JP2009216728A - Photosensitive resin composition, pattern obtained from it, and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for forming a pattern superior in solvent resistance or the like by being sufficiently cured even at a heating temperature of ≤200°C or a cured coating film. <P>SOLUTION: The photosensitive resin composition contains a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a solvent (D). The binder resin (A) is a copolymer making a composition monomer of at least an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride (A1) and an unsaturated compound (A2) having a hydroxyl group. The photopolymerizable compound (B) has a functional group reacted with a hydroxyl group and a compound having a photopolymerizable functional group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition, a pattern obtained from the composition by photolithography, and a display device having the pattern as a photospacer or an interlayer insulating film.

  In a display device such as a liquid crystal display device or a touch panel, a spacer is provided between the color filter and the array substrate to maintain the distance between them. In order to form this spacer, spherical particles are conventionally dispersed, but in recent years, a photo spacer has been proposed. The photospacer is manufactured by photolithography including (1) a photosensitive resin composition coating step, (2) a pre-bake step, (3) an exposure step, (4) a development step, and (5) a post-bake step.

In the photosensitive resin composition used for the photospacer, conventionally, dipentaerythritol hexaacrylate is used as a photopolymerizable compound (see, for example, Patent Document 1). However, when dipentaerythritol hexaacrylate is used, if the post-bake temperature is less than 200 ° C., the pattern is not sufficiently cured, and the pattern is dissolved in the subsequent process using a solvent. Therefore, the photosensitive resin composition containing dipentaerythritol hexaacrylate requires a post-bake temperature exceeding 200 ° C.
JP 2003-302039 A

  In recent years, plastic substrates have been studied for liquid crystal display devices and the like. Considering the heat resistance of the plastic substrate, it is desirable to set the heating temperature in the post-baking process to 200 ° C. or lower. Therefore, the problem to be solved by the present invention is a photosensitive resin composition having excellent solvent resistance even when heated at a low temperature (for example, 200 ° C. or lower) in a post-baking process, a pattern obtained from the photosensitive resin composition, And it is providing the display apparatus using this pattern.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention can form a photosensitive resin composition by combining a specific photopolymerizable compound (B) with a specific binder resin (A). It has been found that curing can be sufficiently promoted even when heated at a low temperature, and solvent resistance can be enhanced, and the present invention has been completed.
The photosensitive resin composition of the present invention is a photosensitive resin composition containing a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a solvent (D), The binder resin (A) is a copolymer having at least an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (A1) and an unsaturated compound (A2) having a hydroxyl group as constituent monomers, The polymerizable compound (B) is a compound having a functional group capable of reacting with a hydroxyl group and a photopolymerizable functional group.

  The photopolymerizable compound (B) is preferably a compound having a functional group capable of photoradical polymerization, and the photopolymerization initiator (C) is preferably a photoradical polymerization initiator. A more preferred photopolymerizable compound (B) is a formaldehyde condensate of melamines modified with at least one group selected from the group consisting of an acryloyl group and a methacryloyl group. These melamines may be further modified with an alkoxyl group.

  The binder resin (A) may be a ternary or higher copolymer composed of the monomer (A1), the monomer (A2), and another monomer (A3). Further, the photosensitive resin composition may contain a thermal acid generator (E).

Moreover, this invention also provides the pattern obtained from the said photosensitive resin composition, and this manufacturing method. In the method for producing a pattern of the present invention, the photosensitive resin composition is coated on a support, the solvent is removed from the composition to form a coating film, and the coating film is masked and exposed to light. After curing and removing the uncured portion of the coating film with a developer, the remaining coating film is heated at a temperature of 150 to 200 ° C.
The present invention also includes a display device in which a photospacer or an interlayer insulating film is configured in the pattern.

  According to the present invention, a photosensitive resin composition containing a binder resin (A) having a hydroxyl group and a photopolymerizable compound (B) having a functional group capable of reacting with a hydroxyl group and a photopolymerizable functional group is used. Further, it can be sufficiently cured even at a post-bake temperature of 200 ° C. or less, and a pattern or a cured coating film having good solvent resistance can be formed.

  The photosensitive resin composition of the present invention comprises a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a solvent (D). The binder resin (A), photopolymerizable compound (B), and photopolymerization initiator (C) may be dissolved or dispersed in the solvent (D). Hereinafter, each component will be described in order.

<Binder resin (A)>
The binder resin (A) includes at least an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (A1) (hereinafter sometimes simply referred to as a monomer (A1)) and an unsaturated compound (A2) having a hydroxyl group ( Hereinafter, it is a copolymer having a monomer as a constituent monomer. When binder resin (A) has a hydroxyl group, it can form a chemical bond with the photopolymerizable compound (B) mentioned later, and can improve a low temperature curing characteristic (solvent resistance).

The unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (A1) includes the following compounds.
For example, unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid;
Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and their anhydrides;
Mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl].
In the present invention, an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride having both a hydroxyl group and a carboxy group such as α-hydroxyalkylacrylic acid (α- (hydroxymethyl) acrylic acid) is used as the monomer (A1). use.
The said monomer (A1) can be used individually or in combination of 2 or more types.
In the present specification, the expression “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. The same applies to “(meth) acryloyl group”, “(meth) acryloyloxy”, and “(meth) acrylate”.

  Preferred monomers (A1) are acrylic acid, methacrylic acid and maleic anhydride. These are excellent in copolymerization reactivity, and the copolymer is excellent in solubility in an alkali developer.

Examples of the unsaturated compound (A2) having a hydroxyl group include the following (1) to (2).
(1) a compound having a hydroxyl group and a (meth) acryloyl group, for example,
(I) (Meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate;
(Ii) Polyol (meth) acrylates such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate;
(Iii) ε-caprolactone adduct of 2-hydroxyethyl (meth) acrylate, compound obtained by adding dibasic acid anhydride and ethylene oxide to 2-hydroxyethyl (meth) acrylate, phenyl glycidyl ether of (meth) acrylic acid Adducts, monocarboxylic acid adducts of glycidyl mono (meth) acrylate, 2-((meth) acryloyloxy) ethyl acetoacetate, and the like.
(2) Aromatic compounds such as allyl alcohol, allyloxyethanol, and hydroxystyrene.
A monomer (A2) can be used individually or in combination of 2 or more types.
Preferred monomers (A2) are (meth) acrylic acid hydroxyalkyl esters, particularly 2-hydroxyethyl (meth) acrylate. A copolymer of 2-hydroxyethyl (meth) acrylate is excellent in heat resistance and transparency.

The binder resin of the present invention may be a binary copolymer of the monomer (A1) and the monomer (A2), but is preferably a ternary system or more obtained by copolymerizing another different monomer (A3). It is a copolymer. Examples of the monomer (A1) and the other monomer (A3) copolymerizable with the monomer (A2) include the following:
(Meth) acrylic acid chain such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate and t-butyl (meth) acrylate Alkyl esters;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the technical field to which the present invention belongs, “dicyclopentanyl (Also called “(meth) acrylate”), (meth) acrylic acid cyclic alkyl esters such as dicyclopentanyloxyethyl (meth) acrylate, isoboronyl (meth) acrylate;
(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
(Meth) acrylonitrile, (meth) acrylamide, etc .;
Unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Styrenes such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene;
Vinyl halides such as vinyl chloride and vinylidene chloride;
Vinyl carboxylates such as vinyl acetate;
Bridged cyclic unsaturated hydrocarbons such as bicyclo [2.2.1] hept-2-ene;
Dienes such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Maleimides such as maleimide propionate, N- (9-acridinyl) maleimide;
Glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, (meth) acrylic acid-3,4-epoxybutyl, acrylic acid-6 7-epoxyheptyl, (meth) acrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, (meth) acrylic acid-β-methylglycidyl, (meth) acrylic acid-β- Epoxylated alkyl esters of acrylic acid or alkyl acrylic acid such as ethyl glycidyl, (meth) acrylic acid-β-propyl glycidyl;
vinyl benzyl glycidyl ethers such as o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether;
These can be used alone or in combination.

  Preferred monomers (A3) are monomers having excellent copolymerization reactivity, such as methyl methacrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene. Etc. Further, these preferred monomers (A3) copolymers have good solubility in an alkali developer.

The ratio of the monomers (A1), (A2), (A3) constituting the binder resin (A) is, for example, as follows.
Monomer (A1); 2 to 40 mol% (preferably 5 to 35 mol%)
Monomer (A2); 2-95 mol% (preferably 5-80 mol%)
Monomer (A3): 0 to 80 mol% (preferably 1 to 60 mol%)
When the ratio of each monomer is adjusted to the above range, the storage stability, developability, solvent resistance, heat resistance, and the like of the binder resin (A) can be improved.

  The binder resin (A) can be produced by a known method. For example, referring to “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and references cited in this document, What is necessary is just to copolymerize a structural monomer. In general, a predetermined amount of the monomer (A1), monomer (A2), polymerization initiator, solvent, and other monomer (A3) as necessary are charged into a reaction vessel, and an inert gas (for example, nitrogen) After replacing the atmosphere in the reaction vessel with, the copolymer can be produced by heating and stirring. The obtained copolymer may be used as the binder resin (A) as it is in the reaction solution or after being concentrated or diluted, and separated from the reaction solution by a method such as reprecipitation, and then used as the binder resin (A). It may be used.

  The weight average molecular weight of the binder resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000 in terms of polystyrene. If it is the molecular weight of the said range, the applicability | paintability of the photosensitive resin composition will improve. Further, when the molecular weight is in the above range, the film thickness of the pixel portion (exposed portion) hardly occurs during development, and the non-pixel portion (non-exposed portion) can be easily removed. As a result, the pattern resolution is improved.

  The molecular weight distribution {weight average molecular weight (Mw) / number average molecular weight (Mn)} of the binder resin (A) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is in the above range, the developability (resolution) of the photosensitive resin composition is improved.

  The content of the binder resin (A) of the present invention is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, based on the solid content in the photosensitive resin composition. If the content is in the above range, the resin dissolves satisfactorily in the alkaline developer, and development residues are less likely to occur on the non-pixel portion of the substrate. In addition, when the content is in the above range, film loss at the pixel portion is less likely to occur during development, and the non-pixel portion is easily removed.

<Photopolymerizable compound (B)>
The present invention is characterized in that a compound having a functional group capable of reacting with a hydroxyl group and a photopolymerizable functional group is used as the photopolymerizable compound (B). When such a compound (B) and the binder resin (A) having a hydroxyl group as described above are combined to constitute a photosensitive resin composition, the composition is sufficiently cured even when the heating temperature is 200 ° C. or less, and has a resistance to resistance. A pattern having excellent solvent properties can be formed.

  Examples of the functional group capable of reacting with a hydroxyl group include an amino group, an isocyanate group, a carboxy group (including an acid anhydride), a formyl group, a hydroxyalkyl group, and an alkoxyalkyl group. The amino group may be an amino group (substituted amino group, modified amino group) in which one or all hydrogen atoms are substituted with an organic group. For example, an alkylamino group; a hydroxyalkylamino such as a methylol group Group; an alkoxyalkylamino group and the like are included. Among these, an amino group, a hydroxyalkyl group (including a hydroxyalkyl group in the hydroxyalkylamino group), an alkoxyalkyl group (including an alkoxyalkyl group in the alkoxyalkylamino group), an isocyanate group, and a carboxy group are preferable.

  The photopolymerizable functional group is divided into a radical polymerizable group and a cationic polymerizable group, and is preferably a radical polymerizable group. Examples of the radical polymerizable group include a vinyl group and a (meth) acryloyl group. Examples of the cationically polymerizable group include a vinyl group, an epoxy group, and an oxetanyl group (oxetane ring), preferably a vinyl group and an epoxy group.

Examples of the photopolymerizable compound (B) include the following (1) to (3).
(1) A compound having an amino group (including a substituted amino group and a modified amino group) and a (meth) acryloyl group.
For example, formaldehyde condensates of (meth) acryloyl group-modified melamines.
(2) A compound having an amino group (including a substituted amino group and a modified amino group) and a (meth) acryloyl group.
For example, t-butylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N-methacryloxy-N, N-dicarboxymethyl-p-phenylenediamine, 2-[(1′-methyl Propylideneamino) carboxyamino] ethyl acrylate and the like.
(3) A compound having a carboxy group (including acid anhydride) and a (meth) acryloyl group.
For example, methacryloxyethyl phthalate, N-methacryloxy-N-carboxymethylpiperidine, 4-methacryloxyethyl trimellitic acid, acryloxyethyl terephthalate, ethylene oxide modified phthalic acid acrylate, ethylene oxide modified succinic acid acrylate, 4-methacryloxyethyl Trimellitic anhydride, etc.

Preferred photopolymerizable compounds (B) are melamines (preferably N, N, N ′, N ′, N ″, N ″ -hexaalkoxyalkylmelamines, especially N, N, N ′, N ′, N ″, N "-Hexamethoxymethylmelamine) is modified with a (meth) acryloyl group and condensed with formaldehyde. The condensate has excellent storage stability, but also excellent low-temperature curability. The formaldehyde condensate of (meth) acryloyl group-modified melamines may be further modified with an alkoxyl group. Formaldehyde condensates of (meth) acryloyl group-modified melamine which may be modified with an alkoxyl group include, for example, alkoxyalkylmelamines (preferably N, N, N ′, N ′, N ″, N ″ -hexaalkoxyalkyl) The alkoxyalkyl-substituted amino group of melamine, particularly N, N, N ′, N ′, N ″, N ″ -hexamethoxymethylmelamine) is substituted with (meth) acrylic acid hydroxyalkyl esters (preferably hydroxyC such as hydroxyethyl acrylate). _1-2 alkyl (meth) acrylate) and, if necessary, an aliphatic alcohol (preferably a C _1-12 alkanol), and the melamine is condensed with formaldehyde. In the present invention, “C _ab ” means “the number of carbons is a or more and b or less”.
The formaldehyde condensate of the (meth) acryloyl group-modified melamines is commercially available under a trade name such as “Nicalac MX-302” (manufactured by Sanwa Chemical Co., Ltd.).

  The content of the photopolymerizable compound (B) of the present invention is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, based on the solid content in the photosensitive resin composition. If it is content of the said range, even if post-baking temperature is low temperature, the pattern or non-pattern film (cured coating film) excellent in solvent resistance can be formed.

<Photopolymerization initiator (C)>
The photopolymerization initiator (C) is classified into a photo radical polymerization initiator (C1) and a photo acid generator (C2). These are properly used depending on the type of the photopolymerizable compound (B). The photopolymerizable compound (B) having a radical polymerizable group is used in combination with a photo radical polymerization initiator, and the photo polymerizable compound (B) having a cationic polymerizable group is used in combination with a photo acid generator (C2). Is done.

<Photoradical polymerization initiator (C1)>
Examples of the photo radical polymerization initiator (C1) include acetophenone compounds, biimidazole compounds, oxime compounds, triazine compounds, and acylphosphine oxide compounds (hereinafter referred to as first photo radical polymerization initiators). ) Is included. A radical photopolymerization initiator may be used independently and may combine 2 or more types.

  Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2. -Methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2- Morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholino Phenyl) -butan-1-one, 2- (3-methylbenzyl) -2-dimethylamino-1- ( -Morpholinophenyl) -butan-1-one, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (2-ethylbenzyl) -2 -Dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (2-Butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (2,3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) ) -Butan-1-one, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (2-chloroben) ) -2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (2-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butane-1- ON, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (4-chlorobenzyl) -2-dimethylamino-1- (4- Morpholinophenyl) -butan-1-one, 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (4-bromobenzyl) -2- Dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (2-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) ) -Butan-1-one, 2- (2-methyl-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (2-methyl-4-) Bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -Butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and the like.

Examples of biimidazole compounds include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis (2-chlorophenyl) -4,4' , 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′- Bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxyphenyl) biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204), and 4,4'5,5'- position of biimidazole compounds phenyl group is substituted by carbalkoxy group (for example, see, eg, JP-A-7-10913 JP.) And the like.
Preferred biimidazole compounds are 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole and the like.

  Specific examples of the oxime compound include O-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, a compound represented by formula (1), a compound represented by formula (2), and the like. It is done.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylphenyl) Thenyl] -1,3,5-triazine, and the like 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acyl phosphine oxide compound include 2,4,6-trimethylbenzoyldiphenyl phosphine oxide.

  The first photoradical polymerization initiator exemplified above (acetophenone compound, biimidazole compound, oxime compound, triazine compound, acylphosphine oxide compound, etc.) is one kind of second photoradical polymerization initiator. Or you may use together with 2 or more types. Examples of the second photo radical polymerization initiator include benzoin compounds, benzophenone compounds, thioxanthone compounds, anthracene compounds, and the like.

  Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

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

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

  Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene.

  Examples of the second photoradical polymerization initiator include 10-butyl-2-chloroacridone, benzyl (= “1,2-diphenylethane-1,2-dione”), phenylglyoxylic acid in addition to the compounds exemplified above. Examples thereof include methyl, titanocene compound, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone and the like.

  As the second photoradical polymerization initiator, a compound having a group capable of causing chain transfer as described in JP-T-2002-544205 can also be used. Examples of such a compound include compounds represented by formulas (3) to (8).

<Photoacid generator (C2)>
Examples of the photoacid generator (C2) include iodonium salt compounds, sulfonium salt compounds, organic halogen compounds (haloalkyl-s-triazine compounds and the like), sulfonic acid ester compounds, disulfone compounds, diazomethanesulfonyl compounds, N-sulfonyloxyimide compounds, Examples include oxime compounds. A preferred photoacid generator (C2) is an oxime compound.

  Examples of the oxime compounds include α- (4-toluenesulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) -4-methoxybenzyl cyanide, α- (camphorsulfonyloxyimino) -4. -Methoxybenzyl cyanide, α-trifluoromethanesulfonyloxyimino-4-methoxybenzyl cyanide, α- (1-hexanesulfonyloxyimino) -4-methoxybenzyl cyanide, α-naphthalenesulfonyloxyimino-4-methoxybenzyl Cyanide, α- (4-toluenesulfonyloxyimino) -4-N-diethylanilyl cyanide, α- (4-toluenesulfonyloxyimino) -3,4-dimethoxybenzylcyanide, α- (4-toluenesulfonyl) Oxyimino) -4-thienyl Cyanides such as anides; α-[(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, (5-tosyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, ( 5-camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-n-propyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, Acetonitriles such as (5-n-octyloxyimino-5-camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile.

<Content of photopolymerization initiator (C)>
The content of the photopolymerization initiator (C) is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass with respect to the total of the binder resin (A) and the photopolymerizable compound (B). is there. If a photoinitiator (C) is used with content of the said range, a pixel pattern with favorable intensity | strength and smoothness can be formed. When the first photoradical polymerization initiator is combined with the second photoradical polymerization initiator, the content means the total amount of the first and second photoradical polymerization initiators.

<Photopolymerization aid (CA)>
The photopolymerization initiator (C) may be combined with a photopolymerization assistant (CA) as necessary. This auxiliary agent (CA) is divided into an auxiliary agent for photoradical polymerization (CA1) and an auxiliary agent for photocationic polymerization (CA2). Preferred assistants (CA1) for photoradical polymerization include a first amine compound (more preferably an aromatic amine compound) and a carboxylic acid compound. Preferred assistants (CA2) for photocationic polymerization include amine compounds (second and third amine compounds). When the photoradical polymerization assistant (CA1) is used, the exposure sensitivity of the photosensitive resin composition is improved, and the productivity of pattern formation is improved. If the photocationic polymerization assistant (CA2) is used, it is possible to prevent the exposure amount when performing photolithography from greatly changing before and after storing the photosensitive composition for a long period of time. Further, by using the auxiliary agent (CA2), it is possible to reduce the dimensional change of the resist pattern due to the deactivation of the photoacid generator when the substrate is left after exposure.

  Examples of the first amine compound used as the photoradical polymerization aid (CA1) include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, 4-dimethylamino Ethyl benzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone ( Common names; Michler's ketone) and aromatic amine compounds such as 4,4′-bis (diethylamino) benzophenone.

  Examples of carboxylic acid compounds include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N- Examples thereof include carboxylic acids having a benzene ring such as phenylglycine and phenoxyacetic acid; aromatic carboxylic acids such as carboxylic acids having a naphthalene ring such as naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid (aromatic heteroacetic acid and the like).

  Examples of the amine compound (second amine compound) that is an auxiliary for cationic photopolymerization (CA2) and exhibits an effect of stabilizing the exposure dose include (for example, 3-amino-1-propanol, 1-amino- 2-propanol, 2-amino-1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 3-methyl-2-amino-1-butanol Amino alcohols such as 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] non Compounds having a diazabicyclo structure such as -5-ene are included.

  As an amine compound (third amine compound) that is an auxiliary for photocationic polymerization (CA2) and exhibits a dimension stabilizing effect, 4-nitroaniline, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2-diphenylethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, 4,4′-diamino -3,3 ', 5,5'-tetraethyl-diphenylmethane, 8-quinolinol, benzimidazole, 2-hydroxybenzimidazole, 2-hydroxyquinazoline, 4-methoxybenzylidene-4'-n-butylaniline, salicylic amide, salicyl Anilide, 1,8-bis (N, N-dimethylamino) naphthalene 1,2-diazine (pyridazine), piperidine, p-amino-benzoic acid, N-acetylethylenediamine, 2-methyl-6-nitroaniline, 5-amino-2-methylphenol, 4-n-butoxyaniline, 3- Ethoxy-n-propylamine, 4-methylcyclohexylamine, 4-tert-butylcyclohexylamine, monopyridines (imidazole, pyridine, 4-methylpyridine, 4-methylimidazole, 2-dimethylaminopyridine, 2-methylaminopyridine 1,6-dimethylpyridine), bipyridines (bipyridine, 2,2′-dipyridylamine, di-2-pyridyl ketone, 1,2-di (2-pyridyl) ethane, 1,2-di (4- Pyridyl) ethane, 1,3-di (4-pyridyl) propane, 1,2-bis (2- Lysyl) ethylene, 1,2-bis (4-pyridyl) ethylene, 1,2-bis (4-pyridyloxy) ethane, 4,4′-dipyridyl sulfide, 4,4′-dipyridyl disulfide, 1,2-bis (4-pyridyl) ethylene, 2,2′-dipicolylamine, 3,3′-dipicolylamine, etc.), ammonium salts (tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetra- and n-hexylammonium hydroxide, tetra-n-octylammonium hydroxide, phenyltrimethylammonium hydroxide, 3- (trifluoromethyl) phenyltrimethylammonium hydroxide, choline, etc.).

  The content of the photopolymerization assistant (CA) is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass with respect to the total of the binder resin (A) and the photopolymerizable compound (B). %.

<Solvent (D)>
The solvent (D) is not particularly limited as long as each component contained in the photosensitive resin composition can be uniformly dispersed or dissolved. Preferred solvents are, for example,
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Alkylene glycol alkyl ether acetates such as ethylene glycol alkyl ether acetate (methyl cellosolve acetate, ethyl cellosolve acetate, etc.), propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, etc. Kind;
Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone;
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin;
Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate;
and cyclic esters such as γ-butyrolactone.
These can be used alone or in combination.

  A preferred solvent (D) is a solvent having a boiling point of 100 to 200 ° C. under atmospheric pressure. As such solvents, alkylene glycol alkyl ether acetates, ketones, and esters can be used, particularly preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, and Examples include methyl 3-methoxypropionate. If a solvent having a boiling point of 100 to 200 ° C. is used, both applicability and drying property of the photosensitive resin composition can be achieved.

  Content of a solvent (D) becomes like this. Preferably it is 60-90 mass% with respect to the whole photosensitive resin composition, More preferably, it is 70-85 mass%. When content of a solvent (D) is made into the said range, the applicability | paintability when a photosensitive resin composition is apply | coated with the coating device mentioned later is favorable.

<Thermal acid generator (E)>
The photosensitive resin composition of the present invention may use a thermal acid generator (E) that generates an acid by the action of heat, if necessary. Examples of the thermal acid generator (E) include onium salts such as sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts. Preferred thermal acid generators (E) are sulfonium salts and benzothiazolium salts. A thermal acid generator (E) can be used individually or in combination of 2 or more types.

<Sulphonium salt>
As the sulfonium salt, a salt represented by the formula (9) is preferable.

In formula (9), R < ¹ > -R < ³ > shows the C1-C10 hydrocarbon group which may be substituted independently mutually. However, at least one of R ^{1 to} R ^{3 is} an optionally substituted aryl group having 6 to 10 carbon atoms. X ⁻ represents a monovalent anion. The carbon number of the hydrocarbon group and aryl group does not include the carbon number of the substituent.

Examples of the hydrocarbon group having 1 to 10 carbon atoms (hereinafter sometimes referred to as a basic hydrocarbon group) include aryl groups such as phenyl group and naphthyl group; aralkyl groups such as benzyl group and naphthylmethyl group; C _{1- A 10} alkyl group; and a C _5-8 cycloalkyl group.

Examples of the substituent bonded to the basic hydrocarbon group include a halogen atom, a C _1-5 alkyl group, a C _3-6 cycloalkyl group, a nitro group, a cyano group, —OR ⁴ , —COR ⁵ , —COOR ⁶ , -NR ⁷ R ⁸ , -OCOOR ⁹ , -OCOR ^{10 and the} like can be mentioned (the R ^{4 to} R ⁸ are independently of each other a hydrogen atom, a C _1-5 alkyl group, a C _3-6 cycloalkyl group. _Represents a C _6-10 aryl group or a C _7-11 aralkyl group, and R ⁹ and R ¹⁰ are independently of each other a C _1-5 alkyl group, a C _3-6 cycloalkyl group, a C _6-10 aryl group, or Represents a C _7-11 aralkyl group).

Examples of the basic hydrocarbon group to which the substituent is bonded include a substituted aryl group, a substituted aralkyl group, a substituted alkyl group, and a substituted cycloalkyl group. Substituted aryl groups include C _1-4 alkylphenyl groups, di-C _1-4 alkylphenyl groups, tri-C _1-4 alkylphenyl groups, C _1-4 alkylnaphthyl groups, chlorophenyl groups, dichlorophenyl groups, and chloro-methylphenyl. Group, chloro-hydroxyphenyl group, chloro-methoxyphenyl group, chloro-acetophenyl group, chloro-carboxyphenyl group, chloro-methoxycarbonylphenyl group, chloro-N, N-dimethylaminophenyl group, chloro-methoxycarbonyloxyphenyl Group, chloro-acetoxyphenyl group, nitrophenyl group, nitro-hydroxyphenyl group, cyanophenyl group, cyano-hydroxyphenyl group, hydroxyphenyl group, dihydroxyphenyl group, trihydroxyphenyl group, C _1-4 alkyl-hydroxyphenyl group The di C _{1 -4} alkyl-hydroxyphenyl group, C _1-6 alkoxyphenyl group, phenoxyphenyl group, benzyloxyphenyl group, acetophenyl group, C _2-6 alkylcarbonylphenyl group, phenylcarbonylphenyl group, benzylcarbonylphenyl group, carboxyphenyl Group, C _1-6 alkoxycarbonylphenyl group, phenoxycarbonylphenyl group, benzyloxycarbonylphenyl group, aminophenyl group, N, N-diC _1-3 alkylaminophenyl group, phenoxycarbonyloxyphenyl group, benzyloxycarbonyloxy Phenyl group, acetoxyphenyl group, cyclohexylcarbonyloxyphenyl group, benzoyloxyphenyl group, benzylcarbonyloxyphenyl group, methoxy-hydroxyphenyl group, aceto-hydroxyphenyl group Group, aceto - hydroxybenzyl group, methoxycarbonyl - hydroxyphenyl group, methoxycarbonyl - hydroxyphenyl group, N, N-dimethylamino - hydroxyphenyl group, methoxycarbonyloxy - hydroxyphenyl group, acetoxy - hydroxybenzyl group, fluoro C _1-3 alkyl-phenyl groups, chloro C _1-3 alkyl-phenyl groups and the like are included.

Examples of the substituted aralkyl group include a C _1-4 alkylbenzyl group, a di C _1-4 alkylbenzyl group, a tri C _1-4 alkylbenzyl group, a chlorobenzyl group, a chloromethylbenzyl group, a dichlorobenzyl group, a nitrobenzyl group, Cyanobenzyl group, hydroxybenzyl group, C _1-4 alkyl-hydroxybenzyl group, diC _1-4 alkyl-hydroxybenzyl group, dihydroxybenzyl group, trihydroxybenzyl group, C _1-6 alkoxybenzyl group, phenoxybenzyl group, Benzyloxybenzyl group, acetobenzyl group, C _2-6 alkylcarbonylbenzyl group, benzoylbenzyl group, benzylcarbonylbenzyl group, carboxybenzyl group, C _1-6 alkoxycarbonylbenzyl group, phenoxycarbonylbenzyl group, benzyloxycarbonylbenzyl group ,amino Njiru group, N, N-di-C _1-3 alkylamino benzyl group, C _1-6 alkoxycarbonyloxy benzyl group, a phenoxycarbonyl oxy group, a benzyl oxy carbonyloxy benzyl group, acetoxy benzyl group, a cyclohexyl carbonyloxy benzyl group, benzoyloxy group, a benzyl carbonyloxy benzyl group, chloro - hydroxybenzyl group, chloro -C _1-2 alkoxybenzyl group, chloro - aceto benzyl group, chloro - carboxy benzyl group, chloro -N, N-dimethylamino benzyl group, Chloro-methoxycarbonyloxybenzyl group, chloro-acetoxybenzyl group, nitro-hydroxybenzyl group, cyano-hydroxybenzyl group, methoxy-hydroxybenzyl group, aceto-hydroxybenzyl group, methoxy Examples include cicarbonyl-hydroxybenzyl group, N, N-dimethylamino-hydroxybenzyl group, methoxycarbonyloxy-hydroxybenzyl group, fluoro C _1-3 alkyl-benzyl group, chloro C _1-3 alkyl-benzyl group and the like.

The substituted alkyl group includes, for example, a fluoro C _1-3 alkyl group, a chloro C _1-4 alkyl group, a nitro C _1-4 alkyl group, a cyano C _1-4 alkyl group, a hydroxy C _1-4 alkyl group, a C _{1- 2} alkoxy C _1-4 alkyl group, aceto C _1-4 alkyl group, cyclohexylcarbonyl C _1-2 alkyl group, phenylcarbonyl C _1-2 alkyl group, benzylcarbonyl C _1-2 alkyl group, carboxy C _1-4 alkyl Group, C _1-4 alkoxycarbonyl C _1-2 alkyl group, cyclohexyloxycarbonyl C _1-2 alkyl group, phenoxycarbonyl C _1-2 alkyl group, benzyloxycarbonyl C _1-2 alkyl group, amino C _1-4 Alkyl group, N, N-dimethylamino C _1-4 alkyl group, C _1-4 alkoxycarbonyloxy C _1-2 alkyl group, cyclohexyloxycarbonyloxy C _1-2 alkyl group, phenoxy Cicarbonyloxy C _1-2 alkyl group, benzyloxycarbonyloxy C _1-2 alkyl group, acetoxy C _1-4 alkyl group, benzoyloxy C _1-2 alkyl group, benzylcarbonyloxy C _1-2 alkyl group, etc. .

Examples of the substituted cycloalkyl group include chlorocyclohexyl group, nitrocyclohexyl group, cyanocyclohexyl group, hydroxycyclohexyl group, C _1-2 alkoxycyclohexyl group, acetocyclohexyl group, carboxycyclohexyl group, amino group A substituted C _5-6 cyclohexyl group such as a cyclohexyl group, an N, N-dimethylaminocyclohexyl group, an acetoxycyclohexyl group is preferred.

As the sulfonium cation composed of the groups R ^{1 to} R ³ and S ⁺ , the following sulfonium cations (i) to (iv) are preferable.
(I) Sulfonium cations having one aryl group and two alkyl groups.
For example, phenyl group, methylphenyl group, chlorophenyl group, dichlorophenyl group, nitrophenyl group, cyanophenyl group, hydroxyphenyl group, methyl-hydroxyphenyl group, methyl-hydroxy-butylphenyl group, dihydroxyphenyl group, methoxyphenyl group, phenoxy Phenyl group, benzyloxyphenyl group, acetophenyl group, benzoylphenyl group, benzylcarbonylphenyl group, methoxycarbonylphenyl group, phenoxycarbonylphenyl group, benzyloxycarbonylphenyl group, N, N-dimethylaminophenyl group, methoxycarbonyloxyphenyl Group, phenoxycarbonyloxyphenyl group, benzyloxycarbonyloxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, - hydroxyphenyl group, and chloro - and one aryl group selected from the group consisting of hydroxyphenyl groups, such as sulfonium cation having two methyl groups.

(Ii) sulfonium cations having a phenyl group, a benzyl group and an alkyl group.
For example, phenyl group, methylphenyl group, chlorophenyl group, chloro-methylphenyl group, nitrophenyl group, cyanophenyl group, hydroxyphenyl group, methyl-hydroxyphenyl group, hydroxy-butylphenyl group, methyl-hydroxy-butylphenyl group, 1 selected from the group consisting of methoxyphenyl group, acetophenyl group, methoxycarbonylphenyl group, N, N-dimethylaminophenyl group, methoxycarbonyloxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, and chloro-hydroxyphenyl group A sulfonium cation having two phenyl groups, a benzyl group and a methyl group;
Phenyl group, chlorophenyl group, cyanophenyl group, hydroxyphenyl group, methoxyphenyl group, acetophenyl group, methoxycarbonylphenyl group, N, N-dimethylaminophenyl group, methoxycarbonyloxyphenyl group, acetoxyphenyl group, and benzoyloxyphenyl A sulfonium cation having one phenyl group selected from the group consisting of a group, a methylbenzyl group, and a methyl group;
Phenyl group, chlorophenyl group, nitrophenyl group, cyanophenyl group, hydroxyphenyl group, methoxyphenyl group, acetophenyl group, methoxycarbonylphenyl group, N, N-dimethylaminophenyl group, methoxycarbonyloxyphenyl group, acetoxyphenyl group, And a sulfonium cation having one phenyl group selected from the group consisting of benzoyloxyphenyl groups, a naphthylmethyl group, and a methyl group;
Phenyl group, chlorobenzyl group, dichlorobenzyl group, nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, methoxybenzyl group, acetobenzyl group, methoxycarbonylbenzyl group, N, N-dimethylaminobenzyl group, methoxycarbonyloxybenzyl A sulfonium cation having a group and one benzyl group selected from the group consisting of an acetoxybenzyl group and a methyl group;
One phenyl group selected from the group consisting of a chlorophenyl group, a dichlorophenyl group, a hydroxyphenyl group, a methyl-hydroxyphenyl group, a methyl-hydroxy-butylphenyl group, and a chloro-hydroxyphenyl group; a chlorobenzyl group or a dichlorobenzyl group; A sulfonium cation having a methyl group;
A sulfonium cation having a nitrophenyl group or a cyanophenyl group, a chlorobenzyl group, and a methyl group;
Selected from the group consisting of hydroxyphenyl group, nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, methoxybenzyl group, acetobenzyl group, methoxycarbonylbenzyl group, dimethylaminobenzyl group, methoxycarbonyloxybenzyl group, and acetoxybenzyl group A sulfonium cation having one benzyl group and a methyl group.

(Iii) A sulfonium cation having a phenyl group and two benzyl groups.
For example, phenyl group, chlorophenyl group, dichlorophenyl group, nitrophenyl group, cyanophenyl group, hydroxyphenyl group, methyl-hydroxyphenyl group, hydroxy-butylphenyl group, methyl-hydroxy-butylphenyl group, methoxyphenyl group, acetophenyl group One phenyl group selected from the group consisting of methoxycarbonylphenyl group, dimethylaminophenyl group, methoxycarbonyloxyphenyl group, acetoxyphenyl group, chloro-hydroxyphenyl group, and chloro-hydroxyphenyl group, and two benzyl groups, Such as sulfonium cations.

(Iv) A sulfonium cation having a phenyl group, an unsubstituted benzyl group and a substituted benzyl group.
For example, one phenyl group selected from the group consisting of phenyl group, nitrophenyl group, cyanophenyl group, hydroxyphenyl group, methyl-hydroxyphenyl group, methyl-hydroxy-butylphenyl group, and chloro-hydroxyphenyl group, and benzyl And a sulfonium cation having a chlorobenzyl group;
A sulfonium having one phenyl group selected from the group consisting of a phenyl group, a methyl-hydroxy-butylphenyl group, a hydroxyphenyl group, a methyl-hydroxyphenyl group, and a chloro-hydroxyphenyl group, a benzyl group, and a dichlorobenzyl group Cations and so on.

X ^{− in the} formula (9) includes, for example, BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , and sulfonate ions (for example, trifluoromethanesulfonate ion, p-toluenesulfonate ion, p-dodecyl). Benzenesulfonate ion, 1-naphthalenesulfonate ion, 1-pyrenesulfonate ion, etc. (preferably trifluoromethanesulfonate ion, p-toluenesulfonate ion, etc.).

Preferred sulfonium salts are 4-acetoxyphenyl / dimethylsulfonium cation, 4-hydroxyphenyl / benzyl / methylsulfonium cation, 4-acetoxyphenyl / benzyl / methylsulfonium cation, 4-hydroxyphenyl / dibenzylsulfonium cation, or 4-acetoxy. and phenyl-dibenzyl sulfonium cation, AsF ₆ ^- is a salt of a ^- or SbF _6. A particularly preferred sulfonium salt is 4-hydroxyphenyl benzyl methylsulfonium hexafluoroantimonate.

  The sulfonium salt is, for example, Sun-Aid SI-60L, SI-80L, SI-100L, SI-110L, SI-145, SI-150, SI-160, SI-180L, SI-250. (The above is manufactured by Sanshin Chemical Industry Co., Ltd.), Adeka optomer SP-170, and SP-172 (manufactured by Adeka Co., Ltd.).

<Benzothiazolium salt>
As the benzothiazolium salt, a salt represented by the formula (10) is preferable.

In formula (10), R ¹¹ and R ¹² represent a monovalent substituent, n represents an integer of 0 to 4, and Y ⁻ represents a monovalent anion.
Examples of R ¹¹ include an optionally substituted hydrocarbon group having 1 to 10 carbon atoms (particularly an optionally substituted benzyl group).
Examples of R ¹² include a halogen atom, a nitro group, a cyano group, an optionally substituted hydrocarbon group having 1 to 5 carbon atoms, —OR ¹³ , —COR ¹⁴ , —COOR ¹⁵ , —NR ¹⁶ R ¹⁷ , -OCOOR ^18, -OCOR ^19, and the like (the R ¹³ to R ¹⁷ each independently represent hydrogen, C _1-5 alkyl, C _3-6 cycloalkyl group, C _6-10 aryl group Or a C _7-11 aralkyl group, and R ¹⁸ and R ¹⁹ are each independently a C _1-5 alkyl group, a C _3-6 cycloalkyl group, a C _6-10 aryl group or a C _7-11 aralkyl group. To express.).

Examples of Y ^{− in the} formula (10) include BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , and sulfonate ions (for example, trifluoromethanesulfonate ion, p-toluenesulfonate ion, p-dodecyl). Benzene sulfonate ion, 1-naphthalene sulfonate ion, 1-pyrene sulfonate ion, etc.).

Preferred benzothiazolium salts include 3-benzylbenzothiazolium cations (eg, 3-benzylbenzothiazolium cation, 3- (4-methoxybenzyl) benzothiazolium cation, 3-benzyl-2-methyl Benzothiazolium cation, 3-benzyl-2-chlorobenzothiazolium cation, 3-benzyl-5-chlorobenzothiazolium cation), AsF ₆ ⁻ , SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , Examples thereof include salts with trifluoromethanesulfonic acid ions or p-toluenesulfonic acid ions. A more preferred benzothiazolium salt is 3-benzylbenzothiazolium hexafluoroantimonate.

<Content of thermal acid generator (E)>
When the thermal acid generator (E) is used, the content thereof is preferably 0.1 to 50% by mass, more preferably 1 with respect to the total of the binder resin (A) and the photopolymerizable compound (B). -30 mass%. If the amount of the thermal acid generator (E) is too small, the effect cannot be exhibited sufficiently. On the other hand, if the amount is excessive, the storage stability of the photosensitive resin composition is lowered.

<Other additives (F)>
The photosensitive resin composition of the present invention may further include additives such as fillers, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, chain transfer agents, and the like as necessary. ) May be added.

  Examples of the filler include glass, silica, alumina, and pigment. When a filler is added, the strength of the coating film obtained from the photosensitive resin composition can be adjusted, and the film can be colored.

  Examples of other polymer compounds include thermosetting resins such as epoxy resins and maleimide resins; and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Can be mentioned. When another polymer compound is added, the strength of the film obtained from the photosensitive resin composition can be adjusted.

As the pigment dispersant, one or more surfactants can be used. The surfactant may be an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a nonionic (nonionic) surfactant.
Preferred surfactants include polyoxyalkylene surfactants (polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, etc.), ester surfactants (sorbitan fatty acid esters, fatty acid modification) Polyesters, etc.), tertiary amine-modified polyurethanes, polyethyleneimines, silicone surfactants, fluorosurfactants and the like.
Surfactants are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), Ftop (manufactured by Tochem Products Co., Ltd.), MegaFuck (manufactured by Dainippon Ink Chemical Co., Ltd.), Fluorard (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.), PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) ) And the like, and these can be used.

  Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl). ) -3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Silanes such as methoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. When the adhesion promoter is used, the adhesion between the film obtained from the photosensitive resin composition and the support (substrate or substrate) can be improved.

  Examples of the antioxidant include 2,2'-thiobis (4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol.

  Ultraviolet absorbers include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

  Examples of the chain transfer agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene. When a chain transfer agent is used, the molecular weight can be controlled during the curing reaction of the photosensitive resin composition.

  The said photosensitive resin composition can be utilized in various field | areas by patterning by exposure. The pattern is, for example, (1) a step of applying the photosensitive resin composition (application step), (2) a step of removing a solvent from the applied photosensitive resin composition to form a coating film (prebaking step), (3) The process of masking the coating and then curing it by exposure (exposure process), (4) The process of washing away uncured parts (development process), and (5) The curing of the remaining coating is accelerated by heating. It is formed by the process to perform (post-baking process). If the photosensitive resin composition of the present invention is used, the post-baking process can be sufficiently cured even if it is performed at a lower temperature (150 to 200 ° C.) than before, and the solvent resistance of the film is increased. Can do. Hereinafter, each process is demonstrated in order.

(1) Coating process In a coating process, the photosensitive resin composition is apply | coated to a board | substrate (support body). As the substrate, a conventionally used glass substrate may be used, but according to the present invention, a plastic substrate can also be used. The photosensitive resin composition of this invention can lower post-baking temperature than before. Therefore, even when a plastic substrate is used, the resin film can be sufficiently cured without causing thermal degradation or thermal deformation of the substrate. For the application of the photosensitive resin composition, for example, a spin coater, a slit & spin coater, a slit coater (sometimes called a die coater or a curtain flow coater), an ink jet, or the like can be used.

(2) Prebaking step In the prebaking step, a smooth coating film is formed by removing volatile components such as a solvent by heating (for example, at a temperature of about 100 ° C for about several minutes). The coating thickness after pre-baking is, for example, about 1 to 6 μm.

(3) Exposure process In an exposure process, it exposes and photopolymerizes partially through the mask according to the target pattern shape. For the exposure, for example, an exposure apparatus such as a mask aligner or a stepper is used. By using these, it is possible to uniformly irradiate the entire exposed portion with parallel light rays and to accurately align the mask and the substrate.
The type of light source is not particularly limited as long as the photopolymerization of the photosensitive resin composition is possible, but usually ultraviolet rays (g-line, h-line, i-line, etc.) are used.

(4) Development step In the development step, an uncured portion of the coating film is removed using an alkaline aqueous solution (developer) to obtain a desired pattern shape. The developing method may be any of a liquid piling method, a dipping method, and a spray method. Further, the substrate may be tilted at an arbitrary angle during development.

  The developer usually contains an alkaline compound and a surfactant. The alkaline compound may be either an inorganic material or an organic material. Examples of inorganic alkaline compounds include hydroxides (sodium hydroxide, potassium hydroxide, etc.), phosphates (disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, etc. ), Silicate (sodium silicate, potassium silicate, etc.), carbonate (sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.), borate (sodium borate, potassium borate, etc.), ammonia Etc. Organic alkaline compounds include, for example, tetraalkylammonium hydroxides (tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, etc.), amines (monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, ethanolamine, etc.). An alkaline compound can be used individually or in combination of 2 or more types.

  The density | concentration of the alkaline compound in a developing solution becomes like this. Preferably it is 0.01-10 mass%, More preferably, it is 0.03-5 mass%.

  As the surfactant for the developer, a nonionic surfactant, an anionic surfactant, a cationic surfactant, or the like can be used. Examples of nonionic surfactants include polyoxyethylene ethers (polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, etc.), other polyoxyethylene derivatives, and oxyethylene / oxypropylene block copolymers. , Fatty acid esters (such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester), polyoxyethylene alkylamine and the like. Examples of the anionic surfactant include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; sodium dodecylbenzenesulfonate and dodecylnaphthalenesulfonate Examples thereof include alkyl aryl sulfonates such as sodium. Examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. Surfactant can be used individually or in combination of 2 or more types.

The concentration of the surfactant in the developer is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and particularly preferably 0.1 to 5% by mass.
After the development, the substrate (support) and the coating film are usually washed with water. By washing with water, the developer and the remainder of the uncured portion are removed.

(5) Post-baking step In the post-baking step, the coating film remaining after development is heated at a temperature of 150 to 200 ° C for about 10 to 300 minutes. The photosensitive resin composition of the present invention is sufficiently cured even at a low post-bake temperature.

  The pattern of the present invention formed as described above is useful as a photospacer or interlayer insulating film used in a liquid crystal display device or the like. In order to form the pattern of the present invention as an interlayer insulating film, a hole forming photomask may be used in the exposure process.

  In addition, the photosensitive resin composition of the present invention can be applied to a substrate (support), and then exposed to a whole surface and heat-cured, or in some cases only by heat-curing to form a film (non-pattern film) that covers the entire coated surface. it can. A non-patterned film (preferably a transparent film) is useful as an overcoat.

  The photosensitive resin composition of the present invention can be sufficiently cured even at a low heating temperature to form a pattern (particularly a photospacer or interlayer insulating film) or a coating film (overcoat) excellent in solvent resistance. Can contribute to energy saving. Moreover, if the photosensitive resin composition of this invention is used, a plastic substrate can be used and the weight reduction of a display apparatus can be achieved. Furthermore, the photosensitive resin composition of the present invention is also excellent in pattern resolution. Therefore, if the photosensitive resin composition of this invention is used, the display apparatus of the outstanding quality can be manufactured with a high yield.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples, and appropriate modifications are made within a range that can meet the above and the following purposes. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.
In Examples, “%” and “part” representing the content or amount used represent “% by mass” and “part by mass” unless otherwise specified.

Synthesis Example 1 <Production of Binder Resin (A)>
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.03 L / min to form a nitrogen atmosphere, 50.00 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 90 ° C. with stirring. . Next, 5.17 parts of methacrylic acid, 15.02 parts of methyl methacrylate, 31.23 parts of 2-hydroxyethyl methacrylate and 26.88 parts of N-cyclohexylmaleimide, 2,2′-azobis (isobutyronitrile) polymerization initiator A solution was prepared by dissolving 4.93 parts in 132.64 parts of propylene glycol monomethyl ether acetate. This solution was dropped into the flask kept at 90 ° C. with a dropping funnel over 1 hour. After completion of the dropwise addition of the solution, the solution was kept at 90 ° C. for 4 hours and then cooled to room temperature to obtain a copolymer (resin Aa) solution. Resin Aa had a weight average molecular weight (Mw) of 10,000 and a dispersity (Mw / Mn) of 2.08.

<Molecular weight measurement of resin Aa>
The weight average molecular weight (Mw), number average molecular weight (Mn) and dispersity (Mw / Mn) of the resin Aa were measured by the GPC method under the following conditions. Mw and Mn were calculated in terms of polystyrene.
Apparatus: K2479 (manufactured by Shimadzu Corporation)
Column: SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector: RI

Example 1 <Production of photosensitive resin compositions 1 to 3>
The binder resin (A), the photopolymerizable compound (B), the photopolymerization initiator (C) and the solvent (D) are mixed so that the composition shown in Table 1 is obtained, and photosensitive resin compositions 1 to 3 are obtained. Manufactured. The thermal acid generator (E) was added so that only the photosensitive resin composition 2 had the composition shown in Table 1.

<Pattern formation>
A 2-inch square glass substrate (Eagle 2000; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol, dried, and then used as a support. On the glass substrate, each of the photosensitive resin compositions 1 to 3 was applied by spin coating. In spin coating, the coating amount was adjusted so that the pattern film thickness after post-baking was 1.5 μm. The applied composition was then pre-baked at 100 ° C. for 3 minutes in a clean oven. After cooling, the distance between the glass substrate on which the coating film was formed and the quartz glass photomask was adjusted to 100 μm, and exposure was performed at an exposure amount of 100 mJ / cm ² (based on 365 nm) in an air atmosphere. TME-150RSK (manufactured by Topcon Corporation) was used as the exposure machine. The photomask has square light-transmitting portions each having a side of 15 μm, and the interval between the squares is 100 μm. After the exposure, the coating film was immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.05% potassium hydroxide at 25 ° C. for 30 seconds for development. The developed coating film was washed with water and then post-baked in an oven at 125 ° C. to 200 ° C. for 40 minutes. After standing to cool, the film thickness of the pattern was measured.
(Non-pattern film formation)
A cured coating film (non-pattern film) was formed on the substrate (film thickness 1.4 to 1.6 μm) in the same manner as the pattern formation except that no photomask was used.

<Characteristic evaluation of patterned or non-patterned film>
The solvent resistance, transmittance, resolution, and taper shape of the pattern or non-pattern film obtained as described above were measured. These results are shown in Table 2. In the solvent resistance test, when the coating film peeled off from the substrate, other evaluations were stopped.

(1) Solvent resistance The film thickness retention rate, transmittance retention rate, and adhesion remaining rate were evaluated as solvent resistance.
(1-1) Film thickness retention and transmittance retention The non-patterned film is immersed in N-methylpyrrolidone at 40 ° C. for 40 minutes, and the film thickness and transmittance are measured before and after that. Film thickness retention and transmittance retention were calculated. A cured coating film having both a film thickness retention ratio and a transmittance retention ratio of 97% or more and 103% or less has good solvent resistance.
Film thickness retention (%) = (film thickness after immersion (μm) / film thickness before immersion (μm)) × 100
Transmittance retention rate (%) = (transmittance after immersion (%) / transmittance before immersion (%)) × 100
(1-2) Adhesive residual rate 100 squares each having a side of 1 mm were produced using a commercially available cutter knife on the coating film after being immersed in 40 ° C N-methylpyrrolidone for 40 minutes. A commercially available cellophane tape was used to perform a peel test, and the number of squares remaining on the substrate without peeling (adhesion remaining rate (%)) was measured.

(2) Transmittance Using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), the film thickness (1.4 to 1.6 μm) of the non-pattern film was accurately measured. Subsequently, the transmittance (%) at 400 nm of this coating film was measured with a microspectrophotometer (OSP-SP200; manufactured by Olympus Corporation), and the transmittance was converted to a value when the film thickness was 1.5 μm. This converted value is shown in Table 2.

(3) Surface smoothness, resolution and taper shape The surface smoothness and resolution of the pattern obtained as described above were evaluated as follows.
The surface smoothness was evaluated by visually observing the pattern surface and evaluating that the gloss was good (◯) and the gloss was not good (x).
The resolution can be determined by observing the pattern using a scanning electron microscope (S-4000; manufactured by Hitachi, Ltd.) so that the base substrate can be seen according to the shape of the non-translucent portion of the photomask. Were evaluated as good (◯), and those that could not be patterned in this way were evaluated as defective (×).
The tapered shape (cross section) of the pattern was observed with the scanning electron microscope.

  As shown from the results in Table 2, the photosensitive resin compositions 1 and 2 (examples of the present invention) had a post-bake temperature of 150 to 200 ° C. compared to the photosensitive resin composition 3 (comparative example). In addition, a cured coating film (non-patterned film) excellent in solvent resistance can be formed. Moreover, the coating film obtained from the photosensitive resin compositions 1 and 2 is excellent also in transparency. From this, it can be seen that the pattern obtained from the photosensitive resin composition of the present invention is also excellent in solvent resistance and transparency. Furthermore, the pattern of the present invention has good surface smoothness and resolution.

  The photosensitive resin composition of the present invention can form a pattern or a cured coating film excellent in solvent resistance, permeability and surface smoothness. The photosensitive resin composition of the present invention has excellent resolution and is suitable as a photospacer forming material. The photosensitive resin composition of the present invention is used for forming an overcoat (transparent film), an interlayer insulating film, a protrusion for controlling liquid crystal alignment, and a coat layer for adjusting the thickness of a colored pattern of a display device. You can also.

Claims (8)

A photosensitive resin composition containing a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a solvent (D),
The binder resin (A) is a copolymer having at least an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (A1) and an unsaturated compound having a hydroxyl group (A2) as constituent monomers,
The photosensitive resin composition, wherein the photopolymerizable compound (B) is a compound having a functional group capable of reacting with a hydroxyl group and a photopolymerizable functional group.   The photosensitive resin composition according to claim 1, wherein the photopolymerizable compound (B) is a compound having a functional group capable of photoradical polymerization, and the photopolymerization initiator (C) is a photoradical polymerization initiator.   The photosensitive resin composition according to claim 2, wherein the photopolymerizable compound (B) is a formaldehyde condensate of melamines modified with at least one group selected from the group consisting of an acryloyl group and a methacryloyl group.   The photosensitive resin composition according to claim 3, wherein the melamine modified with at least one group selected from the group consisting of the acryloyl group and the methacryloyl group is further modified with an alkoxyl group.   Furthermore, the photosensitive resin composition in any one of Claims 1-4 containing a thermal acid generator (E).   The pattern manufactured from the photosensitive resin composition in any one of Claims 1-5. Applying the photosensitive resin composition according to any one of claims 1 to 5 on a support,
Removing the solvent from the composition to form a coating film,
The coating film is cured by exposure after masking,
After removing the uncured portion of the coating film with a developer,
The manufacturing method of the pattern characterized by heating the remaining coating film at the temperature of 150-200 degreeC.   A display device, wherein the photospacer or the interlayer insulating film is constituted by the pattern according to claim 6.