KR20230052225A - Photosensitive composition, cured film using the same, optical filter, picture display unit and solid-state imaging device - Google Patents

Abstract

The purpose of the present invention is to provide a photosensitive composition having excellent pattern formation and capable of forming a cured film with excellent solvent resistance at low-temperature curing. The photosensitive composition of the present invention comprises a resin (A), a polymeric compound (B), a light curing initiator (C), and an organic solvent (D), wherein the resin (A) includes a binder resin (A1) having a block isocyanate group-containing monomer unit (a1) and an acidic group-containing monomer unit (a2) and the polymeric compound (B) includes a polymeric compound (B1) having an acid or hydroxyl group, three or more methacryloyl group and an amine structure.

Description

Photosensitive composition, cured film using the same, optical filter, image display device and solid-state imaging device

The present invention relates to a photosensitive composition and its use.

BACKGROUND OF THE INVENTION One type of optical filter color filter is used in an image display device, a solid-state imaging device, and the like.

Production of the color filter is a step of applying a photosensitive composition to a glass substrate and removing a solvent from this coating film by drying, and irradiating and curing the coating film with radiation through a photomask having a desired pattern shape (hereinafter, exposure (hereinafter referred to as “development”), followed by a step of washing/removing the unexposed portion of the coating film (hereinafter referred to as “development”), and then a step of heat treatment (hereinafter referred to as “post-bake”) to sufficiently cure the cured film. Thus, the first color pattern is obtained. Then, by performing the same operation as this, patterns of different colors are formed, and the color filter is completed.

Post-baking is usually performed at a temperature of 200 to 250°C for about 10 to 60 minutes to promote curing and improve the resistance of the cured film. In recent years, replacement of conventional glass substrates with flexible plastic substrates and formation of color filters on organic semiconductor elements such as organic electroluminescence display elements (organic EL) have been studied, but these members have low heat resistance. For this reason, it is required to form color filters at low temperatures. However, when post-baking is performed at a low temperature, there is a problem in that curing of the film becomes insufficient and the solvent resistance of the cured film deteriorates.

In addition, in the developing step, if the adhesion of the coating film is insufficient, there is a problem in that a defect in the shape of the pattern occurs due to defects or peeling of the exposed portion.

Regarding a composition that can be used for plastic substrates, organic EL, etc., Patent Document 1 discloses a coloring composition containing a polymerizable compound having an alkylene oxide structure. Further, Patent Document 2 discloses a colored resin composition containing C.I. Pigment Violet 19, a red pigment, a yellow pigment, a resin, a polymerization compound, and a polymerization initiator. Further, Patent Document 3 discloses a coloring composition containing a colorant, a polymer, and a polymerizable compound, and having a specific partial structure and a hydroxyl group in at least one selected from the group consisting of a colorant, a polymer, and a polymerizable compound.

Japanese Unexamined Patent Publication No. 2014-142582 Japanese Unexamined Patent Publication No. 2021-103295 Japanese Unexamined Patent Publication No. 2021-102759

However, the compositions described in Patent Literatures 1 to 3 could not satisfy the pattern formability and the solvent resistance of the cured film in low-temperature heat treatment at a level higher than a certain level.

An object of one embodiment of the present invention is to provide a photosensitive composition capable of forming a cured film having excellent pattern formation properties and excellent solvent resistance even at low temperature curing. Another embodiment of the present invention aims to provide a cured film that is a cured product of a photosensitive composition, and an optical filter, an image display device, and a solid-state imaging device having the cured film.

The present invention is a photosensitive composition containing a resin (A), a polymerizable compound (B), a photopolymerization initiator (C) and an organic solvent (D), wherein the polymerizable compound (B) comprises three or more (meth)acrylic compounds. It relates to a photosensitive composition comprising a polymerizable compound (B1) having a loyl group and an amine structure.

Furthermore, the present invention is the photosensitive composition, wherein the polymerizable compound (B) contains a polymerizable compound (B2) other than the polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure. It is about.

Moreover, this invention relates to the said photosensitive composition in which the said polymeric compound (B2) contains the polymeric compound which has 4 or more (meth)acryloyl groups.

Moreover, this invention relates to the said photosensitive composition in which the said binder resin (A1) contains 1-50 mol% of block isocyanate group containing monomeric units (a1) in all structural units.

Further, in the present invention, the content of the polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure is 5 to 80% by mass in 100% by mass of the polymerizable compound (B). It relates to the photosensitive composition.

Moreover, this invention relates to the said photosensitive composition containing a coloring agent (E).

Moreover, this invention relates to the said photosensitive composition in which the said resin (A) further contains a dispersion resin (A3).

In addition, the present invention is a photosensitive composition used for formation of a cured film obtained by exposure and post-baking at a temperature of 130 ° C. or lower,

The photosensitive composition contains a resin (A), a polymerizable compound (B), a photopolymerization initiator (C) and an organic solvent (D),

The resin (A) contains a binder resin (A1) having a block isocyanate group-containing monomeric unit (a1) and an acidic group-containing monomeric unit (a2),

It is related with the said photosensitive composition in which the said polymeric compound (B) contains the polymeric compound (B1) which has an acidic group or a hydroxyl group, and has three or more (meth)acryloyl groups and an amine structure.

Moreover, this invention relates to the cured film which is a hardened|cured material of the said photosensitive composition.

Further, the present invention relates to an optical filter having the cured film.

Further, the present invention relates to an image display device having the optical filter.

Further, the present invention relates to a solid-state imaging device having the optical filter.

According to the present invention described above, it is possible to provide a photosensitive composition capable of forming a cured film having excellent pattern formation properties and excellent solvent resistance even at low temperature curing. In addition, the present invention can provide a cured film, an optical filter, an image display device, and a solid-state imaging device.

Hereinafter, the form for implementing the photosensitive composition of this invention is demonstrated in detail. In addition, the present invention is not limited to the following embodiments, and can be modified and implemented within a range capable of solving the subject.

In the present specification, "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" means unless otherwise specified. , "acryloyl and/or methacryloyl", "acryl and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylate", respectively. / or methacrylamide”. Also, "C.I." means a color index (C.I.; published by The Society of Dyersand Colourists). The polymerizable unsaturated group is an ethylenically unsaturated double bond.

Regarding the molecular weight of the compound in the present invention, the low molecular weight compound whose molecular weight can be specified is the value calculated by calculation (food amount) or the molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), and the molecular weight A compound having a distribution of is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography in the case of using tetrahydrofuran as a solvent.

A monomer is a compound that forms a resin by polymerization. The monomer is in an unreacted state, and the monomer unit is in a state in which the monomer forms a resin after polymerization.

<Photosensitive composition>

The photosensitive composition according to one embodiment of the present invention is a photosensitive composition containing a resin (A), a polymerizable compound (B), a photopolymerization initiator (C) and an organic solvent (D), wherein the polymerizable compound (B), and a polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure.

Moreover, it is also preferable to use the photosensitive composition of this invention for formation of the cured film obtained by exposure and the post-bake at 130 degreeC or less temperature.

Although the mechanism which can solve the subject of this invention in the photosensitive composition of the said structure is not clear, it is guessed as follows.

In the photosensitive composition, the photopolymerization initiator is decomposed by light to generate active species. This active species is added to the polymerizable compound to newly generate an active species, which proceeds in a chain manner and polymerizes. However, when these active species are inactivated by an external factor, the polymerization reaction is stopped. When the active species are radicals, oxygen inhibits polymerization (also called oxygen inhibition). Since oxygen is in a triplet state as a ground state, it has high reactivity with radicals and reacts easily with radical active species to form hydroxyperoxy radicals. Since this hydroxyperoxy radical is inferior in reactivity with a polymerizable compound, advancing of a polymerization reaction is inhibited.

Usually, since optical filters such as color filters are produced in an atmospheric atmosphere, polymerization is inhibited by oxygen in the exposure step, and polymerization does not sufficiently proceed. However, subsequent heat treatment at a high temperature promotes polymerization. However, in the case of heat treatment at a low temperature, it was necessary to sufficiently advance polymerization in the exposure step in order to obtain sufficient resistance.

Since the polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure has a nitrogen atom in its molecule, hydrogen is easily drawn out to generate carbon radicals. Therefore, when the generated hydroxyperoxy radical withdraws hydrogen from the polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure, the newly generated carbon radical initiates polymerization. In addition, since the generated carbon radicals can also capture oxygen, there is also an effect of reducing the oxygen concentration. It is presumed that sufficient solvent resistance was obtained even when the subsequent heat treatment was performed at a low temperature because inhibition of polymerization by oxygen was suppressed by these mechanisms and polymerization proceeded sufficiently. In addition, since the amine structure has polarity, it is estimated that the adhesion to the base material is improved.

[Resin (A)]

The resin (A) is used, for example, for the purpose of dispersing particles such as a pigment in the photosensitive composition or for imparting resistance to a cured film. In addition, the resin (A) used mainly for dispersing particles such as pigments is also referred to as a dispersion resin, and the resin (A) used for imparting resistance to a cured film is also referred to as a binder resin. However, this use of resin (A) is an example, and it may be used for other purposes.

4,000-40,000 are preferable and, as for the weight average molecular weight (Mw) of resin (A), 4,000-35,000 are more preferable.

The content of the resin (A) is preferably from 5 to 70% by mass, and more preferably from 10 to 60% by mass, based on 100% by mass of the non-volatile matter of the photosensitive composition.

Resin (A) can be used individually or in combination of 2 or more types.

Resin (A) includes resin (A1), resin (A2), resin (A3) and resin (A4).

(Resin (A1))

Resin (A) is a resin (A1) having a block isocyanate group-containing monomeric unit (a1) and an acidic group-containing monomeric unit (a2) as a binder resin (hereinafter, simply referred to as resin (A1)) from the viewpoint of solvent resistance. It is preferable to include. Thereby, even at low temperature, hardening advances more and the solvent resistance of a cured film improves more.

Resin (A1) is preferably a random copolymer. The molecular structure of a random copolymer is usually chain-shaped.

A "random copolymer" refers to a copolymer in which two or more constituent units are arranged in disorder.

Since block resins and graft polymers (also referred to as comb polymers) have functional sites such as colorant adsorption sites and steric repulsion sites, molecules tend to aggregate due to the action of intermolecular forces between functional sites. On the other hand, in a random polymer, since two or more constituent units are randomly arranged, intermolecular force is weak and molecules are presumed to spread easily in an irregular shape. In the photosensitive composition, the random polymer diffuses as a whole and exists. Therefore, the photosensitive composition of this embodiment can form a film with a smooth surface and high cohesive force. This contributes to improvements in substrate adhesion, pattern shape, and solvent resistance after the low-temperature baking step.

The method for producing Resin (A1) is not particularly limited, and a known method can be used. For example, it is obtained by copolymerizing the monomer which forms a block isocyanate group containing monomeric unit (a1), the monomer which forms an acidic group containing monomeric unit (a2), and the other monomer which can be copolymerized with these optionally.

[block isocyanate group-containing monomer unit (a1)]

The block isocyanate group-containing monomer is a monomer in which the isocyanate group of the isocyanate group-containing monomer is protected with a compound (hereinafter also referred to as a blocking agent) that desorbs with heat.

The isocyanate group-containing monomer is, for example, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanate Nato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, methacryloyl isocyanate, etc. can be heard Equimolar reaction products of 2-hydroxyalkyl (meth)acrylates and diisocyanate compounds can also be used. Among these, 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are preferable.

Blocking agents include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, urea compounds, imine compounds, and bisulfite compounds. can be heard

Examples of the oxime compound include formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, and benzophenone oxime, with methyl ethyl ketoxime being preferred. .

Examples of the lactam compound include ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam.

Phenolic compounds include, for example, phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, 2-hydroxymethyl benzoate, 4- Methyl hydroxybenzoate, p-naphthol, p-nitrophenol, etc. are mentioned, and 3,5-xylenol, methyl 2-hydroxybenzoate, and methyl 4-hydroxybenzoate are preferable.

Examples of the alcohol compound include methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, and furfuryl alcohol.

Examples of the amine compound include diphenylamine, phenylnaphthylamine, aniline, and carbazole.

Examples of the active methylene compound include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone, with diethyl malonate being preferable.

Pyrazole, methylpyrazole, 3,5-dimethylpyrazole, etc. are mentioned as a pyrazole compound, 3,5-dimethylpyrazole is preferable.

Examples of the mercaptan compound include butyl mercaptan, thiophenol, and tert-dodecyl mercaptan.

The imidazole compound is, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl- 2-phenylimidazole etc. are mentioned.

Examples of the imide compound include succinimide, maleic acid imide, maleimide, and phthalimide.

Examples of the urea compound include urea, thiourea, and ethylene urea.

As for an imine compound, ethyleneimine, polyethyleneimine, etc. are mentioned, for example.

Examples of the bisulfite compound include sodium bisulfite and potassium bisulfite.

These blocking agents can be used individually or in combination of 2 or more types.

The blocking agent is preferably at least one selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. And, from the viewpoint of protection reaction and deprotection reaction, at least one selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds is more preferred.

Examples of the block isocyanate group-containing monomer include the following compounds. In addition, this invention is not limited to these.

[Tue 1]

Commercially available block isocyanate group-containing monomers are available from Showa Denko K.K. manufactured by Karenz MOI-DEM (desorption temperature of blocking agent: 85 to 95 ° C.), MOI-BP (desorption temperature of blocking agent: 105 to 115 ° C.), MOI-BM (desorption temperature of blocking agent: 125 to 135 ° C.) etc. can be mentioned.

The content of the block isocyanate group-containing monomeric unit (a1) is preferably 1 to 50 mol%, and more preferably 5 to 40 mol%, based on the total constituent units of the resin (A1), from the viewpoint of solvent resistance.

[Acidic Group-Containing Monomer Unit (a2)]

Examples of the acidic group of the acidic group-containing monomer include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyl group is preferable.

Acidic group-containing monomers include, for example, (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, Maleic anhydride, fumaric acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethylphthalic acid, 2-acryloyloxyethylhexylhydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylic acid amide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, 2-(meth)acryloyloxyethyl acid phosphate, and the like.

The content of the acidic group-containing monomeric unit (a2) is preferably from 1 to 50 mol%, more preferably from 5 to 40 mol%, in all the structural units of the resin (A1), from the viewpoint of developability.

Resin (A1) may contain the following monomeric units other than the block isocyanate group-containing monomeric unit (a1) and the acidic group-containing monomeric unit (a2). For example, a hydroxyl group-containing monomer unit (a3), an epoxy group-containing monomer unit (a4), a polymerizable unsaturated group-containing monomer unit (a5), an alicyclic hydrocarbon-containing monomer unit (a6), a monomer represented by general formula (1) unit (a7) and other monomeric units (a8).

[Tue 2]

In General Formula (1), R ₁ represents a hydrogen atom or a methyl group. R ₂ represents an alkylene group having 2 or 3 carbon atoms. n represents the integer of 1-15. When n is 2 or more, a plurality of R ₂ may be the same or different.

[hydroxyl group-containing monomeric unit (a3)]

The hydroxyl group-containing monomer is, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate. Acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy -3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, etc. are mentioned.

[Epoxy group-containing monomeric unit (a4)]

Examples of the epoxy group-containing monomer include oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate , 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate, 3-(3,4-epoxycyclohexylmethyl Oxy) propyl (meth)acrylate etc. are mentioned.

[Polymerizable unsaturated group-containing monomer unit (a5)]

Examples of the method of making the resin (A1) contain the polymerizable unsaturated group-containing monomeric unit (a5) include methods (i) to (iii) shown below.

<Method (i)>

There is a method (i) in which an acidic group of an acidic group-containing monomer is added to the epoxy group of the epoxy-group-containing monomeric unit (a4) contained in the resin (A1).

<Method (ii)>

There is a method (ii) in which an epoxy group of an epoxy group-containing monomer is added to the acidic group of the acidic group-containing monomeric unit (a2) contained in the resin (A1).

Moreover, what made the acid anhydride react with the hydroxyl group produced by the reaction of methods (i) and (ii) is also useful as a polymerizable unsaturated group containing monomeric unit (a5).

As for an acid anhydride, tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride etc. are mentioned, for example.

<Method (iii)>

There is a method (iii) in which the isocyanate group of the isocyanate group-containing monomer is reacted with the hydroxyl group of the hydroxyl group-containing monomeric unit (a3) contained in the resin (A1).

Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate. can be heard

[Alicyclic Hydrocarbon Containing Monomer Unit (a6)]

Alicyclic hydrocarbon-containing monomers include, for example, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl Oxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, etc. are mentioned.

[monomer unit (a7) represented by general formula (1)]

Examples of the monomer represented by the general formula (1) include ethylene oxide (EO) or propylene oxide (PO) modified (meth)acrylates of paracumylphenol.

[Other monomer units (a8)]

Other monomers forming the monomer unit (a8) include, for example, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, iso Butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, benzyl ( meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, EO or PO modified (meth)acrylate of phenol, EO or PO modified (meth)acrylate of nonylphenol, dimethyl acrylic acid esters such as aminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate;

aromatic vinyl compounds such as styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, and vinylnaphthalene;

(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acrylamide (meth)acrylamides such as ilmorpholine;

vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;

fatty acid vinyls such as vinyl acetate and vinyl propionate;

Phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3- Maleimide coumarin, 4,4'-bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N, N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl- 3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzoimidazolyl)phenyl] N-substituted maleimides such as maleimide and 9-maleimide acridine;

Dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl -2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(2 -Ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, etc. are mentioned.

These monomers can be used individually or in combination of 2 or more types.

Resin (A1) can be used individually or in combination of 2 or more types.

From a viewpoint of solvent resistance, 4,000-40,000 are preferable and, as for the weight average molecular weight (Mw) of resin (A1), 4,000-35,000 are more preferable.

From a developable viewpoint, 30-200 mgKOH/g is preferable and, as for the acid value of resin (A1), 40-180 mgKOH/g is more preferable. "Acid value" is the number of milligrams of potassium hydroxide required to neutralize 1 g of resin solid content, and can be obtained by potentiometric titration in accordance with JIS K 0070.

The content of the resin (A1) is preferably 5% by mass or more, and more preferably 10 to 100% by mass, based on 100% by mass of the resin (A), from the viewpoint of solvent resistance.

(Resin (A2))

Resin (A2) does not have the block isocyanate group-containing monomer unit (a1) described above as a binder resin, and is selected from an alicyclic hydrocarbon-containing monomer unit (a6) and a monomer unit (a7) represented by general formula (1) It is resin (A2) (henceforth simply called resin (A2)) which has at least 1 sort(s) of monomeric unit and an acidic-group containing monomeric unit (a2).

Resin (A2) may contain monomer units other than the above-mentioned (a1), (a2), (a6) and (a7). For example, the monomeric units of (a3) to (a5) and (a8) described above are exemplified. Among these, those having a polymerizable unsaturated group-containing monomeric unit (a5) are preferable from the viewpoint of solvent resistance.

Resin (A2) can be used individually or in combination of 2 or more types.

From a viewpoint of solvent resistance, 4,000-40,000 are preferable and, as for the weight average molecular weight (Mw) of resin (A2), 4,000-35,000 are more preferable.

From a developable viewpoint, 30-200 mgKOH/g is preferable and, as for the acid value of resin (A2), 40-180 mgKOH/g is more preferable.

(Resin (A3))

Resin (A3) is a dispersion resin for dispersing particles such as a pigment.

The resin (A3) is preferably a resin having an adsorbing group having a high affinity for particles such as a pigment. It is preferable that the adsorption group has at least one of a basic group and an acidic group.

Examples of the basic group include groups containing nitrogen atoms such as primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases, and nitrogen-containing heterocycles.

The acidic group includes, for example, a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

Examples of the resin species of the resin (A3) include urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, and polysiloxanes. , long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkylenimine) with polyester having a free carboxyl group, and salts thereof Water-soluble resins such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, water-soluble polymer compounds, poly Ester type, modified polyacrylate type, ethylene oxide/propylene oxide addition compound, phosphoric acid ester type, etc. are mentioned.

As for the structure of resin (A3), a random structure, a block structure, a graft structure, a comb-shaped structure, and a star-shaped structure etc. are mentioned, for example. Among these, a block structure or a comb structure is preferable from the viewpoint of dispersion stability.

"Graft resin (also referred to as comb resin)" refers to a resin having a polymer different from the main chain as a side chain on a molecular chain serving as the main chain, for example, as a side chain in (AA ... AA) serving as the main chain ( It is a polymer having BB...BB). In addition, "block copolymer" refers to a copolymer composed of a linear polymer having a plurality of different single polymers as partial constituent components (blocks), for example, (AA...AA) - (BB...BB) - ( AA…AA) have the same structure. The main chain may be made of a polymer or the like, and is preferably made of polyester, for example.

Resin (A3) is preferably a graft resin or a block copolymer rather than a random copolymer. In these polymers, the colorant can be more finely dispersed because functional sites such as the colorant adsorption site and the steric repulsion site exist as a constant mass.

Resin (A3) is preferably a resin having a polymerizable unsaturated group from the viewpoint of solvent resistance.

Resin (A3) is specifically, BYK JAPAN KK. Manufacturing Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, or Anti-Terra-U203, 204, or 4, BYK-P1 P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen, etc., SOLSPERSE3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 227000, 26000, 26000, 26000, 26000, 26000, or BASF Japan Ltd. Manufacturing EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 43000, 43100, 43100, 43100 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Anojino Comoto Inc. Manufactured by AJISPER PA111, PB711, PB821, PB822, PB824, etc., Japanese Unexamined Patent Publication No. 2008-029901, Japanese Unexamined Patent Publication No. 2009-155406, Japanese Unexamined Patent Publication No. 2010-185934, Japanese Unexamined Patent Publication No. 2011-157416, International Publication No. 2008/007776, Japanese Unexamined Patent Publication No. 2008-029901, Japanese Unexamined Patent Publication No. 2009-155406, Japanese Unexamined Patent Publication No. 2010-185934, Japanese Unexamined Patent Publication No. 2011-157416, Japanese Unexamined Patent Publication 2012-255128 , Japanese Unexamined Patent Publication No. 2009-251481, Japanese Unexamined Patent Publication No. 2007-23195, Japanese Unexamined Patent Publication No. 1996-143651, Japanese Unexamined Patent Publication No. 2017-206689, Japanese Unexamined Patent Publication No. 2019-095548, etc. can be heard

Resin (A3) can be used individually or in combination of 2 or more types.

The amount of resin (A3) used is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass, based on 100 parts by mass of the coloring agent. When used in an appropriate amount, the film formability is further improved.

Moreover, in one Embodiment, it is preferable that content of resin (A3) is 2-33 mass % in 100 mass parts of non-volatile matter of the photosensitive composition.

The weight average molecular weight of the resin (A3) in terms of polystyrene is preferably 4,000 or more and less than 100,000, and is preferably 5,000 or more and 30,000 from the viewpoints of dispersion stability, development unevenness, solvent resistance, and development speed, since the weight average molecular weight in terms of polystyrene is not limited to the molecular weight as long as the problem can be solved. The following is more preferable.

(Resin (A4))

Resin (A4) is resin other than Resin (A1) - (A3).

The resin (A4) is not particularly limited, and known resins can be used. For example, (meth)acrylic resin, styrene resin, styrene-(meth)acrylic resin, epoxy resin, urethane resin, polycarbonate resin, polyester resin, polyether resin, polyimide resin, polyamideimide resin, cyclic olefin Resin etc. are mentioned, It can use individually or in combination of 2 or more types.

[Polymerizable compound (B)]

Examples of the polymerizable compound (B) include monomers and oligomers having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group of an ethylenically unsaturated double bond.

(Polymerizable compound (B1) having 3 or more (meth)acryloyl groups and an amine structure)

The amine structure in the polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure (hereinafter, simply referred to as the polymerizable compound (B1)) is a primary amine, a secondary amine, and a tertiary amine. Among these, tertiary amines are preferred. In addition, the amine structure of the polymerizable compound (B1) does not include an amide structure, an imide structure, and a urethane structure in which a carbonyl group is directly bonded to a nitrogen atom.

The number of (meth)acryloyl groups in the polymerizable compound (B1) is not particularly limited as long as it is three or more, but from the viewpoint of pattern formation, the upper limit is preferably 16 or less.

Polymeric compound (B1) can be used individually or in combination of 2 or more types.

The content of the polymerizable compound (B1) is preferably 1% by mass or more, more preferably 5 to 80% by mass, based on 100% by mass of the polymerizable compound (B), from the viewpoint of pattern formation and solvent resistance. - 60 mass % is especially preferable.

Examples of the polymerizable compound (B1) include tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, and tris(2-hydroxy-3-methacryloyloxypropyl)amine. However, the Michael addition reaction product of (meth)acrylate compound (X) and amine compound (Y), etc. are mentioned.

The (meth)acrylate compound (X) is, for example, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth) Acrylates, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaeryth Lithol hexa(meth)acrylate, diglycerin tri(meth)acrylate, diglycerin tetra(meth)acrylate, trimethylolpropanealkylene oxide-modified tri(meth)acrylate, ditrimethylolpropanealkylene oxide-modified tree, and Tetra(meth)acrylate, pentaerythritolalkylene oxide-modified tri and tetra(meth)acrylate, diglycerin alkylene oxide-modified tri and tetra(meth)acrylate, dipentaerythritolalkylene oxide-modified tetra, penta and Hexa (meth)acrylate etc. are mentioned.

As for the alkylene oxide unit in the said alkylene oxide modification, ethylene oxide, a propylene oxide, a butylene oxide, etc. are mentioned.

Moreover, as (meth)acrylate compound (X), the (meth)acrylate compound which has an acidic group is also mentioned.

(Meth)acrylate compound (X) can be used individually or in combination of 2 or more types.

The amine compound (Y) is, for example, n-propylamine, n-butylamine, n-hexylamine, benzylamine, aminocaproic acid, monoethanolamine, 2-(2-aminoethoxy)ethanol, o- primary amines such as aminophenol, m-aminophenol, and p-aminophenol;

Dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, morpholine, piperidine, 1-methylpiperazine, proline, N-methylethanolamine, N-acetylethanolamine, Secondary amines, such as diethanolamine, 3-aniline phenol, and 4-aniline phenol, etc. are mentioned.

The amine compound (Y) is preferably a secondary amine, particularly preferably a secondary amine having a hydroxyl group, from the viewpoint of solvent resistance. Although the detailed mechanism of this is unknown, the presence of a hydroxyl group makes it difficult for the polymerizable compound (B1) to contain dissolved oxygen, and oxygen inhibition by hydroxyperoxy radicals generated when oxygen is irradiated with ultraviolet rays in the exposure step It is estimated that solvent resistance is improved because a film with a high crosslinking density is obtained because the photocrosslinking reaction proceeds efficiently.

An amine compound (Y) can be used individually or in combination of 2 or more types.

The method for producing the Michael addition reaction product of the (meth)acrylate compound (X) and the amine compound (Y) is not particularly limited, and a known method can be used. For example, the method described in International Publication No. 2006/075754, Japanese Patent Publication No. 2008-545859, Japanese Unexamined Patent Publication No. 2017-066347, etc. is mentioned.

The polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure may have an acidic group or/and a hydroxyl group. A method of introducing an acidic group or/and a hydroxyl group is, for example, a method of using a compound having an acidic group or/and a hydroxyl group in the (meth)acrylate compound (X) or amine compound (Y), or Michael addition After reaction, the method of adding an acid anhydride, etc. are mentioned.

When the polymerizable compound having an amine structure has an acidic group, the acid value is preferably 1 to 200 mgKOH/g.

When the polymerizable compound having an amine structure has a hydroxyl group, the hydroxyl value is preferably 5 to 500 mgKOH/g, more preferably 10 to 200 mgKOH/g, from the viewpoint of pattern formation.

Commercially available products of the polymerizable compound (B1) are available from TOAGOSEI CO., LTD. Manufacture Aronix MT-3041 (hydroxyl value: 156 mgKOH/g), MT-3042, etc. are mentioned.

(Polymerizable compound (B2) other than the polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure)

The photosensitive composition of the present invention is a polymerizable compound (B2) other than the polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure as the polymerizable compound (B) from the viewpoint of solvent resistance (hereinafter , also simply referred to as polymerizable compound (B2)) is preferably included.

The polymerizable compound (B2) is, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylol Propane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO modified tri(meth)acrylate, trimethylolpropane EO modified tri(meth)acrylate ) Acrylate, isocyanuric acid EO modified tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1, 6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa (meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol EO modified penta(meth)acrylate, dipentaerythritol PO modified penta(meth)acrylate, tricyclodecanyl(meth) Acrylates, (meth)acrylic acid esters of methylolized melamine, various acrylic acid esters and methacrylic acid esters such as epoxy (meth)acrylate, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol Trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, etc. are mentioned. Among these, it is preferable to include a polymerizable compound having 4 or more (meth)acryloyl groups from the viewpoints of reactivity and solvent resistance.

In addition, the polymerizable compound (B2) may contain an acidic group. As an acidic group, a sulfonic acid group, a carboxy group, a phosphoric acid group, etc. are mentioned.

Examples of the polymerizable compound containing an acidic group include esterified products of poly(meth)acrylates containing free hydroxyl groups of polyhydric alcohols and (meth)acrylic acids, and dicarboxylic acids; Esterified substances of polyhydric carboxylic acids and monohydroxyalkyl (meth)acrylates, and the like are exemplified.

The polymerizable compound containing an acidic group is trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaeryth monoester products containing free carboxyl groups of monohydroxyoligoacrylates such as ritolpentamethacrylate or monohydroxyoligomethacrylates and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and terephthalic acid; Propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, Tricarboxylic acids such as benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate Oligoester products containing free carboxy groups with monohydroxy monoacrylates or monohydroxy monomethacrylates such as the like are exemplified.

In addition, the polymerizable compound (B2) may contain a urethane bond. For example, polyfunctional urethane acrylate obtained by reacting polyfunctional isocyanate with (meth)acrylate having a hydroxyl group, or polyfunctional isocyanate obtained by reacting polyfunctional isocyanate with alcohol and further reacting (meth)acrylate having a hydroxyl group. Functional urethane acrylate etc. are mentioned.

As the (meth)acrylate having a hydroxyl group, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, isocyanuric acid EO modified di( meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol EO modified penta(meth)acrylate, Dipentaerythritol PO modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloyl Propyl methacrylate, a reaction product of an epoxy group-containing compound and carboxy (meth)acrylate, a hydroxyl group-containing polyol polyacrylate, and the like are exemplified.

Moreover, as polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, etc. are mentioned.

As a commercial item of polymeric compound (B2), Nippon Kayaku Co., Ltd. Manufactured by KAYARADR-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA- 2C, D-310, D-330, DPCA-20, DCPA-30, DCPA-60, DCPA-120, TOAGOSEI CO., LTD. Manufacturing Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400 , M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-520, M-521, M-211B, M-101A, M -5300, M-5400, M-5700, Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405, #2500, and kyoeisha manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD chemical co., ltd. Manufactured by AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, SHIN-NAKAMURA CHEMICAL CO., LTD. NK ESTETR A-9300, ABE-300, A-DOG, A-DCP, A-BPE-4, UA-160TM manufactured by Miwon Specialty Chemical Co., Ltd. MiramerHR6060, 6100, 6200 manufactured by DAICEL-ALLNEX LTD. Manufactured by EBECRYL40, 130, 140, 145, Osaka Gas Chemicals Co., Ltd. Manufactured OGSOLEA-0200, 0300, GA-5060, GA-2800, etc. are mentioned.

Among these, Aronix M-305, M-306, M-400, M-402, M-403, M-404, M-405, M-406 and M-450 having a hydroxyl group are particularly preferred. Although the detailed mechanism is unknown, since the hydroxyl groups they have reduce the amount of dissolved oxygen in the photosensitive composition and the effect of reducing oxygen inhibition at the time of ultraviolet exposure is obtained, photocrosslinking is promoted and solvent resistance is estimated to improve.

It is more preferable that the polymerizable compound (B2) contains a polymerizable compound having a dendrimer structure or a hyperbranched structure from the viewpoint of solvent resistance.

A polymerizable compound having a dendrimer structure has a chemical structure constituting the core (hereinafter also referred to as a core portion) repeatedly branching regularly to the outside thereof, and having a chemical structure in which a polymerizable unsaturated group is bonded to the terminal. It has a spherical, highly controlled chemical structure and molecular weight.

The hyperbranch structure has a chemical structure similar to that of the dendrimer structure. Therefore, compared to general straight-chain polymerizable compounds, since the distance between the polymerizable unsaturated groups in the molecule is short and the density is high, it is less susceptible to oxygen inhibition, responds more sufficiently to exposure, and even at low temperature curing. It is estimated that a cured film having excellent solvent resistance is obtained.

The polymerizable compound having a dendrimer structure or a hyperbranched structure preferably has an average of 6 to 18 polymerizable unsaturated groups, and particularly preferably an average of 6 to 11, from the viewpoint of solvent resistance.

In the polymerizable compound having a dendrimer structure or a hyperbranch structure, from the viewpoint of solvent resistance, the polymerizable unsaturated group is preferably at least one selected from the group consisting of a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. And, a (meth)acryloyl group is more preferable.

The polymerizable compound having a dendrimer structure or a hyperbranch structure can be used alone or in combination of two or more.

The content of the polymerizable compound having a dendrimer structure or a hyperbranched structure is preferably 10% by mass or more, and more preferably 20 to 100% by mass, based on 100% by mass of the polymerizable compound (B2), from the viewpoint of solvent resistance.

As the polymerizable compound having a dendrimer structure or a hyperbranched structure, an appropriately synthesized compound may be used, or a commercial item may be used.

As a method for synthesizing the dendrimer structure, a divergent method in which synthesis proceeds outward from the core and a convergent method in which synthesis proceeds inward from the terminal polymerizable unsaturated group, a combination of these two it is known For example, using the convergent method, as the first step, 2-(4-hydroxyphenoxyethyl)-acrylate and 5-hydroxyisophthalic acid are coupled, and in the second step, trimesic acid and coupling By doing so, a polymerizable compound having a dendrimer structure can be obtained.

As a method for synthesizing the hyperbranched structure, it is obtained by self-condensation of ABx-type molecules having a total of three or more two types of substituents in one molecule. For example, hyperbranched polyester is obtained by polycondensation using 3,5-dihydroxybenzoic acid as a raw material. In this case, a polymerizable compound having a hyperbranched structure is obtained by reacting (meth)acrylic acid thereto, although a hydroxyl group is present at the terminal.

Commercially available polymeric compounds having a dendrimer structure or hyperbranch structure include, for example, Viscoat #1000LT (dendrimer structure, average number of acryloyl groups: 14) manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD., manufactured by Miwon Specialty Chemical Co., Ltd. MiramerSP-1106 (dendrimer structure, average number of acryloyl groups 18), MiramerSP-1108 (dendrimer structure, average number of acryloyl groups 13), CN2301 (hyperbranch structure, average number of acryloyl groups 9), CN2302 ( Hyperbranch structure, average number of acryloyl groups 16), CN2303 (hyperbranch structure, average number of acryloyl groups 6), CN2304 (hyperbranch structure, average number of acryloyl groups 18), Etercure6361-100 (hyperbranch structure, average number of acryloyl groups 18) manufactured by Eternal Materials Branch structure, average number of acryloyl groups 8), Etercure6362-100 (hyperbranch structure, average number of acryloyl groups 12), Etercure6363 (hyperbranch structure, average number of acryloyl groups 16), EtercureDR-E522 (hyperbranch structure, average number of acryloyl groups) The number of acryloyl groups 15) etc. are mentioned.

The mass ratio of the polymerizable compound (B1) and the polymerizable compound (B2) is preferably B1:B2 = 4:96 to 96:4, and more preferably 12:88 to 96:4.

The content of the polymerizable compound (B) is preferably from 1 to 60% by mass, and more preferably from 2 to 50% by mass, based on 100% by mass of the non-volatile matter of the photosensitive composition.

[Photoinitiator (C)]

The photosensitive composition of the present invention contains a photopolymerization initiator (C). Accordingly, the photosensitive composition can be cured by irradiation with active energy rays.

The photopolymerization initiator (C) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2 -Methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino) -1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[ acetophenone-based compounds such as 4-(4-morpholinyl)phenyl]-1-butanone;

2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis( Trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl) -s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s -Triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6 triazine-based compounds such as triazine or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;

1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)9H- oxime compounds such as carbazol-3-yl]- and 1-(O-acetyloxime);

acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide;

quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; Alternatively, titanocene-based compounds and the like are exemplified.

Commercially available products include Omnirad 907, 369E, and 379EG manufactured by IGM Resins as acetophenone-based compounds, and Omnirad 819 manufactured by IGM Resins as acylphosphine-based compounds, TPO, and oxime-based compounds manufactured by BASF Japan Ltd. IRGACUREOXE-01, 02, 03, 04 manufactured by ADEKA CORPORATION, N-1919, NCI-730, 831, 930 manufactured by Changzhou Tronly New Electronic Materials Co., Ltd. TRONLYTRPBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, 3057 manufactured by IGM Resins, Omnirad 1312, 1314, 1316 manufactured by Samyang Corporation, SPI-02, 03, 04 manufactured by Samyang Corporation , 05, 06, 07, DFI-020, 306, and EOX-01 manufactured by Daito Chemix Corporation.

Further, Japanese Unexamined Patent Publication No. 2007-210991, Japanese Unexamined Patent Publication No. 2009-179619, Japanese Unexamined Patent Publication No. 2010-037223, Japanese Unexamined Patent Publication No. 2010-215575, Japanese Unexamined Patent Publication No. 2011-020998, International Publication No. The oxime type compound of 2015/036910, international publication 2021/175855, etc. is also mentioned.

When the photosensitive composition of this invention contains the coloring agent (E) mentioned later, it is more preferable to contain an oxime type compound as a photoinitiator (C).

As for the specific example of an oxime type compound, the following are mentioned, for example. In addition, this invention is not limited to these.

[Tue 3]

[Tuesday 4]

[Tuesday 5]

[Tue 6]

The content of the photopolymerization initiator (C) is preferably from 0.5 to 100 parts by mass, more preferably from 1 to 50 parts by mass, particularly from 2 to 25 parts by mass, from the viewpoint of photocurability with respect to 100 parts by mass of the polymerizable compound (B). desirable.

[Organic Solvent (D)]

The photosensitive composition of the present invention contains an organic solvent (D).

The organic solvent (D) is not particularly limited as long as it satisfies the solubility and coatability of each component contained in the photosensitive composition of the present invention, and known compounds can be used.

The organic solvent (D) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3 -Butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3 ,5-trimethylcyclohexanone, 3-ethoxyethylpropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutylacetate, 3 -Methoxybutanol, 3-methoxybutylacetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n -Butyl alcohol, n-butylbenzene, n-propylacetate, N-methylpyrrolidone, o-xylene, toluene, o-chlorotoluene, benzene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene , p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene Glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotert-butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether , ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, di Ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol Monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters. Among these, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diacetone, from the viewpoint of solubility and coatability of the resin. Alcohols, such as alcohol, and ketones, such as cyclohexanone, are preferable.

It is preferable that the photosensitive composition of this invention does not substantially contain organic solvents which are aromatic hydrocarbons (toluene, xylene, benzene, chlorobenzene, etc.) from an environmental viewpoint. Substantially not containing is 50 mass ppm or less in the photosensitive composition, it is preferable to be 30 mass ppm or less, and it is more preferable to set it as 10 mass ppm or less.

Organic solvent (D) can be used individually or in combination of 2 or more types.

It is preferable to contain content of the organic solvent (D) to such an extent that the non-volatile content of the photosensitive composition becomes 5 to 50% by mass.

[Colorant (E)]

The photosensitive composition of the present invention may contain a coloring agent (E). Accordingly, the transmittance of each wavelength region of the optical filter can be controlled, and color separation and shielding properties are improved.

The coloring agent (E) may be either a pigment or a dye, and may be used in combination.

(Pigment)

The pigment is preferably a compound classified as a pigment in color index.

The red pigment is, for example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, pigments described in Japanese Patent Laid-Open No. 2014-134712, and Japanese Patent No. 6368844 A pigment etc. are mentioned. Among these, pigments described in C.I. Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296 and Japanese Unexamined Patent Publication No. 2014-134712 from the viewpoint of heat resistance, light resistance, and transmittance. , pigments described in Japanese Patent No. 6368844 are preferred, C.I. Pigment Red 177, 254, 291, 295, 296, pigments described in Japanese Patent Laid-Open No. 2014-134712, and pigments described in Japanese Patent No. 6368844 more preferable

Orange pigments include, for example, C.I. Pigment Orange 36, 38, 43, 64, 71, 73 and the like.

Yellow pigments are, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 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, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, Japanese Unexamined Patent Publication No. 2012-226110, Japanese Unexamined Patent Publication No. 2017-171912, Japanese Patent The pigment described in Unexamined-Japanese-Patent No. 2017-171913, Unexamined-Japanese-Patent No. 2017-171914, Unexamined-Japanese-Patent No. 2017-171915, etc. are mentioned. Among these, pigments described in C.I. Pigment Yellow 138, 139, 150, 185, 231, 233 and Japanese Unexamined Patent Publication No. 2012-226110 are preferable.

Green pigments, for example, C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63 etc. are mentioned. Among these, C.I. Pigment Green 36, 58, 59, 62, 63 are preferable.

The blue pigment is, for example, C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferable.

The purple pigment is, for example, C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 etc. are mentioned. Among these, C.I. Pigment Violet 19 and 23 are preferable.

As for the black pigment, C.I. Pigment Black 1, 6, 7, 12, 20, 31, 32 etc. are mentioned specifically,. Further, disclosed in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, Japanese Patent Publication No. 2012-515234, Japanese Patent Application Laid-Open No. 1-170601, Japanese Patent Laid-Open No. 2-34664, etc. Compounds are also included.

When the photosensitive composition of the present invention is used for an infrared transmission filter, the colorant (E) contains two or more pigments selected from the group consisting of a red pigment, a yellow pigment, a blue pigment, a green pigment, and a purple pigment, and It is desirable to indicate

As a combination showing black, the following aspects are mentioned, for example.

(1) It contains a yellow pigment and a purple pigment.

(2) It contains a red pigment, a yellow pigment, and a purple pigment.

(3) It contains a red pigment, a yellow pigment, and a blue pigment.

(4) It contains a red pigment, a yellow pigment, and a green pigment.

(5) It contains a yellow pigment, a blue pigment, and a purple pigment.

(6) It contains a red pigment, a yellow pigment, a blue pigment, and a purple pigment.

In addition, titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, red iron oxide (III), cadmium red, ultramarine blue, Prussian blue, chromium oxide rust, cobalt rust, amber, synthetic iron black, etc. Inorganic pigments of can also be used.

(dyes)

Dyes include, for example, acid dyes, direct dyes, basic dyes, form dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Dye etc. are mentioned. Moreover, these derivatives and lake pigments obtained by forming dyes into lakes are also exemplified.

The acidic dye preferably has an acidic group such as sulfonic acid or carboxylic acid. Further, a salt-formation compound that is a salt of an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound is preferable. Moreover, the salt-formation compound which is a salt of the resin component which has these functional groups and an acidic dye is also preferable. In addition, a photosensitive composition having excellent resistance (light resistance and solvent resistance) is easily obtained by modifying the salt-formation compound into a sulfonic acid amide compound through sulfonamidation.

Further, a salt-formation compound of an acid dye and a compound having an onium salt group is also preferable because of its excellent resistance (light resistance, solvent resistance). In addition, the compound having an onium base group is preferably a resin having a cationic group.

The basic dye can be used by itself, but a salt-formation compound that forms a salt with an organic acid, perchloric acid, or a metal salt thereof is preferable. Salt-formation compounds of basic dyes are preferable because they are excellent in resistance (light resistance, solvent resistance) and affinity with pigments. Further, in the salt-formation compound of the basic dye, the anion component functioning as a counter ion is an organic sulfonic acid, an organic sulfuric acid, a phosphorus anion compound containing a fluorine group, a boron anion compound containing a fluorine group, a nitrogen anion compound containing a cyano group, and a halogenated hydrocarbon group-containing compound. An anion compound having a conjugate base of an organic acid and a salt-formation compound obtained by forming an acidic dye are preferred. Moreover, resistance improves more when a salt-formation compound contains a polymerizable unsaturated group in a molecule|numerator.

The chemical structure of dyes, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone-based dyes, anthraquinone-based dyes, anthrapyridone-based dyes, etc.), carbonium-based dyes (diphenylmethane-based dyes, triphenylmethane-based dyes, xanthene-based dyes, acridine-based dyes, etc.), quinoneimine-based dyes ( Oxazine-based dyes, thiazine-based dyes, etc.), azine-based dyes, polymethine-based dyes (oxonol-based dyes, merocyanine-based dyes, arylidene-based dyes, styryl-based dyes, cyanine-based dyes, squarylium-based dyes, croconium-based dyes dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and their A dye structure derived from a dye selected from metal complex dyes and the like is exemplified.

Among these, from the viewpoint of color characteristics such as color, color separability, color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes A dye structure derived from a dye selected from dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferable, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrrome A dye structure derived from a dye selected from tene-based dyes and phthalocyanine-based dyes is more preferable.

A coloring agent (E) can be used individually or in combination of 2 or more types.

5-70 mass % is preferable in 100 mass % of the non-volatile matter of a photosensitive composition, and, as for content of a coloring agent (E), 10-60 mass % is more preferable.

(Pigment Refinement)

It is preferable to micronize and use a pigment. The miniaturization method is not particularly limited, and for example, wet grinding, dry grinding, and dissolution/precipitation methods can all be used. Among these, salt milling treatment by a kneader method, which is one type of wet grinding, is preferable. As for the average primary particle diameter calculated|required by TEM (transmission electron microscope) of a micronized pigment, 5-90 nm is preferable. Moreover, as for an average primary particle diameter, from a viewpoint of dispersibility and a contrast ratio, 10-70 nm is more preferable.

The salt milling treatment is a mechanical process while heating a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneading machine such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. It is a treatment of removing water-soluble inorganic salts and water-soluble organic solvents by washing with water after kneading. The water-soluble inorganic salt functions as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt at the time of salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution, and a sharp particle size distribution.

Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, and sodium sulfate, and sodium chloride (table salt) is preferable from the viewpoint of cost. The amount of water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, more preferably 300 to 1,000 parts by mass, based on both treatment efficiency and production efficiency, based on 100 parts by mass of the pigment.

The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (miscibles) in water and does not substantially dissolve the inorganic salt to be used. However, since the temperature rises during salt milling and the solvent becomes easily evaporated, a high boiling point solvent having a boiling point of 120°C or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl Ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol Monoethyl ether, liquid polypropylene glycol, and the like are used. The amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, based on 100 parts by mass of the pigment.

In the salt milling process, you may add resin as needed. The type of the resin is not particularly limited, and examples thereof include natural resins, modified natural resins, synthetic resins, and synthetic resins modified by natural resins. Among these, those that are solid at room temperature and insoluble in water are preferable, and partially soluble in the above organic solvents are preferable. As for the addition amount of resin, 2-200 mass parts is preferable with respect to 100 mass parts of pigments.

[sensitizer (F)]

The photosensitive composition of this invention can contain a sensitizer (F).

The sensitizer (F) is, for example, a chalcone-based compound, an unsaturated ketone represented by dibenzalacetone, etc., a 1,2-diketone-based compound represented by benzyl or camphorquinone, a benzoin-based compound, a fluorene-based compound, Naphthoquinone-based compounds, anthraquinone-based compounds, xanthene-based compounds, thioxanthene-based compounds, xanthone-based compounds, thioxantone-based compounds, coumarin-based compounds, ketocoumarin-based compounds, cyanine-based compounds, merocyanine-based compounds, oxonol-based compounds Polymethine pigments such as compounds, acridine-based compounds, azine-based compounds, thiazine-based compounds, oxazine-based compounds, indoline-based compounds, azulene-based compounds, azulenium-based compounds, squarylium-based compounds, porphyrin-based compounds, tetraphenylporphyrin-based Compound, triarylmethane-based compound, tetrabenzoporphyrin-based compound, tetrapyrazinoporphyrazine-based compound, phthalocyanine-based compound, tetraazaporphyrazine-based compound, tetraquinoxaliloporphyrazine-based compound, naphthalocyanine-based compound, subphthalocyanine-based compound Compound, pyrylium-based compound, thiopyrylium-based compound, tetrapyrine-based compound, annulene-based compound, spiropyran-based compound, spirooxazine-based compound, thiospiropyran-based compound, metal arene complex, organic ruthenium complex, or benzophenone-based compound etc. can be mentioned. Among these, from the viewpoints of developability and pattern formation, thioxanthone-based compounds and benzophenone-based compounds are preferable.

Thioxanthone compounds, for example, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro -4-propoxythioxanthone etc. are mentioned. Among these, 2,4-diethylthioxanthone is preferable.

As for a benzophenone type compound, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2-amino benzophenone etc. are mentioned, for example. Among these, 4,4'-bis (diethylamino) benzophenone is preferable.

A sensitizer (F) can be used individually or in combination of 2 or more types.

The content of the sensitizer (F) is preferably 10 to 400 parts by mass, more preferably 20 to 300 parts by mass, based on 100 parts by mass of the photopolymerization initiator (C), from the viewpoint of pattern formation.

[Dye Derivative (G)]

The photosensitive composition of the present invention may contain a dye derivative (G).

The pigment derivative (G) includes, for example, a compound having a structure in which a part of the pigment is substituted with an acidic group, a basic group, a neutral group or the like. The dye derivative (G) is, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group, or a phosphoric acid group, and these amine salts, a sulfonamide group or a compound having a basic substituent such as a tertiary amino group at the terminal, a phenyl group or a phthal and compounds having neutral substituents such as imide alkyl groups.

The dye is, for example, a diketopyrrolopyrrole compound, a phthalocyanine compound, an anthraquinone compound, a quinacridone compound, a dioxazine compound, a perinone compound, a perylene compound, a thiazine indigo compound, a triazine compound, and a benzimida. A zolone compound, a benzoisoindole compound, an isoindoline compound, an isoindolinone compound, a quinophthalone compound, a naphthol compound, a squarylium compound, a threne compound, a naphthalocyanine compound, etc. are mentioned.

Specifically, as a pyrrolopyrrole pigment derivative, Japanese Patent Application Laid-open No. 2001-220520, International Laid-open No. 2009/081930, International Laid-open No. 2011/052617, International Laid-open No. 2012/102399, Japanese Patent Laid-Open 2017- Publication No. 156397, International Publication No. 2018/101189, As phthalocyanine-based pigment derivatives, Japanese Patent Application Publication No. 2007-226161, International Publication No. 2016/163351, Japanese Patent Application Publication No. 2017-165820, Japanese Patent No. 5753266 , As an anthraquinone-based pigment derivative, Japanese Patent Laid-Open No. 63-264674, Japanese Patent Laid-Open No. 09-272812, Japanese Patent Laid-Open No. 10-245501, Japanese Patent Laid-Open No. 10-265697, Japanese Patent Publication No. 2007-079094, International Publication No. 2009/025325, as quinacridone-based pigment derivatives, Japanese Unexamined Patent Publication No. 48-54128, Japanese Unexamined Patent Publication No. 03-9961, Japanese Unexamined Patent Publication No. 2000-273383 , Japanese Patent Laid-Open No. 2011-162662 as a dioxazine-based pigment derivative, Japanese Patent Laid-Open No. 2007-314785 as a thiazine-based pigment derivative, and Japanese Unexamined Patent Publication No. 61-246261 as a triazine-based pigment derivative, Japan Japanese Unexamined Patent Publication No. 11-199796, Japanese Unexamined Patent Publication No. 2003165922, Japanese Unexamined Patent Publication No. 2003-168208, Japanese Unexamined Patent Publication No. 2004-217842, Japanese Unexamined Patent Publication No. 2007-314681, as benzoisoindole-based pigment derivatives , Japanese Unexamined Patent Publication No. 2009-57478, as quinophthalone-based pigment derivatives, Japanese Unexamined Patent Publication No. 2003-167112, Japanese Unexamined Patent Publication No. 2006-291194, Japanese Unexamined Patent Publication No. 2008-31281, Japanese Unexamined Patent Publication 2012- 226110, as a naphthol-based pigment derivative, Japanese Patent Laid-Open No. 2012-208329, Japanese Patent Laid-Open No. 2014-5439, as a squarylium-based pigment derivative, International Publication No. 2020/054718, as an azo-type pigment derivative, Japan Japanese Unexamined Patent Publication No. 2001-172520, Japanese Unexamined Patent Publication No. 2012-172092, Japanese Unexamined Patent Publication No. 2004-307854 as an acidic substituent, Japanese Unexamined Patent Publication 2002-201377, and Japanese Unexamined Patent Publication 2003-171594 as a basic substituent Publication, Japanese Unexamined-Japanese-Patent No. 2005-181383, Unexamined-Japanese-Patent No. 2005-213404, etc. can mention the well-known pigment derivative described. In addition, although these documents may describe as a derivative, a pigment derivative, a dispersing agent, a dispersing aid, a pigment dispersing agent, or simply a compound, etc., it is synonymous with a pigment derivative (G).

Dye derivative (G) can be used individually or in combination of 2 or more types.

[Thermosetting compound (H)]

The photosensitive composition of the present invention may contain a thermosetting compound (H). As a result, the thermosetting compound (H) reacts in the heating step to increase the crosslinking density, thereby improving heat resistance.

The thermosetting compound (H) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (H) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, an epoxy compound and an oxetane compound are preferable.

Commercially available products are, for example, Mitsui Chemicals, Inc. Manufactured by TECHMORE VG3101L, Nippon Kayaku Co., Ltd. EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Mitsubishi Chemical Corporation Epikote 807, 815, 825, 827, 828, 190P, 191P, 1004, 1256, JER1032H60, 157S65, 0, 157S65 152, 154, CELLOXIDE 2021 manufactured by Daicel Corporation, EHPE-3150, TTA3150 manufactured by Tetra-Chem, DENACOL EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521 manufactured by Nagase Chemtex Corporation , 611, 612, 614, 614B, 622, 711, 721, TEPIC-L, H, S manufactured by Nissan Chemical Industries, Ltd., and the like.

From the viewpoint of chemical resistance, epoxy compounds having an alicyclic structure are preferred, and among these, EHPE-3150 is particularly preferred. By having an alicyclic structure, penetration of chemicals can be suppressed.

Furthermore, by blending the epoxy compound with the polymerizable compound (B1) having a (meth)acryloyl group and an amine structure, the chemical resistance is further improved although the mechanism is unknown.

The content of the epoxy compound (H1) is preferably 0.5 to 30 parts by mass, and more preferably 1.0 to 20 parts by mass with respect to 100 parts by mass of the non-volatile matter of the photosensitive coloring composition from the viewpoint of solvent resistance.

The content of the epoxy compound (H1) is preferably from 0.5 to 50% by mass, and more preferably from 1 to 40% by mass, based on 100% by mass of the non-volatile matter of the photosensitive composition.

The content of the oxetane compound (H2) is preferably from 0.5 to 50% by mass, and more preferably from 1 to 40% by mass, based on 100% by mass of the non-volatile matter of the photosensitive composition.

A thermosetting compound (H) can be used individually or in combination of 2 or more types.

[Curing Agent (Curing Accelerator)]

In the photosensitive composition of the present invention, a curing agent (curing accelerator) may be used in combination to assist curing of the thermosetting compound (H). Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds.

A hardening|curing agent can be used individually or in combination of 2 or more types.

The content of the curing agent is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the thermosetting compound (H).

[Thiol chain transfer agent (I)]

The photosensitive composition of the present invention may contain a thiol chain transfer agent (I). When the thiol-based chain transfer agent (I) is used in combination with the photopolymerization initiator (C), during radical polymerization after light irradiation, thiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated, and the photosensitivity of the photosensitive composition is improved.

The thiol chain transfer agent (I) is preferably a polyfunctional thiol having two or more thiol groups (SH groups), and more preferably a polyfunctional thiol having four or more thiol groups. When the number of functional groups increases, photocuring becomes easier from the surface to the deepest part of the film.

Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropionate. Cionate, trimethylolpropanetrithioglycolate, trimethylolpropanetrithiopropionate, trimethylolpropanetris(3-mercaptobutyrate), pentaerythritol tetrakithioglycolate, pentaerythritol tetrakithiopropio nate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N- dibutylamino)-4,6-dimercapto-s-triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane trithiopropionate, and pentaerythritol tetrakisthio Propionate etc. are mentioned.

Thiol-type chain transfer agent (I) can be used individually or in combination of 2 or more types.

The content of the thiol chain transfer agent (I) is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass, based on 100 parts by mass of the non-volatile matter of the photosensitive composition. When an appropriate amount is contained, the photosensitivity is improved and wrinkles are less likely to occur on the surface of the cured film.

[Polymerization inhibitor (J)]

The photosensitive composition of this invention can contain a polymerization inhibitor (J).

The polymerization inhibitor (J) is, for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3 -Ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butyl Alkyl catechol compounds such as catechol, 2-t-butylcatechol, 3-t-butylcatechol, 4-t-butylcatechol, and 3,5-di-t-butylcatechol; 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n- Alkylresorcinol compounds such as butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di- Alkylhydroquinone compounds such as t-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine and tribenzylphosphine, trioctylphosphine oxide, triphenyl and phosphine oxide compounds such as phosphine oxide, phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite, pyrogallol, and phloroglucine.

As for content of a polymerization inhibitor (J), 0.01-0.4 mass % is preferable in 100 mass % of the non-volatile matter of the photosensitive composition.

[Ultraviolet rays absorbent (K)]

The photosensitive composition of the present invention may contain a UV absorber (K).

The ultraviolet absorber (K) is an organic compound having an ultraviolet ray absorbing function, and includes benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicyl A rate organic compound etc. are mentioned.

The content of the ultraviolet absorber (K) is preferably 5 to 70% by mass based on 100% by mass of the total of the photopolymerization initiator (C) and the ultraviolet absorber (K).

[Antioxidant (L)]

The photosensitive composition of the present invention may contain an antioxidant (L). The antioxidant (L) prevents the photopolymerization initiator (C) and the thermosetting compound (H) in the photosensitive coloring composition from being oxidized by a thermal process during thermal curing or ITO annealing to prevent yellowing.

Examples of the antioxidant (L) include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferable.

Antioxidant (L) can be used individually or in combination of 2 or more types.

As for content of antioxidant (L), 0.5-5.0 mass % is preferable in 100 mass % of the non-volatile matter of the photosensitive composition. When contained in an appropriate amount, transmittance, spectral characteristics, and sensitivity are improved.

[Leveling agent (M)]

The photosensitive composition of the present invention may contain a leveling agent (M). Thereby, the wettability and dryness with respect to the board|substrate at the time of coating are further improved. Examples of the leveling agent (M) include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

Examples of the silicone surfactant include straight-chain polymers formed of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains and terminals.

Commercially available products are, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377 manufactured by BYK. , 378, 3455, UV3510, 3570, Dow Corning Toray Co., Ltd. Manufactured by FZ-7002, 2110, 2122, 2123, 2191, 5609, Shin-Etsu Chemical Co., Ltd. Manufactured by X-22-4952, X-22-4272, X-226266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22- 4515, KF-6004, KP-341, etc. are mentioned.

Examples of the fluorine-based surfactant include a surfactant or leveling agent having a fluorocarbon chain.

Commercially available products are, for example, AGC SEIMI CHEMICAL CO., LTD. SURFLON S-242, 243, 420, 611, 651, 386 manufactured by DIC Corporation, Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, 576, R-40-LM manufactured by DIC Corporation , R-41, RS-72-K, DS-21, FC-4430, 4432 manufactured by Sumitomo 3M Limited, Mitsubishi Materials Electronic Chemicals Co., Ltd. EF-PP31N09 manufactured by, EF-PP33G1, EF-PP32C1, 602A manufactured by FTERGENT manufactured by NEOS COMPANY LIMITED, etc. are mentioned.

Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether , polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxy Ethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphoric acid ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan Bitane Trioleate, Sorbitan Sesquioleate, Polyoxyethylene Sorbitan Monolaurate, Polyoxyethylene Sorbitan Monopalmitate, Polyoxyethylene Sorbitan Monostearate, Polyoxyethylene Sorbitan Tristearate, Polyoxyethylene Sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitol tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distea rate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkyl imidazoline and the like.

Commercial products include, for example, EMULGEN 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A- 90, B-66, PP-290, LATEMUL PD-420, PD-430, PD-430S, PD-450, RHEODOL SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP- O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TWP120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW -IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, EMANON 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH -60(K), ameet 102, 105, 105A, 302, 320, Amino PK-02S, L-02, Homogenol L-95, ADEKA Pluronic® L-23, 31, 44, 61 manufactured by ADEKA CORPORATION , 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, kyoeisha chemical co., ltd. manufactured (meth)acrylic acid-based (co)polymer Polyflow No.75, No.90, No.95, and the like.

Cationic surfactants include, for example, alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

As for a commercial item, Acetamine 24 by Kao Corporation, Kotamine 24P, 60W, 86P CONC, etc. are mentioned, for example.

Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of a styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, and the like. there is.

Examples of commercially available products include FTERGENT 100 and 150 manufactured by NEOS COMPANY LIMITED, Adeka Hop YES-25 manufactured by ADEKA CORPORATION, Adeka Cole TS-230E, PS-440E, and EC-8600.

Amphoteric surfactants include, for example, alkyl betaines such as lauric acid amide propyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine, and lauryldimethylamine oxide. Alkylamine oxides, such as these, etc. are mentioned.

Examples of commercially available products include AMPHITOL 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N manufactured by Kao Corporation.

A leveling agent (M) can be used individually or in combination of 2 or more types.

The content of the leveling agent (M) is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass in 100% by mass of the non-volatile matter of the photosensitive composition. When an appropriate amount is contained, the coatability of the photosensitive composition and the adhesive balance are further improved.

[Storage Stabilizer (N)]

The photosensitive composition of the present invention may contain a storage stabilizer (N). This stabilizes the viscosity of the photosensitive composition over time. The storage stabilizer (N) is, for example, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, Organic phosphines, such as tetraphenyl, phosphite, etc. are mentioned.

As for content of a storage stabilizer (N), 0.05-5 mass % is preferable in 100 mass % of the non-volatile matter of the photosensitive composition.

[adhesion improver (O)]

The photosensitive composition of the present invention may contain an adhesion improver (O). Thereby, the adhesiveness of a cured film and a base material improves. Moreover, it becomes easy to form a pattern with a narrow width by the photolithography method.

As for the adhesion improving agent (0), a silane coupling agent etc. are mentioned, for example. Examples of the silane coupling agent include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane. (meth)acrylic silanes such as methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. Epoxysilanes, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl) -Aminosilanes such as hydrochloride of 2-aminoethyl-3-aminopropyltrimethoxysilane, mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, p-sti Styryls such as yltrimethoxysilane, ureides such as 3-ureidpropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxysilane, etc. Silane coupling agents, such as isocyanates, are mentioned.

Adhesion improver (O) can be used individually or in combination of 2 or more types.

The content of the adhesion improver (O) is preferably from 0.05 to 5% by mass in 100% by mass of the non-volatile matter of the photosensitive composition.

[Method for producing photosensitive composition]

In the photosensitive composition of the present invention, when using a colorant (E), for example, a dispersion is prepared by adding a resin (A), an organic solvent (D) and a colorant (E) and performing a dispersion treatment. After that, the dispersion can be prepared by blending and mixing the resin (A), the polymerizable compound (B), the photopolymerization initiator (C), and the like. In addition, the timing of blending each material is arbitrary. Further, the dispersing step may be performed a plurality of times.

Examples of the disperser that performs the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular type bead mill, or an attritor.

The average dispersed particle diameter (secondary particle diameter) of the colorant (E) in the dispersion is preferably 30 to 200 nm, and more preferably 40 to 200 nm. When it has an appropriate particle diameter, it is easy to obtain a photosensitive composition with high dispersion stability.

The method for measuring the average dispersed particle size (secondary particle size) is, for example, Nikkiso Co., Ltd.'s Microtrac UPA-EX150 employing a dynamic light scattering method (FFT power spectrum method), and the particle permeability is measured in an absorption mode. , the particle shape is non-spherical, and the D50 particle diameter is the average diameter. The diluting solvent for measurement is preferable because it is easy to obtain a result with little non-uniformity when the organic solvent used for dispersion is respectively used and the sample treated with ultrasonic waves is measured immediately after sample preparation.

The photosensitive composition is obtained by means such as centrifugal separation, filtration with a sinter filter or membrane filter, and coarse particles of 5 µm or more, preferably 1 µm or more, more preferably 0.5 µm or more, and mixing. It is desirable to perform the removal of the dust. The photosensitive composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

<cured film>

The cured film of the present invention is a cured product of a photosensitive composition. The cured film of the present invention can be used for an optical filter.

[Method for producing cured film]

The manufacturing method of a cured film is not specifically limited, For example, the process (1) of apply|coating a photosensitive composition on a board|substrate and forming the layer of a composition, the process of exposing this layer to light in a pattern shape through a mask (2) ), a step (3) of alkali developing the unexposed portion to form a patterned cured film, and a method of performing a step (4) of heating the pattern (post-bake). In the present invention, the formation of the cured film is preferably performed at a temperature of 130° C. or less, and more preferably at a temperature of 100° C. or less throughout the entire process.

Hereinafter, the manufacturing method of a cured film is demonstrated in detail.

(Process (1))

In step (1) of forming a layer of a composition, a photosensitive composition is applied onto a substrate by, for example, spin coating, roll coating, slit coating, casting coating, or inkjet coating, if necessary. Dry (prebake) for 10 to 120 seconds at a temperature of 50 to 100 ° C. using an oven, hot plate, etc. according to the method.

As for the said board|substrate, a glass substrate, a resin substrate, a silicon substrate etc. are mentioned, for example. Examples of the resin substrate include a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a polyimide substrate. An organic light emitting layer may be formed on these substrates. The silicon substrate may have, for example, imaging elements such as CCD and CMOS formed on the surface. Further, on the substrate, if necessary, an undercoating layer may be provided for improving adhesion to the upper layer, preventing diffusion of substances, and flattening the surface of the substrate.

The film thickness of the layer is not particularly limited, but it is preferable to apply so as to be 0.05 to 10.0 μm after drying, and more preferably to be applied so that it is 0.3 to 5.0 μm.

(Process (2))

An exposure process exposes the layer obtained at process (1) to a specific pattern through a mask, for example using exposure apparatuses, such as a stepper. In this way, a cured film is obtained.

Examples of the radiation used for exposure include ultraviolet rays such as g-line (wavelength 436 nm), h-line (wavelength 405 nm), and i-line (wavelength 365 nm). In addition, light with a wavelength of 300 nm or less can also be used. Examples of light having a wavelength of 300 nm or less include KrF rays (wavelength of 248 nm) and ArF (wavelength of 193 nm). In the exposure, light may be continuously irradiated and exposed, or light irradiation and pause may be repeatedly exposed (pulse exposure) in cycles of a short time (for example, millisecond level or less).

(Process (3))

When the cured film obtained in step (2) is subjected to alkali development treatment, the layer of the composition in the unexposed portion is eluted into aqueous alkali solution, and only the cured portion remains, resulting in a patterned cured film. The developer is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline , pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene and the like.

The concentration of the alkali developing solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass.

11-13 are preferable and, as for pH of alkaline developing solution, 11.5-12.5 are more preferable. When used at an appropriate pH, pattern roughness and peeling are suppressed, and the remaining film rate after development is improved.

Developing methods include, for example, a dip method, a spray method, and a paddle method. The developing temperature is preferably 15 to 40°C. In addition, it is preferable to wash with pure water after alkali development.

(Process (4))

The heat treatment (postbake) sufficiently cures the patterned cured film obtained in step (3) by heating. 130 degrees C or less is preferable, and, as for the heating temperature of a post-bake, 100 degrees C or less is more preferable. The lower limit of the heating temperature is not particularly limited as long as curing can be accelerated, but is preferably 50°C or higher. The heating time is not particularly limited, but is preferably 5 minutes to 1 hour.

<Optical filter>

The optical filter of the present invention has a cured film formed from the photosensitive composition of the present invention. An optical filter can be used for various purposes. For example, it can be used for a color filter, a black matrix, an infrared transmission filter, an infrared cut filter, a light blocking filter, a microlens, a color filter having a circular polarizing function for an organic EL display device, and the like.

For example, a color filter has the cured film of this invention as red, green, and blue pixels by appropriately selecting the kind of coloring agent (E) to be used. Also, similarly, a magenta pixel, a cyan pixel, a yellow pixel, a white pixel, a gray pixel, and a black pixel may be included. Also, it may have a clear pixel. The optical filter of the present invention can be manufactured by the same method as the cured film described above.

<Image Display Device>

The image display device of the present invention includes the optical filter of the present invention. As for an image display device, a liquid crystal display, an organic electroluminescent display, etc. are mentioned, for example. The form used for the image display device is not particularly limited as long as it functions as an image display device. For example, the configuration described in “Next-generation liquid crystal display technology (authored by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd., 1994) and the like are exemplified. For definitions of image display devices and details of each image display device, see, for example, "Electronic display device (authored by Sasaki Akio, published by Kogyo Chosakai Publishing Co., Ltd., 1990)", "display device (authored by Ibuki Sumiaki)" , Sangyo Tosho Publishing Co., Ltd., published in the first year of Heisei)” and the like.

<Solid-state imaging device>

The solid-state imaging device of the present invention includes the optical filter of the present invention.

The form used for the solid-state imaging device is not particularly limited, but, for example, a plurality of photodiodes constituting a light-receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.), polysilicon, etc. It has a transfer electrode, has a photodiode and a light-shielding film opening only the light-receiving portion of the photodiode on the transfer electrode, and has a device protective film made of silicon nitride or the like formed to cover the entire surface of the light-shielding film and the photodiode light-receiving portion on the light-shielding film; It is a configuration having a filter on the protective film. Further, a configuration in which a concentrating unit (for example, a micro lens, as described below) is provided on the device protective film and under the filter (on the side close to the substrate) may be provided, or a configuration in which the condensing unit is provided on the filter may be used. Further, the filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned by partitions in a lattice shape, for example. The barrier rib in this case preferably has a low refractive index for each color pixel.

An imaging device having a solid-state imaging device of the present invention can be used for various purposes, such as, for example, digital cameras, electronic devices having an imaging function (mobile phones, smart phones, etc.), in-vehicle cameras, monitoring cameras, and optical sensors. .

[Example]

Hereinafter, the present invention will be described in more detail in Examples. However, the present invention is not limited to these. In addition, "part" is a "mass part", and "%" is a "mass %".

In addition, in this invention, a non-volatile matter or non-volatile matter concentration refers to the mass residue after oven standing at 230 degreeC for 30 minute(s).

Prior to Examples, each measurement method will be described.

Measurements of the weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH/g), and amine value (mgKOH/g) of the resin are as follows.

(average molecular weight of resin)

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. Using HLC-8220GPC (manufactured by TOSOH CORPORATION) as an apparatus, two separation columns are connected in series, and "TSK-GELSUPERHZM-N" is used as an eluent at an oven temperature of 40 ° C. Measurement was performed at a flow rate of 0.35 ml/min using a tetrahydrofuran (THF) solution. The sample was dissolved in a solvent composed of 1% by mass of the above eluent, and 20 µl of the sample was injected. Molecular weight is a polystyrene conversion value.

Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of the resin solution, stir to dissolve uniformly, use a 0.1 mol/L aqueous KOH solution as a titrant, and use an automatic titration device ("COM-555" manufactured by HIRANUMA Co., Ltd.) ), and the acid value (mgKOH/g) was measured based on the method of JIS K 0070. Then, the acid value per non-volatile content of the resin was calculated from the acid value of the resin solution and the concentration of the non-volatile content of the resin solution.

(amine value of resin)

The amine titer of resin is the value obtained by converting the total amine titer (mgKOH/g) measured in accordance with the method of ASTMD2074 into non-volatile matter.

"Amine value" is the number of milligrams of potassium hydroxide equivalent to hydrochloric acid required to neutralize the basic nitrogen contained in 1 g of the solid dispersant, and can be obtained by potentiometric titration in accordance with ASTM D 2074.

<Preparation of Resin (A)>

(Resin (A1-1) solution)

257.3 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet pipe, followed by stirring while purging with nitrogen, and the temperature was raised to 78°C. Next, 22.4 parts of dicyclopentanyl methacrylate, a monomer forming the alicyclic hydrocarbon-containing monomer unit (a6), 17.2 parts of methacrylic acid, a monomer forming the acidic group-containing monomer (a2), and other monomer units ( 49.8 parts of methyl methacrylate, which is a monomer forming a8), and Karenz MOI-DEM, a monomer forming monomer unit (a1) containing a block isocyanate group (malonic acid-2-[[[2-, manufactured by Showa Denko K.K.) methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester) with 63.0 parts and 11.0 parts of 2,2'-azobis(2,4-dimethylvale ronitrile) (polymerization initiator) was added and dissolved in 78.7 parts of PGMAc and was added dropwise into the flask from the dropping funnel. After completion of the dropping, the mixture was stirred at 78°C for 3 hours.

Then, PGMAc was added so that the non-volatile content might be 40 mass %, and the resin (A1-1) solution was prepared. Resin (A1-1) had an acid value of 111 mgKOH/g and a weight average molecular weight of 9,500.

(Resin (A1-2) to (A1-4) solution)

Resins (A1-2) to (A1-4) were synthesized so as to have a molar ratio with each constituent component shown in Table 1, and PGMAc was added to make the non-volatile content 40% by mass.

[Table 1]

(Resin (A2-1) solution)

196 parts of cyclohexanone was added to a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube, and a stirring device in a separable four-necked flask, the temperature was raised to 80 ° C, and the inside of the reaction vessel was substituted with nitrogen, From the dropping tube, 20.2 parts of methacrylic acid as a monomer forming the acidic group-containing monomer unit (a2), 21.8 parts of 2-hydroxyethyl methacrylate as a monomer forming the hydroxyl group-containing monomer unit (a3), general formula (1 ) 38.9 parts of Aronix M-110 (paracumylphenol EO modified acrylate manufactured by TOAGOSEI CO., LTD.), 39.0 parts of benzyl methacrylate, a monomer forming other monomer units (b8), n- A mixture of 35.8 parts of butyl methacrylate and 1.0 part of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. It was made to react for 3 hours after completion|finish of dripping. After cooling to room temperature, PGMAc was added so that the non-volatile content would be 40 mass %, and the resin (A21) solution of random polymer was prepared. Resin (A2-1) was an acid value of 81 mgKOH/g and a weight average molecular weight of 28,000.

(Resin (A2-2) and (A2-3) solution)

Random polymer resins (A2-2) and (A2-3) were synthesized so as to have a molar ratio with each component shown in Table 2, and PGMAc was added to make the non-volatile content 40% by mass.

[Table 2]

GMA+AA described in Table 2 represents a polymerizable unsaturated group-containing monomeric unit (b5) obtained by adding acrylic acid (hereinafter also referred to as AA) to an epoxy group of glycidyl methacrylate (hereinafter also referred to as GMA). GMA + AA + THPA represents a polymerizable unsaturated group-containing monomeric unit (b5) obtained by reacting the hydroxyl group of GMA + AA with tetrahydrophthalic anhydride (hereinafter also referred to as THPA).

(Resin (A3-1) solution)

108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 part of monobutyltin oxide as a catalyst were added to a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, and the mixture was replaced with nitrogen gas. Then, it was made to react at 120 degreeC for 5 hours (1st process). It was confirmed by the measurement of the acid value that 95% or more of the acid anhydrides were half esterified. Next, 160 parts of the compound obtained in the first step in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were added, the inside of the reaction vessel was heated to 80°C, and 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. and reacted for 12 hours (second step). It was confirmed that 95% reacted by non-volatile content measurement. Finally, 500 parts of the 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part of hydroquinone were added, and IR was applied to the isocyanate group at 2270 cm ^-1 . The reaction was performed until disappearance of the peak of was confirmed (third step). After confirmation of the peak disappearance, the reaction solution was cooled and a resin (A3-1) solution having a non-volatile content of 30% by mass and having a comb-shaped structure was obtained by adjusting the non-volatile content with PGMAc. Resin (A3-1) had an acid value of 68 mgKOH/g and an unsaturated double bond equivalent of 1,593 and a weight average molecular weight of 13,000.

(Resin (A3-2) solution)

10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc were added to a reaction vessel equipped with a gas inlet pipe, temperature, condenser, and stirrer. , replaced by nitrogen gas. The inside of the reaction vessel was heated and stirred at 50°C, and 12 parts of 3-mercapto-1,2-propanediol was added. It heated up to 90 degreeC, and reacted for 7 hours, adding the solution which added 0.1 part of 2,2'- azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate (following, PGMAc). It was confirmed that 95% reacted by non-volatile content measurement. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst were added and reacted at 100°C for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydrides were half-esterified, the reaction was terminated, and PGMAc was added and diluted so that the non-volatile content was 30% by mass, and a resin (A3-2) solution having a comb structure was obtained. Resin (A3-2) had an acid value of 70 mgKOH/g and a weight average molecular weight of 8,500.

(Resin (A3-3) solution)

30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were put into a reaction device equipped with a gas inlet pipe, condenser, stirring blades, and thermometer. Then, the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the inside of the system was substituted with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were introduced, and the temperature was raised to 110°C under a nitrogen stream to initiate polymerization of the first block (block B). After polymerization for 4 hours, the polymerization solution was sampled, the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content. Next, to this reaction apparatus, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (Showa Denko Materials co., Ltd. Manufacture, FANCRYL FA-711MM) was added, stirred while maintaining under a nitrogen atmosphere at 110°C, and the reaction was continued. Two hours after the introduction of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled, the non-volatile content was measured, and the polymerization conversion rate of the second block (A block) was calculated from the non-volatile content. After confirming that the content was 98% or higher, the reaction solution was cooled to room temperature to stop polymerization. PGMAc was added and diluted so that it might become 30 mass % of non-volatile content by the non-volatile content measurement, and the resin (A3-3) solution was obtained. Resin (A3-3) of block structure had an amine value of 57 mgKOH/g and a number average molecular weight of 4,500.

<Preparation of polymerizable compound (B)>

(Polymerizable compound (B1-3))

To a four-necked flask equipped with a thermometer, stirrer and reflux tube, 250 parts (0.247 mol) of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by TOAGOSEI CO., LTD., Aronix M-402) ) was added, and after adding 17.3 parts (0.134 mol) of di-n-butylamine at room temperature, the mixture was reacted at 50°C for 4 hours to obtain a polymerizable compound (B1-3). The reaction was performed in an air/nitrogen mixed atmosphere. The hydroxyl value was 30 mgKOH/g.

(Polymerizable compound (B1-5) having an amine structure)

In a four-necked flask equipped with a thermometer, stirrer and reflux tube, 118 parts (0.247 mol) of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (manufactured by TOAGOSEI CO., LTD., Aronix M-305) were added. After adding and adding 17.3 parts (0.134 mol) of di-n-butylamine at room temperature, reaction was performed at 50 degreeC for 4 hours, and the polymeric compound (B-1) which has a hydroxyl group and an amine structure was obtained. The reaction was performed in an air/nitrogen mixed atmosphere. The hydroxyl value was 155 mgKOH/g.

(Polymerizable compound (B1-6) having an amine structure)

To a four-necked flask equipped with a thermometer, stirrer and reflux tube, 250 parts (0.247 mol) of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by TOAGOSEI CO., LTD., Aronix M-402) ) was added, and after adding 14.1 parts (0.134 mol) of diethanolamine at room temperature, reaction was performed at 50°C for 4 hours to obtain a polymerizable compound (B1-5) having a hydroxyl group and an amine structure. The reaction was performed in an air/nitrogen mixed atmosphere. The hydroxyl value was 125 mgKOH/g.

(Polymerizable compound having an amine structure (B1-7))

In a four-necked flask equipped with a thermometer, stirrer and reflux tube, 118 parts (0.247 mol) of a mixture of pentaerythritol pentaacrylate and pentaerythritol hexaacrylate (manufactured by TOAGOSEI CO., LTD., Aronix M-305) were added. After adding and adding 14.1 parts (0.067 mol) of diethanolamine at room temperature, reaction was performed at 50 degreeC for 4 hours, and the polymeric compound (B-2) which has a hydroxyl group and an amine structure was obtained. The reaction was performed in an air/nitrogen mixed atmosphere. The hydroxyl value was 180 mgKOH/g.

(polymerizable compound (B2-8))

400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 part of N,N-dimethylbenzylamine were added to a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet pipe, thermometer, and dropping pipe, and heated to 70°C. The temperature was raised, and a mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After dripping, it was made to react at the temperature of 50-70 degreeC for 8 hours, and disappearance of the isocyanate absorption of 2180 cm ^<-1> was confirmed by IR. Then, 35 parts of mercaptoacetic acid and 0.6 part of 4-methoxyphenol were added and reacted at a temperature of 50 to 60°C for 6 hours to obtain a polymerizable compound (B2-8) having an acidic group and a urethane bond. PGMAc was added so that the non-volatile content might be 50% by mass.

<Manufacture of coloring agent (E)>

(micronized blue pigment (E-2))

100 parts of C.I. Pigment Blue 15:6, 1,000 parts of sodium chloride and 100 parts of diethylene glycol were put into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 50°C for 12 hours. This mixture was added to 3,000 parts of hot water, stirred with a high-speed mixer for about 1 hour while heating to about 70 ° C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then kept at 80 ° C for 24 hours. By drying and pulverizing, a micronized blue pigment (E-2) was obtained.

(micronized purple pigment (E-3))

100 parts of C.I. Pigment Violet 23, 1,000 parts of sodium chloride and 100 parts of diethylene glycol were put into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 70°C for 12 hours. This mixture was added to 3,000 parts of hot water, stirred with a high-speed mixer for about 1 hour while heating to about 70 ° C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then kept at 80 ° C for 24 hours. A micronized purple pigment (E-3) was obtained by drying and pulverizing.

(micronized red pigment (E-4))

100 parts of C.I. Pigment Red 254, 1,200 parts of sodium chloride and 120 parts of diethylene glycol were put into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 60 ° C. for 6 hours. Next, the kneaded mixture was added to 3,000 parts of warm water, stirred with a high-speed mixer for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then at 80 ° C. It was dried for 24 hours and pulverized to obtain a finely divided red pigment (E-4).

(micronized red pigment (E-5))

100 parts of C.I. Pigment Red 177, 1,200 parts of sodium chloride and 120 parts of diethylene glycol were put into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 60 ° C. for 6 hours. Next, this mixture was added to 3,000 parts of warm water, stirred with a high-speed mixer for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then heated to 24 ° C. It was dried for an hour and then pulverized to obtain a micronized red pigment (E-5).

(micronized yellow pigment (E-6))

100 parts of C.I. Pigment Yellow 138, 1,000 parts of sodium chloride and 100 parts of diethylene glycol were put into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 80°C for 6 hours. This mixture was added to 3,000 parts of hot water, stirred with a high-speed mixer for 1 hour while heating at 80 ° C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C for 24 hours. , to obtain a micronized yellow pigment (E-6) by pulverization.

(micronized yellow pigment (E-7))

100 parts of C.I. Pigment Yellow 139, 800 parts of sodium chloride and 100 parts of diethylene glycol were put into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 70°C for 12 hours. This mixture was added to 3,000 parts of hot water, stirred with a high-speed mixer for about 1 hour while heating to about 70 ° C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then kept at 80 ° C for 24 hours. By drying and pulverizing, a micronized yellow pigment (E-7) was obtained.

(micronized green pigment (E-8))

100 parts of C.I. Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were put into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 70°C for 6 hours. This kneaded material was put into 3,000 parts of warm water, stirred with a high-speed mixer for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then heated at 80 ° C. overnight ( By drying and pulverizing on one light night, a micronized green pigment (E-8) was obtained.

<Preparation of dispersion>

(Dispersion 1)

After stirring and mixing the following raw materials to be uniform, using zirconia beads with a diameter of 0.5 mm, after dispersing in an Eiger mill (Eiger Japan co., ltd "Mini Model M-250MKII") for 3 hours, a hole diameter of 1.0 μm It filtered with a filter of , and produced dispersion 1. The organic solvent (D-1) is PGMAc.

Carbon black (#850 manufactured by Mitsubishi Chemical Corporation): 15.0 parts

Resin (A3-1) solution: Part 15.0

Resin (A3-2) solution: Part 5.0

Pigment Derivative (G-1): 0.5 part

Organic solvent (D-1): Part 64.5

#850 manufactured by Mitsubishi Chemical Corporation is carbon black having an average primary particle diameter of 17 nm and a specific surface area of 220 m 2 /g.

Pigment Derivative (G-1): Structure shown below

[Tue 7]

(Dispersion 2-8)

Dispersions 2 to 8 were produced in the same manner as in Dispersion 1, except that the raw materials and amounts described in Table 3 were changed.

[Table 3]

Pigment derivative (G-2) of Table 3: the following structure

[Tue 8]

Pigment derivative (G-3) of Table 3: the following structure

[Tue 9]

Pigment derivative (G-4) of Table 3: the following structure

[Tue 10]

<Preparation of photosensitive composition>

[Example 1]

(Photosensitive composition 1)

The following raw materials were mixed and stirred, and filtered with a filter having a pore diameter of 1.0 µm to obtain the photosensitive composition 1.

Dispersion 2: Part 32.0

Dispersion 3: Part 2.0

Resin (A1-2) solution: Part 5.0

Polymerizable compound (B1-1): Part 1.0

Polymerizable compound (B2-1): Part 4.0

Photopolymerization initiator (C-1): 0.4 parts

Sensitizer (F): 0.6 part

Leveling agent (M): Part 1.0

Organic Solvent (D): Part 54.0

[Examples 2 to 58, Comparative Example 1]

(Photosensitive compositions 2 to 59)

Photosensitive compositions 2 to 59 were produced in the same manner as in Example 1, except that the photosensitive composition 1 of Example 1 was changed to the raw materials and amounts described in Tables 4-1 to 4-6.

[Table 4-1]

[Table 4-2]

[Table 4-3]

[Table 4-4]

[Table 4-5]

[Table 4-6]

About each raw material described in Table 4-1 - Table 4-6, it is as follows.

[Polymerizable compound (B)]

(Polymerizable compound (B1))

B1-1: Aronix MT-3041 (containing hydroxyl group manufactured by TOAGOSEI CO., LTD.)

B1-2: Aronix MT-3042 (manufactured by TOAGOSEI CO., LTD., containing hydroxyl groups)

B1-4: tris (acryloyloxyethyl) amine

(Polymerizable compound (B2))

B2-1: Etercure6361-100 (manufactured by Eternal Materials, a polymeric compound having a hyperbranched structure with an average number of acryloyl groups of 8)

B2-2: CN2303 (manufactured by SARTOMER, a polymerizable compound having a hyperbranched structure with an average number of acryloyl groups of 6)

B2-3: Etercure6363 (manufactured by Eternal Materials, a compound having a hyperbranched structure with an average number of acryloyl groups of 16)

B2-4: MiramerSP-1106 (manufactured by Miwon Specialty Chemical Co., Ltd, a polymerizable compound having a dendrimer structure with an average number of acryloyl groups of 18)

B2-5: Viscoat #1000LT (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD., a polymerizable compound having a dendrimer structure with an average number of acryloyl groups of 14)

B2-6: Aronix M-402 (manufactured by TOAGOSEI CO., LTD., containing a hydroxyl group of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)

B2-7: Aronix M-520 (manufactured by TOAGOSEI CO., LTD., a pentafunctional acrylate having an acidic group)

B2-9: Aronix M-309 (manufactured by TOAGOSEI CO., LTD., trimethylolpropane triacrylate)

B2-10: Aronix M-306 (manufactured by TOAGOSEI CO., LTD., containing a hydroxyl group of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate)

[Photoinitiator (C)]

C-1: photopolymerization initiator of the above formula (8)

C-2: photopolymerization initiator of the above formula (9)

C-3: photopolymerization initiator of the above-mentioned formula (10)

C-4: Omnirad369E (manufactured by IGMResins, an acetophenone compound)

[Organic Solvent (D)]

D-1: 30 parts of propylene glycol monomethyl ether acetate

D-2: 30 parts of cyclohexanone

D-3: 10 parts of ethyl 3-ethoxypropionate

D-4: 10 parts of propylene glycol monomethyl ether

D-5: 10 parts of cyclohexanol acetate

D-6: 10 parts of dipropylene glycol methyl ether acetate

In the above, (D-1) to (D-6) were respectively mixed in the above parts by mass to obtain the organic solvent (D).

[sensitizer (F)]

F-1: KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd., thioxanthone-based compound)

F-2: CHEMARKDEABP (manufactured by Chemark Chemical, benzophenone-based compound)

As mentioned above, (F-1) and (F-2) were mixed in the same quantity, respectively, and it was set as the sensitizer (F).

[Leveling agent (M)]

M-1: BYK-330 (manufactured by BYK JAPAN KK., silicone surfactant)

M-2: Megafac F-551 (manufactured by DIC Corporation, fluorine-based surfactant)

As mentioned above, each 1 part of (M-1) and (M-2) was mixed, and the mixed solution which melt|dissolved in 98 parts of PGMAc was used as the leveling agent (M).

[Thermosetting compound (H)]

H-1: EHPE-3150 (manufactured by Daicel Corporation, epoxy compound)

H-2: DENACOL EX-611 (manufactured by Nagase Chemtex Corporation, epoxy compound)

<Evaluation of photosensitive composition>

About the obtained photosensitive compositions 1-49 (Examples 1-48, Comparative Example 1), pattern formation property and solvent resistance were evaluated by the following method. Table 5 shows the evaluation results.

[Evaluation of pattern formation: adhesion]

The obtained photosensitive composition was applied to a glass substrate (EAGLE 2000 manufactured by Corning Inc.) having a length of 100 mm × a width of 100 mm and a thickness of 0.7 mm by spin coating so that the film thickness after drying was 2.0 μm, and the composition was heated at 70° C. for 1 minute. dried on a hot plate. Then, after cooling the substrate to room temperature, it was exposed to light at an illuminance of 30 mW/cm 2 and 50 mJ/cm 2 using a high pressure mercury lamp through a photomask having a stripe pattern of 5 μm to 25 μm in width at intervals of 5 μm. Thereafter, the substrate was subjected to spray development using an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C, followed by washing with ion-exchanged water and air drying. Spray development was performed in the shortest time possible for pattern formation without leaving development on the film in each photosensitive composition.

The patterns of the resulting substrates having a width of 5, 10, 15, 20, and 25 μm were observed under an optical microscope to confirm the minimum line width of the remaining pattern. The evaluation criteria are as follows, and three or more are considered practical.

5: A thin wire of 10 μm or less remains.

4: Fine lines of 15 μm or more remain.

3: Fine wires of 20 μm or more remain.

2: A thin wire of 25 µm remains.

1: Fine lines do not remain.

[Evaluation of solvent resistance (1): post-bake at 130 ° C]

The obtained photosensitive composition was coated on a glass substrate (EAGLE 2000 manufactured by Corning Inc.) having a length of 100 mm × a width of 100 mm and a thickness of 0.7 mm by spin coating so that the film thickness after drying was 2.0 μm, and the composition was heated at 70° C. for 1 minute. dried on a hot plate. Then, after cooling this board|substrate to room temperature, it exposed to ultraviolet rays using the high-pressure mercury-vapor lamp lamp at the illumination intensity of 30 mW/cm<2>, 50 mJ/cm<2>, through the photomask of the 100 micrometer width stripe pattern. Further, after cooling the substrate to room temperature, spray development was performed using an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C, followed by washing with ion-exchanged water and air drying. Thereafter, in a clean oven, it was postbaked at 130°C for 60 minutes to obtain a substrate for evaluation.

The obtained substrate for evaluation was immersed in propylene glycol monomethyl ether acetate at room temperature for 15 minutes, then washed with ion-exchanged water and air-dried, and a stripe pattern portion having a width of 100 μm was observed using an optical microscope. The evaluation criteria are as follows, and three or more are considered practical.

5: No change in appearance or color.

4: Although wrinkles etc. occur slightly, there is no change in color.

3: Wrinkles and the like occur in parts, but there is no change in color.

2: Wrinkles and the like occur on the entire surface, and the color is slightly faded.

1: Peeling or discoloration occurred.

[Evaluation of solvent resistance (2): 100 ° C post-bake]

The obtained photosensitive composition was applied to a glass substrate (EAGLE 2000 manufactured by Corning Inc.) having a length of 100 mm × a width of 100 mm and a thickness of 0.7 mm by spin coating so that the film thickness after drying was 2.0 μm, and the composition was heated at 70° C. for 1 minute. dried on a hot plate. Then, after cooling this board|substrate to room temperature, it exposed to ultraviolet rays using the high-pressure mercury-vapor lamp lamp at the illumination intensity of 30 mW/cm<2>, 50 mJ/cm<2>, through the photomask of the 100 micrometer width stripe pattern. Further, after cooling the substrate to room temperature, spray development was performed using an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C, followed by washing with ion-exchanged water and air drying. Thereafter, in a clean oven, it was postbaked at 100°C for 60 minutes to obtain a substrate for evaluation. The obtained substrate for evaluation was immersed in propylene glycol monomethyl ether acetate at room temperature for 15 minutes, then washed with ion-exchanged water and air-dried, and a stripe pattern portion having a width of 100 μm was observed using an optical microscope. The evaluation criteria are as follows, and three or more are considered practical.

5: No change in appearance or color.

4: Although wrinkles etc. occur slightly, there is no change in color.

3: Wrinkles and the like occur in parts, but there is no change in color.

2: Wrinkles and the like occur on the entire surface, and the color is slightly faded.

1: Peeling or discoloration occurred.

[Evaluation of solvent resistance (3): 90 ° C post-baking]

The obtained photosensitive composition was applied to a glass substrate (EAGLE 2000 manufactured by Corning Inc.) having a length of 100 mm × a width of 100 mm and a thickness of 0.7 mm by spin coating so that the film thickness after drying was 2.0 μm, and the composition was heated at 70° C. for 1 minute. dried on a hot plate. Then, after cooling this board|substrate to room temperature, it exposed to ultraviolet rays using the high-pressure mercury-vapor lamp lamp at the illumination intensity of 30 mW/cm<2>, 50 mJ/cm<2>, through the photomask of the 100 micrometer width stripe pattern. Further, after cooling the substrate to room temperature, spray development was performed using an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C, followed by washing with ion-exchanged water and air drying. Thereafter, in a clean oven, it was postbaked at 90°C for 60 minutes to obtain a substrate for evaluation. The obtained substrate for evaluation was immersed in propylene glycol monomethyl ether acetate at room temperature for 15 minutes, then washed with ion-exchanged water and air-dried, and a stripe pattern portion having a width of 100 μm was observed using an optical microscope. The evaluation criteria are as follows, and three or more are considered practical. Evaluation standard

6: No change in appearance or color.

5: Although wrinkles etc. occur very slightly, there is no change in color.

4: Although wrinkles etc. occur slightly, there is no change in color.

3: Wrinkles and the like occur in parts, but there is no change in color.

2: Wrinkles and the like occur on the entire surface, and the color is slightly faded.

1: Peeling or discoloration occurs.

[Table 5]

Claims (12)

A photosensitive composition comprising a resin (A), a polymerizable compound (B), a photopolymerization initiator (C) and an organic solvent (D),
The resin (A) includes a binder resin (A1) having a block isocyanate group-containing monomeric unit (a1) and an acidic group-containing monomeric unit (a2),
The photosensitive composition in which the said polymeric compound (B) contains the polymeric compound (B1) which has an acidic group or a hydroxyl group, and has three or more (meth)acryloyl groups and an amine structure. According to claim 1,
The photosensitive composition in which the said polymeric compound (B) contains polymeric compounds (B2) other than the polymeric compound (B1) which has three or more (meth)acryloyl groups and an amine structure. According to claim 2,
The photosensitive composition in which the said polymeric compound (B2) contains the polymeric compound which has 4 or more (meth)acryloyl groups. According to claim 1,
The photosensitive composition in which the said binder resin (A1) contains 1-50 mol% of block isocyanate group containing monomeric units (a1) in all structural units. According to claim 1,
The photosensitive composition in which content of the polymeric compound (B1) which has three or more (meth)acryloyl groups and an amine structure is 5-80 mass % in 100 mass % of the said polymeric compound (B). According to claim 1,
A photosensitive composition comprising a colorant (E). According to claim 1,
The photosensitive composition, wherein the resin (A) further comprises a dispersion resin (A3). As a photosensitive composition used for formation of a cured film obtained by exposure and post-baking at a temperature of 130 ° C. or lower,
The photosensitive composition contains a resin (A), a polymerizable compound (B), a photopolymerization initiator (C) and an organic solvent (D),
The resin (A) includes a binder resin (A1) having a block isocyanate group-containing monomer unit (a1) and an acidic group-containing monomer unit (a2), and the block isocyanate group-containing monomer unit (a1) is a binder resin ( 1 to 50 mol% of all structural units of A1),
The photosensitive composition in which the said polymeric compound (B) contains the polymeric compound (B1) which has an acidic group or a hydroxyl group, and has three or more (meth)acryloyl groups and an amine structure. A cured film that is a cured product of the photosensitive composition according to any one of claims 1 to 8. An optical filter comprising the cured film according to claim 9. An image display device comprising the optical filter according to claim 10 . A solid-state imaging device comprising the optical filter according to claim 10 .