1-phenylethylamino)} vanadium oxide phthalocyanine Abbreviation; VOPc (2, 5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {Ph (CH ₃ ) CHNH} ₄
4,5-octakis (2,5-dichlorophenoxy) -3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (benzylamino)} vanadium oxide phthalocyanine Abbreviation; VOPc (2,5-Cl ₂ PhO ) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄

  Compound (1) is a compound having a visible light transmittance of 65% or more, more preferably 70% or more in a solution whose concentration is adjusted so that the minimum transmittance of 750 to 1050 nm is 10% or less. It is preferable. Among the compounds specifically exemplified above as the compound (1), in particular, 4,5-octakis (phenylthio) -3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (n-hexylamino)} copper Phthalocyanine, 4,5-octakis (phenylthio) -3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (2-ethylhexylamino)} copper phthalocyanine, 4,5-octakis (4-chlorophenylthio) -3 , 6- {Tetrakis (2,6-dimethylphenoxy) -tetrakis (n-hexylamino)} copper phthalocyanine and 4,5-octakis (2-methylphenylthio) -3,6- {tetrakis (2,6- Dimethylphenoxy) -tetrakis (n-hexylamino)} copper phthalocyanine is preferred.

The production method of compound (1) is not particularly limited, and known methods such as those described in JP-A No. 2000-26748, JP-A No. 2001-10689, and JP-A No. 2007-56105 are used. it can. For example, the method for producing compound (1) includes a method in which a phthalonitrile compound and a metal salt are cyclized in a molten state or in an organic solvent, and then the cyclized reaction product is further reacted with an amino compound. .
Compound (1) is “IR-17”, “IR-10”, “IR-10A”, “IR-12”, “IR-14”, whose title is “EEX Color” manufactured by Nippon Shokubai Co., Ltd. Etc. ".

Content of compound (1) is a mass fraction with respect to a coloring agent (A), Preferably it is 50-100%, More preferably, it is 60-100%, More preferably, it is 75-100%. .
When it is in the above range, the color density when it is used as an optical filter is sufficient, and a necessary amount of a binder polymer can be contained in the photosensitive resin composition, which is preferable.

  When used for a solid-state imaging device or a liquid crystal display device, the colorant (A) may further contain a dye and / or pigment different from the compound (1) within a range not impairing the color characteristics. The dyes and / or pigments may be used alone or in combination of two or more.

Examples of the dye include acid dyes, basic dyes, direct dyes, sulfur dyes, vat dyes, naphthol dyes, reactive dyes, and disperse dyes, which can be selected from conventionally known dyes for use in color filters.
Examples of the dye include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, JP 2592207, US Pat. No. 808,501, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6 -51115 gazette, Unexamined-Japanese-Patent No. 6-194828, etc. are mentioned.
The chemical structure of the dye includes pyrazole azo, anilino azo, aryl azo, pyrazolo triazole azo, pyridone azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, cyanine, polymethine, Phenothiazine, pyrrolopyrazole, azomethine, xanthene, phthalocyanine, quinophthalone, benzopyran, indigo, dioxazine, coumarin, squarylium, preferably pyrazole azo, anilinoazo, pyrazolotriazole azo , Pyridone azo, anthraquinone, anthrapyridone, phthalocyanine, dioxazine, quinophthalone, xanthene, more preferably pyrazole azo, pyridone azo, Taroshianin system, quinophthalone, and the like xanthene.

Examples of the pigment include organic pigments and inorganic pigments, and compounds classified as pigments by Color Index (published by The Society of Dyers and Colorists).
Specifically, for example, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7 and 36;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7. Among them, C.I. I. Pigment yellow 138, 139, 150, C.I. I. Pigment red 177, 209, 254, C.I. I. Pigment red violet 23, C.I. I. Pigment blue 15: 6 and C.I. I. It is preferable that at least one pigment selected from CI Pigment Green 36 is contained. These pigments may be used alone or in combination of two or more.

  Among the above-mentioned pigments, organic pigments may be rosin-treated, surface treated with a pigment derivative or pigment dispersant introduced with an acidic group or basic group, or grafted onto the pigment surface with a polymer compound, if necessary. Treatment, atomization treatment by a sulfuric acid atomization method, or the like, cleaning treatment by an organic solvent or water for removing impurities, removal treatment by ion exchange method of ionic impurities, or the like may be performed.

  As the pigment dispersant, commercially available surfactants can be used, and examples include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, and amphoteric surfactants. Each is used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFuck (manufactured by Dainippon Ink & Chemicals, Inc.), Fluorado (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.), PB821 (manufactured by Ajinomoto Co., Inc.), etc. Is mentioned.

The content of the dye and / or pigment different from the compound (1) is a mass fraction with respect to the colorant (A), preferably 0.01 to 50%, more preferably 0.01 to 40%. More preferably, it is 0.01 to 25%.
The content of the colorant (A) is preferably 0.1 to 70%, more preferably 1 to 60%, and further preferably 3 to 30% with respect to the solid content of the photosensitive resin composition. It is.

  The photosensitive resin composition of the present invention contains a binder resin (B). The binder resin (B) preferably contains a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. The content of the structural unit derived from the (meth) acrylic acid is preferably 16 mol% or more and 40 mol% or less, more preferably 18 in terms of mole fraction in all the structural units constituting the binder resin (B). It is from mol% to 38 mol%.

  Examples of the other monomer that leads to the constituent unit of the binder resin other than the constituent unit derived from (meth) acrylic acid include, for example, aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, and unsaturated compounds. Carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, monoacryloyl group or mono at the end of the polymer molecular chain Examples thereof include macromonomers having a methacryloyl group, units represented by the formula (I), and units represented by the formula (II).

(In Formula (I) and Formula (II), R ^{13 to} R ¹⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

Specific examples of the binder resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, and methacrylic acid / styrene. / Benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / constituent component represented by formula (I) (wherein, in formula (I), R ¹³ represents a methyl group and R ¹⁴ represents a hydrogen atom) / Benzyl methacrylate copolymer, component represented by formula (I) (wherein, in formula (I), R ¹³ represents a methyl group and R ¹⁴ represents a hydrogen atom). / Benzyl methacrylate copolymer, methacrylic acid / constituent component represented by formula (II) (here, formula (I In I), R ¹⁵ represents a methyl group, and R ¹⁶ represents a hydrogen atom.) / Styrene copolymer / tricyclodecanyl methacrylate copolymer and the like are preferable.

  The acid value of binder resin (B) used by this invention is 50-150 normally, Preferably it is 60-135, Most preferably, it is 70-135. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic acid polymer, and is usually obtained by titration with an aqueous potassium hydroxide solution. it can.

  Content of binder resin (B) is a mass fraction with respect to solid content of the photosensitive resin composition, and is 15-35 mass% normally, Preferably it is 18-33 mass%, More preferably, it is 21. It is -31 mass%.

Binder resin having a component represented by the formula (I), for example, methacrylic acid / a component represented by the formula (I) (wherein, in the formula (I), R ¹³ represents a methyl group, R ¹⁴ represents a hydrogen atom.) / A benzyl methacrylate copolymer is obtained by polymerizing methacrylic acid and benzyl methacrylate to obtain a two-component polymer, and the resulting two-component polymer is represented by the formula (III). (Wherein, R ¹⁴ represents a hydrogen atom in formula (III)).

Methacrylic acid / constituent component represented by formula (II) (wherein, in formula (II), R ¹⁵ represents a methyl group and R ¹⁶ represents a hydrogen atom) / styrene copolymer / tricyclo The decanyl methacrylate copolymer can be obtained by reacting benzyl methacrylate, methacrylic acid, or a monomethacrylate copolymer having a tricyclodecane skeleton with glycidyl methacrylate.

The weight average molecular weight in terms of polystyrene of the binder resin is usually 5,000 to 35,000, preferably 6,000 to 30,000, and particularly preferably 7,000 to 28,000.
In particular, the binder resin (B) represented by the formula (IV) is preferable.

  The photosensitive resin composition of this invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) is a compound that can be polymerized by an active radical, an acid, or the like generated from the photopolymerization initiator (D) when irradiated with light. Examples thereof include compounds having a saturated bond.

The photopolymerizable compound (C) is preferably a trifunctional or higher polyfunctional photopolymerizable compound. Examples of the trifunctional or higher polyfunctional photopolymerizable compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. Is mentioned.
Moreover, the compound which has 1 or more allyl group or methallyl group in a molecule | numerator can also be used as said photopolymerizable compound (C). Examples of compounds having one or more allyl groups or methallyl groups in the molecule include (meth) allyl ethers, (meth) allyl esters, (meth) allyl (iso) cyanurates, (meth) allyl carbonates, and the like. Can be mentioned. Among these, compounds having two or more allyl groups or methallyl groups in the molecule are preferable.
Specific examples of (meth) allyl ethers include trimethylolpropane di (meth) allyl ether, pentaerythritol tri (meth) allyl ether, etc., as well as epoxy groups of allyl glycidyl ether with polyvalent carboxylic acids or acid anhydrides thereof. A compound reacted with can also be used.
Specific examples of (meth) allyl esters include di (meth) allyl phthalate, di (meth) allyl isophthalate, di (meth) allyl terephthalate, di (meth) allyl maleate, di (meth) allyl fumarate, Examples include di (meth) allyl endomethylene tetrahydroanhydrophthalate and tri (meth) allyl trimellitate.
Specific examples of (meth) allyl (iso) cyanurates include tri (meth) allyl isocyanurate, di (meth) allyl monoglycidyl isocyanurate, mono (meth) allyl diglycidyl isocyanurate and the like.
Specific examples of (meth) allyl carbonates include diethylene glycol bis (meth) allyl carbonate.
Preferred are pentaerythritol tri (meth) allyl ether, tri (meth) allyl isocyanurate, di (meth) allyl monoglycidyl isocyanurate and the like.

  The photopolymerizable compound (C) may be used alone or in combination of two or more, and the content thereof is 5 to 90% by mass with respect to the solid content of the photosensitive resin composition. It is preferable that there is, more preferably 10 to 80% by mass, still more preferably 20 to 70% by mass.

The photosensitive resin composition of the present invention contains a photopolymerization initiator (D). Examples of the photopolymerization initiator (D) include acetophenone compounds, active radical generators, and acid generators.
Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropane-1. -One, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 -[4- (1-methylvinyl) phenyl] propan-1-one oligomers, and the like, preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and the like. It is done.

  An active radical generator generates an active radical when irradiated with light. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, oxime compounds, and compounds having a mercapto group.

  Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl ] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) ) Such -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the oxime compounds include O-acyloxime compounds, and specific examples thereof include 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O—. Benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1-one oxime-O-acetate 1- (4-phenylsulfanyl-phenyl) -butan-1-one oxime-O-acetate and the like.

Examples of the compound having a mercapto group include thioglycolic acid and / or an ester of (α-, β-) mercaptopropionic acid and a polyhydroxy compound.
Specific examples include hexanedithiool, decanedithiol, butanediol bismercaptoacetate, butanediol bismercaptopropionate, butanediol bismercaptobutanoate, trimethylolpropane tristhiomercaptoacetate, trimethylolpropane trismercaptopropio. , Trimethylolpropane trismercaptobutanoate, pentaerythritol tetrakismercaptoacetate, pentaerythritol tetrakismercaptopropionate, pentaerythritol tetrakismercaptobutanoate, dipentaerythritol hexakismercaptoacetate, dipentaerythritol hexakismercaptopropionate Dipentaerythritol hexakis mercaptobutanoe , Trismercaptoacetoxyethyl isocyanurate, trismercaptopropionyloxyethyl isocyanurate, trismercaptobutanoyloxyethyl isocyanurate, 2-di-n-butylamino-4,6-dimercapto-s-triazine, etc. Examples thereof include mercaptoacetate, mercaptopropionate, mercaptobutanoate and the like, which are polyvalent hydroxy compounds. Preferred examples include pentaerythritol tetrakismercaptopropionate, pentaerythritol tetrakismercaptobutanoate, dipentaerythritol hexakismercaptopropionate and dipentaerythritol hexakismercaptobutanoate, and particularly preferred is dipentaerythritol hexakis. Mercaptopropionate is mentioned.

  Examples of active radical generators other than those exemplified above include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2′-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. can also be used. .

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl, Onium salts such as methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.

  Among the compounds described above as the active radical generator, there are compounds that generate an acid simultaneously with the active radical. For example, a triazine photopolymerization initiator is also used as an acid generator.

  Content of a photoinitiator (D) is a mass fraction with respect to the total amount of binder resin (B) and a photopolymerizable compound (C), Preferably it is 0.1-20 mass%, More preferably Is 1 to 15% by mass.

The photosensitive resin composition of the present invention may further contain a photopolymerization initiation assistant (F). The photopolymerization initiation assistant (F) is a compound that is usually used in combination with the photopolymerization initiator (D), and is used to accelerate the polymerization of the photopolymerizable compound that has been polymerized by the photopolymerization initiator. is there.
Examples of the photopolymerization initiation assistant (F) include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.
Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylbenzoate. Aminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4, Examples thereof include 4′-bis (ethylmethylamino) benzophenone, and among these, 4,4′-bis (diethylamino) benzophenone is preferable.

  Examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  The photopolymerization initiation assistant (F) may be used alone or in combination of two or more. Moreover, as a photopolymerization start adjuvant (F), a commercially available thing can also be used, and as a commercially available photopolymerization start adjuvant (F), brand name "EAB-F" (Hodogaya Chemical Industry ( Etc.).

  Examples of the combination of the photopolymerization initiator (D) and the photopolymerization initiation assistant (F) in the photosensitive resin composition of the present invention include, for example, diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone, 2-methyl 2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4,4 '-Bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one / 4,4'-bis (diethylamino) benzophenone, 1-hydroxycyclohexyl phenyl ketone 4,4′-bis (diethylamino) benzophenone, oligomer of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one / 4,4′-bis (diethylamino) benzophenone 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone and the like, preferably 2-methyl-2-morpholino-1 -(4-Methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone.

  When using these photoinitiators (F), the amount used is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol, per 1 mol of photopolymerization initiator (D). .

  The photosensitive resin composition of the present invention contains a solvent (E). Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones other than the above, alcohols, esters, amides, N-methylpyrrolidone, dimethylsulfoxide, and the like.

  Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. , Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, methoxybutyl acetate, methoxy pentyl acetate, anisole, phenetole, and the like methyl anisole.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, and cyclohexanone.
Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diacetone alcohol, and glycerin.

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3 -Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2- Ethyl methyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutane Examples include methyl acid, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone.
Examples of the amides include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone and diacetone alcohol are preferable, and it is more preferable to use these in combination.
Furthermore, the said solvent may be used individually or in combination of 2 or more types.

  Content of the solvent (E) in a photosensitive resin composition is a mass fraction with respect to the photosensitive resin composition, Preferably it is 70-95 mass%, More preferably, it is 75-90 mass%.

The photosensitive resin composition of this invention can also contain a hardening | curing agent (G) as needed.
Examples of the curing agent (G) include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, and other aromatic epoxy resins. , Alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxy resins such as epoxidized oil, brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof Aliphatic, cycloaliphatic or aromatic epoxy compounds, epoxy compounds such as triglycidyl isocyanurate, carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, bisoxetane cyclohexanedicarboxylate , Bis [3- (3-ethyloxetanyl) methyl] ether, 1,4-bis {3- (3-ethyloxetanyl) methoxy} benzene, 1,4-bis [3- (3-ethyloxetanyl) methoxy] Oxetane compounds such as methylbenzene, 1,4-bis [3- (3-ethyloxetanyl) methoxy] cyclohexane, 1,4-bis [3- (3-ethyloxetanyl) methoxy] methylcyclohexane, alkoxymethylated melamine resin, Also included are alkoxymethylated amino resins such as alkoxymethylated urea resins. Here, as the alkoxymethylated melamine resin, methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, etc., as alkoxymethylated urea resin, for example, methoxymethylated Examples include methylol compounds such as urea resin, ethoxymethylated urea resin, propoxymethylated urea resin, and butoxymethylated urea resin.

The photosensitive resin composition of the present invention may further contain a surfactant (H). Examples of the surfactant (H) include at least one selected from the group consisting of silicone surfactants excluding those having a fluorine atom, fluorine surfactants, and silicone surfactants having a fluorine atom.
Examples of the silicone surfactant excluding those having a fluorine atom include surfactants having a siloxane bond. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH28PA, 29SHPA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Torresilicone Co., Ltd.), KP321, KP322, KP323 , KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by GE Toshiba Silicone Co., Ltd.).

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Florard (trade name) FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFuck (trade name) F142D, F171, F172, F173, F177, F177, F183, R30 (large) Nippon Ink Chemical Co., Ltd.), Ftop (trade name) EF301, EF303, EF351, EF352, EF352 (manufactured by Shin-Akita Kasei), Surflon (tradename) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100 (all trade names: manufactured by BM Chemie) and the like.
Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by Dainippon Ink & Chemicals, Inc.) and the like can be mentioned.
These surfactants may be used alone or in combination of two or more.
Content of surfactant (H) is a mass fraction with respect to the photosensitive resin composition, Preferably it is 0.0005-0.6 mass%, More preferably, it is 0.001-0.5 mass%. is there.

Examples of a method for forming an optical filter pattern using the photosensitive resin composition of the present invention include a photolithography method and an ink jet method. Examples of the photolithography method include a manufacturing method having the following steps.
(1) The process of apply | coating the photosensitive resin composition for near-infrared absorbers in any one of Claims 1-7 on a board | substrate (2) From the apply | coated photosensitive resin composition layer for near-infrared absorbers Step of removing solvent (3) Step of exposing photosensitive resin composition layer for near infrared absorber after removal of solvent through mask (4) Photosensitive resin composition layer for near infrared absorber after exposure (5) A step of heating the photosensitive resin composition layer for near-infrared absorbing material after development to obtain an optical filter The pattern of the optical filter can also be obtained by an inkjet method using an inkjet device. Can be formed.

  According to the photosensitive resin composition of the present invention, it is possible to obtain a coating film that selectively absorbs the near infrared region partially.

<< Method of manufacturing near-infrared absorbing optical filter >>
The photosensitive resin composition is, for example, an optical filter that can be applied on a substrate directly or through another layer as described below, and can be exposed and developed to transmit near infrared rays at an arbitrary position. A negative pattern can be formed. Examples of the substrate include a transparent glass plate, a silicon wafer, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a resin substrate such as a polyimide substrate. On the substrate, a black matrix, a coloring pattern, a transparent pattern for adjusting a film thickness, a TFT, and the like may be formed.
The layer made of the photosensitive resin composition can be formed by, for example, a method of applying the photosensitive resin composition on the substrate.
The coating is performed by, for example, a spin coating method, a casting coating method, a roll coating method, a slit and spin coating method, a slit coating method, a die coating method, or a curtain flow coating method. After application, the photosensitive resin composition layer is formed by volatilizing volatile components such as a solvent by drying by heating (pre-baking), vacuum drying, or a combination of both. The thickness of the photosensitive resin composition layer is not particularly limited, and is 0.01 to 20 μm, preferably 0.5 to 5 μm.
Next, the photosensitive resin composition layer is irradiated with radiation through a mask. The mask pattern is appropriately selected according to the target pattern of the cured resin pattern. Examples of the radiation include visible light, ultraviolet light, far ultraviolet light, and X-rays. For example, ultraviolet light such as g-line and i-line is preferably used. For the radiation irradiation, it is preferable to use a device such as a mask aligner or a stepper, for example.
After irradiation with radiation, the photosensitive resin composition is developed. Development can be performed on the exposed photosensitive resin composition layer by, for example, a paddle method, an immersion method, a spray method, or a shower method.
As the developer, an alkaline aqueous solution is usually used. As the alkaline aqueous solution, an aqueous solution of an alkaline compound is used, and the alkaline compound may be an inorganic alkaline compound or an organic alkaline compound.

The alkaline compound may be either an inorganic or organic alkaline compound. Examples of inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, and carbonic acid. Sodium, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia and the like can be mentioned.
Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Is mentioned. These inorganic alkaline compounds and organic alkaline compounds can be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The surfactant in the alkaline developer may be any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.
Specific examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Examples thereof include oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.
Specific examples of anionic surfactants include higher alcohol sulfate salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.
Specific examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride.
These surfactants can be used alone or in combination of two or more.
The concentration of the surfactant in the alkali developer is preferably in the range of 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass.

  Next, the photosensitive resin composition layer is washed with water after development, and further subjected to a post-baking step at 50 to 240 ° C., preferably 150 to 230 ° C. for 10 to 60 minutes as necessary to obtain pixels. It is done.

By using the photosensitive resin composition of the present invention, a film can be formed on the substrate through the above-described steps.
In the obtained film, the angle of the film with respect to the substrate is preferably less than 90 degrees, more preferably 60 to 85 degrees.

  Since the photosensitive resin composition of the present invention has good sensitivity, it can be suitably used as an optical filter in display devices such as liquid crystal display devices, electroluminescence, and plasma display panels by patterning.

  Therefore, by incorporating the optical filter thus obtained in a display device such as a liquid crystal display device, an excellent quality display device can be manufactured with a high yield.

  The optical filter of the present invention can be used for a solid-state imaging device such as a CCD, and is particularly suitable for a CCD device, a CMOS device, or the like having a high resolution exceeding 1 million pixels. The optical filter of the present invention can also be used as, for example, a near-infrared absorption filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for collecting light.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.

The components used in this example are as follows, and may be omitted below.
(A-1); 4,5-octakis (phenylthio) -3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (n-hexylamino)} copper phthalocyanine phthalocyanine abbreviation; CuPc (PhS) ₈ {2 , 6- (CH ₃ ) ₂ PhO} ₄ (CH ₃ (CH ₂ ) ₅ NH) ₄ : (e-ex color IR-17; manufactured by Nippon Shokubai Co., Ltd.)
(A-2); 4,5-octakis (2,5-dichlorophenoxy) -3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (DL-1-phenylethylamino)} vanadium oxide phthalocyanine phthalocyanine Abbreviation: VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {Ph (CH ₃ ) CHNH} ₄ : (e-excolor IR-10A; manufactured by Nippon Shokubai Co., Ltd.) )
(A-3); 4,5-octakis (2,5-dichlorophenoxy) -3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (benzylamino)} vanadium oxide phthalocyanine phthalocyanine abbreviation; VOPc (2 , 5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ : (e-excolor IR-12; manufactured by Nippon Shokubai Co., Ltd.)

<Synthesis of Resin (B-1)>
182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and the atmosphere in the flask was replaced with nitrogen from air. The temperature of propylene glycol monomethyl ether acetate was raised to 100 ° C. 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) ), A mixed solution consisting of 136 g of propylene glycol monomethyl ether acetate and 3.6 g of azobisisobutyronitrile was prepared. The obtained mixed solution was dropped into propylene glycol monomethyl ether acetate which was heated, and the obtained solution was continuously stirred at 100 ° C. Next, the atmosphere in the flask was replaced from nitrogen to air. To the obtained solution, 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% based on the carboxyl group of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone. And the reaction was continued at 110 ° C. to obtain a resin solution containing a resin (B-1) having a solid content acid value of 79 mgKOH / g. The weight average molecular weight of the resin (B-1) in terms of polystyrene measured by GPC was 3.0 × 10 ⁴ .

About the measurement of the polystyrene conversion weight average molecular weight of said resin, it carried out on condition of the following using GPC method.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent; THF
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Example 1
[Preparation of photosensitive resin composition 1]
(A) Colorant: Dye (A-1) 10 parts (B) Resin: Resin solution (B-1) 157 parts (C) Photopolymerizable compound: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Photopolymerization initiator: Irgacure 907 (manufactured by Ciba Japan Co., Ltd.) 15 parts (E) Solvent: 289 parts of 4-hydroxy-4-methyl-2-pentanone is mixed to prepare photosensitive resin composition 1 (Hereinafter sometimes abbreviated as “Composition 1”).

[Formation of pattern]
The composition 1 was applied by spin coating on a 2-inch square glass substrate (Eagle 2000; manufactured by Corning) and prebaked at 100 ° C. for 3 minutes. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Corporation), the interval between the substrate coated with the composition 1 and a quartz glass photomask having a pattern described in each evaluation item below is set to 100 μm. The substrate was irradiated with light at an exposure amount of 300 mJ / cm ² (based on 365 nm) in an air atmosphere.
After the light irradiation, the coating film was immersed and developed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23 ° C. for 80 seconds and washed with water.
Here, the spectral characteristics ((x, y) in the xy chromaticity coordinates) of the CIE XYZ color system using the C light source of the substrate on which the coating film of the obtained composition 1 was formed were measured with a colorimeter (OSP). -SP-200; Olympus Corporation).
After the measurement, post-baking was performed in an oven at 220 ° C. for 20 minutes. After standing to cool, the film thickness of the obtained cured pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.) and found to be 2.2 μm. Further, the spectral characteristics ((x, y) in xy chromaticity coordinates) of the CIE XYZ color system using a C light source were measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation). did.

[Evaluation]
About the spectral characteristic of the coating film on the obtained glass substrate, xy chromaticity coordinates (x, y) were measured in the same manner as described above, and the fading in post-baking was evaluated according to the following criteria. The results are shown in Table 1.
○: No fading (chromaticity change before and after post-baking ΔEab ≦ 5)
X: Fading (change in chromaticity ΔEab> 5 before and after post-baking)
Further, a heat resistance test (200 ° C., 2 hours) and a light resistance test (Xe lamp, 48 hours) were performed to calculate a chromaticity change ΔEab. The results are shown in Table 2.

Example 2
A photosensitive resin composition 2 was obtained in the same manner as in Example 1 except that the dye (A-1) was replaced with the dye (A-2). A coating film was obtained in the same manner as in Example 1. The results are shown in Table 1.

Example 3
A photosensitive resin composition 3 was obtained in the same manner as in Example 1 except that the dye (A-1) was replaced with the dye (A-3). A coating film was obtained in the same manner as in Example 1. The results are shown in Table 1.

From Table 1, it was confirmed from Examples 1 to 3 that in the coating film formed using the photosensitive resin composition of the present invention, fading was small even in post-baking, and a normal film could be produced. .
From Table 2, in the coating film formed using the photosensitive resin composition of the present invention, excellent heat resistance and light resistance could be confirmed.

Example 4
A color filter having red pixels, blue pixels, green pixels, and a black matrix is formed on a TFT substrate constituting the liquid crystal display device. A solid-state image sensor is formed on the black matrix.
The photosensitive resin composition is applied onto the color filter, and after removal of the solvent, the near-photosensitive resin is passed through a mask designed so that an optical filter made of the photosensitive resin composition does not remain on the solid-state imaging device. The composition layer is exposed, developed, and post-baked to form an optical filter without a film on the solid-state imaging device. A typical liquid crystal display device is listed.

  According to the present invention, it is possible to absorb near infrared rays having a wavelength of 800 to 1000 nm and to form a fine pattern.

Claims (10)

  Near infrared containing a colorant (A) containing a phthalocyanine compound having an absorption maximum wavelength in the near infrared region, a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E) Photosensitive resin composition for absorbent material. The photosensitive resin composition for near-infrared absorbers according to claim 1, wherein the phthalocyanine compound is a compound represented by the formula (1).

[In the formula (1), any one of 3 to 5 groups selected from the group consisting of Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ and Z ¹⁶ are independently OR ^1. 3 or 4 groups independently of each other represent NHR ³ and the remainder represents a fluorine atom.
Z ² , Z ³ , Z ⁶ , Z ⁷ , Z ¹⁰ , Z ¹¹ , Z ¹⁴ and Z ¹⁵ each independently represent OR ¹ or SR ² .
R ¹ and R ² each independently represent an aryl group having 6 to 20 carbon atoms. The hydrogen atom contained in the aryl group is a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, or a carbon number of 3 It may be substituted with -20 cycloalkyl groups or cyano groups.
R ³ represents a linear or branched alkyl group having 1 to 20 carbon atoms. The hydrogen atom contained in the alkyl group is a halogen atom, a linear or branched alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or cyano. It may be substituted with a group.
M represents a metal atom, a metal oxide, or a metal halide.
n represents 0 or 1. ] Any 3 to 5 groups selected from the group consisting of Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ and Z ¹⁶ independently represent OR ¹ and the rest are NHR ^The photosensitive resin composition for near-infrared absorbers of Claim 2 showing ³ . Any four groups selected from the group consisting of Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ and Z ¹⁶ represent OR ¹ independently of each other, and the rest independently of each other The photosensitive resin composition for near-infrared absorbers of Claim ² showing NHR2. Z ² , Z ³ , Z ⁶ , Z ⁷ , Z ¹⁰ , Z ¹¹ , Z ¹⁴ and Z ¹⁵ each represent SR ² independently of one another. Resin composition. R ¹ and R ² represent a phenyl group which may be substituted with a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms. The photosensitive resin composition for near-infrared absorbers in any one of 2-5.
  The photosensitive resin composition for near-infrared absorbers in any one of Claims 2-6 in which n represents 1 and M represents copper or vanadyl.   The optical filter formed using the photosensitive resin composition for near-infrared absorbers in any one of Claims 1-7. The manufacturing method of the optical filter which has the following processes.
(1) The process of apply | coating the photosensitive resin composition for near-infrared absorbers in any one of Claims 1-7 on a board | substrate (2) From the apply | coated photosensitive resin composition layer for near-infrared absorbers Step of removing solvent (3) Step of exposing photosensitive resin composition layer for near infrared absorber after removal of solvent through mask (4) Photosensitive resin composition layer for near infrared absorber after exposure (5) A step of heating the photosensitive resin composition layer for near-infrared absorbing material after development to obtain an optical filter   A liquid crystal display device having the optical filter according to claim 8.