JP5205940B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition.

  A spacer is provided between the color filter substrate and the array substrate constituting the display device, such as a liquid crystal display device or a touch panel, in order to maintain a distance between the substrates. For this spacer, spherical particles such as glass beads and plastic beads are used.

  However, when such spherical particles are used, the spherical particles are randomly distributed on the glass substrate, so that the TFT element or the electrode is damaged, or if the spherical particles are present in the transmissive pixel portion, the incident light is incident. The contrast of the liquid crystal display element may be lowered due to light scattering. Therefore, it has been proposed to form spacers with a photosensitive resin composition instead of using spherical particles. According to this method, since the spacer can be formed at an arbitrary place, the above-mentioned problems can be solved.

  As such a photosensitive resin composition, a spacer forming composition containing an acrylic copolymer having a carboxyl group and a glycidyl ether group as a binder resin is known (Patent Document 1).

Japanese Patent Laid-Open No. 11-133600

  An object of the present invention is to provide a photosensitive resin composition capable of forming a fine line width pattern with a small increase in viscosity during storage.

  As a result of studying to find a photosensitive resin composition that can solve the above-mentioned problems, the present inventors have found that a photosensitive resin composition containing a certain binary copolymer has a small increase in viscosity during storage, It has been found that a pattern with a fine line width can be formed.

［式（Ｉ）および式（ＩＩ）中、Ｒは、それぞれ独立に、水素原子または水酸基で置換されていてもよい炭素数１〜４のアルキル基を表し、Ｘは、それぞれ独立に、単結合またはヘテロ原子を含んでもよい炭素数１〜６のアルキレン基を表す。］
［４］光重合開始剤（Ｃ）の含有量は、バインダー樹脂（Ａ）および光重合性化合物（Ｂ）の合計量に対して、０．１〜４０質量％である［１］〜［３］のいずれか記載の感光性樹脂組成物。
［５］［１］〜［４］のいずれか記載の感光性樹脂組成物を用いて形成されるパターン。
［６］［５］記載のパターンを含む液晶表示装置。 That is, the present invention provides the following [1] to [6].
[1] Binder resin (A), photopolymerizable compound (B), photopolymerization initiator (C) and solvent (D) are contained, and binder resin (A) is unsaturated carboxylic acid and / or unsaturated carboxylic acid. The photosensitive resin composition which is a copolymer of an acid anhydride (A1) and an aliphatic polycyclic epoxy compound (A2).
[2] The photosensitive resin composition according to [1], wherein the aliphatic polycyclic epoxy compound (A2) is a compound having an epoxy group on the ring of the aliphatic polycyclic compound and having an unsaturated bond. .
[3] At least one compound selected from the group consisting of the compound represented by formula (I) and the compound represented by formula (II) as the monomer (A2) having an aliphatic polycyclic epoxy group The photosensitive resin composition according to [1] or [2].

[In the formulas (I) and (II), each R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group, and each X independently represents a single bond. Alternatively, it represents a C 1-6 alkylene group which may contain a hetero atom. ]
[4] The content of the photopolymerization initiator (C) is 0.1 to 40% by mass with respect to the total amount of the binder resin (A) and the photopolymerizable compound (B) [1] to [3 ] The photosensitive resin composition in any one of these.
[5] A pattern formed using the photosensitive resin composition according to any one of [1] to [4].
[6] A liquid crystal display device comprising the pattern according to [5].

  According to the photosensitive resin composition of the present invention, the increase in viscosity during storage is small, and a pattern with a fine line width can be formed.

  Hereinafter, the present invention will be described in detail.

The photosensitive resin composition of the present invention contains a binder resin (A), a photopolymerizable compound (B) and a photopolymerization initiator (C), and optionally other additives (F) and a solvent (D). Is.
It is preferable that the photosensitive resin composition of the present invention is mainly used as a pattern forming material, and a binder resin (A), a photopolymerizable compound (B) and a photopolymerization initiator (C), and optionally other additions. The agent (F) is preferably dissolved or dispersed in the solvent (D).

  The binder resin (A) used in the photosensitive resin composition of the present invention is an unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (A1), a monomer having an aliphatic polycyclic epoxy group (A2). It is preferable that it has alkali solubility.

Specific examples of the unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (A1) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid;
Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
And anhydrides of the aforementioned unsaturated dicarboxylic acids;
Unsaturated mono [(meth) acryloyloxy of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Alkyl] esters;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxyl group in the same molecule, such as α- (hydroxymethyl) acrylic acid.

  Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from the viewpoints of copolymerization reactivity and high solubility in an aqueous alkali solution. These may be used alone or in combination of two or more.

The aliphatic polycyclic epoxy compound (A2) is a compound having an epoxy group on the ring of the aliphatic polycyclic compound, and the aliphatic polycyclic epoxy compound (A2) is an aliphatic polycyclic compound. A compound having an epoxy group on the ring of the formula compound and having an unsaturated bond is preferred.
Examples of the aliphatic polycyclic compound include dicyclopentane, tricyclodecane, norbornane, isonorbornane, bicyclooctane, bicyclononane, bicycloundecane, tricycloundecane, bicyclododecane, tricyclododecane, and the like. Is preferably a compound of 8 to 12, more preferably at least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II).

In the formula (I) and the formula (II), each R independently represents a C 1-4 alkyl group which may be substituted with a hydrogen atom or a hydroxyl group.
X represents each independently a C1-C6 alkylene group which may contain a single bond or a hetero atom.

R is specifically a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group;
Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1-hydroxy-isopropyl group, And hydroxyl group-containing alkyl groups such as 2-hydroxy-isopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group and 4-hydroxy-n-butyl group. It is done. Among these, Preferably a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group is mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

X is specifically a single bond; an alkylene group such as a methylene group, an ethylene group or a propylene group;
Examples thereof include heteroatom-containing alkylene groups such as oxymethylene group, oxyethylene group, oxypropylene group, thiomethylene group, thioethylene group, thiopropylene group, aminomethylene group, aminoethylene group, and aminopropylene group. Of these, a single bond, a methylene group, an ethylene group, an oxymethylene group, and an oxyethylene group are preferable, and a single bond and an oxyethylene group are more preferable.

  Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15), preferably the formula (I-1) and the formula (I-3). , Formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15), and more preferably formula (I-1), formula (I-7), Formula (I-9), and Formula (I-15) are mentioned.

  Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15), preferably the formula (II-1) and the formula (II-3). , Formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15), more preferably formula (II-1), (II-7), Formula (II-9), and Formula (II-15) are mentioned.

  At least one compound selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II) can be used alone and can be mixed in an arbitrary ratio. In the case of mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, more preferably 20:80 to Formula (I) :( II). 80:20.

  The binder resin (A) used in the present invention is a copolymer of (A1) and (A2).

The binder resin (A) used in the present invention is a copolymer obtained by copolymerizing (A1) and (A2), and the ratio of the constituent components derived from each constitutes the copolymer. It is preferable that it is in the following range in terms of mole fraction with respect to the total number of moles of constituent components to be formed.
Structural units derived from (A1); 5-75 mol%
Structural unit derived from (A2); 25-95 mol%
Moreover, it is more preferable in the ratio of the said structural component being the following ranges.
Structural units derived from (A1); 10-70 mol%
Structural unit derived from (A2); 30 to 90 mol%

  When the ratio of the constituent components is within the above range, the storage stability of the photosensitive resin composition, the resolution of the pattern obtained from the composition, developability, solvent resistance, heat resistance and mechanical strength are increased. There is a tendency to improve.

The binder resin (A) is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972). And it can manufacture with reference to the cited reference described in the said literature.
Specifically, a predetermined amount of units (A1) and (A2) constituting the copolymer, a polymerization initiator and a solvent are charged into a reaction vessel, and oxygen is replaced with nitrogen, so that in the absence of oxygen. The polymer is obtained by stirring, heating, and heat-retaining. In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and took out as solid (powder) by methods, such as reprecipitation. Things may be used.

The weight average molecular weight in terms of polystyrene of the binder resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the binder resin (A) is in the above range, the coating property tends to be good, the film is less likely to be lost during development, and the non-pixel part is easily removed during development. This is preferable because the resolution tends to be good.
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. The molecular weight distribution in the above range is preferable because the developability tends to be good and the resolution is excellent.
The content of the binder resin (A) used in the photosensitive resin composition of the present invention is a solid content in the photosensitive resin composition (refers to solid components at 25 ° C. among the components in the composition). The mass fraction is preferably 5 to 90 mass%, more preferably 10 to 70 mass%. When the content of the binder resin (A) is in the above range, the solubility in the developer is sufficient, and a development residue is hardly generated on the non-pixel portion of the substrate. This is preferable because the film loss is less likely to occur, and the non-pixel portion tends to be easily removed.

Examples of the photopolymerizable compound (B) contained in the photosensitive resin composition of the present invention include monofunctional monomers, bifunctional monomers, and other trifunctional or more polyfunctional monomers.
Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone and the like.
Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and bisphenol A. Examples thereof include bis (acryloyloxyethyl) ether and 3-methylpentanediol di (meth) acrylate.
Specific examples of other trifunctional or higher polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, one or more caprolactone modified in the molecule In addition, a trifunctional or higher polyfunctional monomer, a trifunctional or higher polyfunctional monomer modified with 3 or more alkylene oxides in the molecule, and the like can be given.

In this specification, caprolactone modification means that a caprolactone ring-opening polymer or a ring-opening polymer is introduced between the alcohol-derived site of the (meth) acrylate compound and the (meth) acryloyloxy group. means.
The alkylene oxide modification is an alkylene glycol or a dehydrated condensate thereof and a ring-opened product of an alkylene oxide or a ring-opening weight between an alcohol-derived site of the (meth) acrylate compound and a (meth) acryloyloxy group. It means that coalescence is introduced.

Examples of the tri- or higher functional monomer modified with one or more caprolactone in the molecule include KAYARAD DPCA-20, KAYARAD DPCA-40, KAYARAD DPCA-60, and KAYARAD DPCA-120 (all Nippon Kayaku Co., Ltd.) ) And NK ester AD-TMP-4CL (manufactured by Shin-Nakamura Chemical Co., Ltd.).
In the polyfunctional monomer having 3 or more functional groups modified with 3 or more alkylene oxides in the molecule, preferable alkylene oxides include ethylene oxide and propylene oxide.

Among these, a polyfunctional monomer having two or more functions is preferably used. These photopolymerizable compounds (B) can be used alone or in combination of two or more.
Content of a photopolymerizable compound (B) is a mass fraction with respect to the total amount of binder resin (A) and a photopolymerizable compound (B), Preferably it is 1-90 mass%, More preferably, it is 10-80. % By mass. It is preferable that the content of the photopolymerizable compound (B) is in the above range because the strength, smoothness, and reliability of the pixel portion tend to be good.

  As the photopolymerization initiator (C) contained in the photosensitive resin composition of the present invention, acetophenone compounds, biimidazole compounds, oxime compounds, triazine compounds, and acylphosphine oxide compounds are preferably used. When the photopolymerization initiator auxiliary agent (C-1) is used in combination with these photopolymerization initiators (C), the resulting photosensitive resin composition has a higher sensitivity. This is preferable because the productivity of the pattern is improved.

  Examples of the acetophenone compound 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-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methylbenzyl) -2- Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2 Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl) -2- Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,3-dimethylbenzyl)- 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-chlorobenzyl) ) -2-Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromobenzyl) -2-dimethylamino-1- 4-morpholinophenyl) -butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethylamino-1- ( 4-morpholinophenyl) -butanone, 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-bromobenzyl) -2-dimethylamino-1- ( 4-morpholinophenyl) -butanone, 2- (2-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- ( 4-morpholinophenyl) -butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -buta Non, 2- (2-methyl-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1 -(4-morpholinophenyl) -butanone, 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1- [ 4- (1-methylvinyl) phenyl] propan-1-one oligomer and the like.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 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′-tetraphenylbiimidazole, 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 ( bird (Lucoxyphenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Imidazole compounds (see, for example, JP-A-7-10913). Preferably, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5 5'-tetraphenylbiimidazole is mentioned.

Examples of the oxime compound include O-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, a compound represented by formula (3), a compound represented by formula (4), and the like. .

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4 -Methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2 , 4-Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4- Diethylamino-2-methylphenol Nyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, and the like. .

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Moreover, as long as the effects of the present invention are not impaired, a photopolymerization initiator or the like usually used in this field can be further used together. Examples of the photopolymerization initiator include benzoin compounds and benzophenones. Compounds, thioxanthone compounds, anthracene compounds, and the like.

  More specifically, the following compounds can be mentioned, and these may be used alone or in combination of two or more.

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

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

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

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

  Other examples of the photopolymerization initiator include 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compounds. .

Further, as a photopolymerization initiator having a group capable of causing chain transfer, a photopolymerization initiator described in JP-T-2002-544205 can be used.
As a photoinitiator which has the group which can raise | generate the said chain transfer, the photoinitiator of following formula (5)-(10) is mentioned, for example.

また、光および／または熱カチオン重合開始剤を使用することができる。
光および／または熱カチオン重合開始剤は、オニウムカチオンとルイス酸由来のアニオンとから構成されているものも使用することができる。

In addition, light and / or thermal cationic polymerization initiators can be used.
As the light and / or thermal cationic polymerization initiator, those composed of an onium cation and an anion derived from a Lewis acid can also be used.

  Specific examples of the onium cation include diphenyliodonium, bis (p-tolyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl) iodonium, bis (P-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, phenyl (p-octadecyloxyphenyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, triphenylsulfonium, tris (p- Tolyl) sulfonium, tris (p-isopropylphenyl) sulfonium, tris (2,6-dimethylphenyl) sulfonium, tris (p-tert-butylphenyl) sulfonium, tris (p-si Nophenyl) sulfonium, tris (p-chlorophenyl) sulfonium, dimethyl (methoxy) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxy) sulfonium, dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecanoxy) sulfonium, Dimethyl (isopropoxy) sulfonium, dimethyl (tert-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluoromethoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromo Propoxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, dimethyl (8-nitroo) Yloxy) sulfonium, dimethyl (18-trifluoromethyl octadecanoic oxy) sulfonium, dimethyl (2-hydroxy-isopropoxyphenyl) sulfonium or dimethyl (tris (trichloromethyl) methyl) and the like sulfonium.

  Preferred onium cations include bis (p-tolyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium or tris (p-tert-butylphenyl). ) Sulfonium and the like.

Specific examples of the Lewis acid-derived anion include hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, and tetrakis (pentafluorophenyl) borate. Preferred anions derived from Lewis acids include hexafluoroantimonate or tetrakis (pentafluorophenyl) borate.
The onium cation and Lewis acid-derived anion can be arbitrarily combined.

Specific examples of the cationic polymerization initiator include diphenyliodonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-octylphenyl) iodonium hexa Fluorophosphate, bis (p-octadecylphenyl) iodonium hexafluorophosphate, bis (p-octyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodonium hexafluorophosphate, phenyl (p-octadecyloxyphenyl) iodonium Hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophos , Methyl naphthyl iodonium hexafluorophosphate, ethyl naphthyl iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tolyl) sulfonium hexafluorophosphate, tris (p-isopropylphenyl) sulfonium hexafluorophosphate, tris (2, 6-dimethylphenyl) sulfonium hexafluorophosphate, tris (p-tert-butylphenyl) sulfonium hexafluorophosphate, tris (p-cyanophenyl) sulfonium hexafluorophosphate, tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthylsulfonium Hexafluorophosphate, diethylnaphthyls Honium hexafluorophosphate, dimethyl (methoxy) sulfonium hexafluorophosphate, dimethyl (ethoxy) sulfonium hexafluorophosphate, dimethyl (propoxy) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluoro Phosphate, dimethyl (octadecanoxy) sulfonium hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (tert-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclopentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium Hexafluorophosphate, dimethyl (fluoromethoxy) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexafluorophosphate, dimethyl (3-bromopropoxy) sulfonium hexafluorophosphate, dimethyl (4-cyanobutoxy) sulfonium hexafluorophosphate, Dimethyl (8-nitrooctyloxy) sulfonium hexafluorophosphate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluorophosphate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluorophosphate, dimethyl (tris (trichloromethyl) methyl) Sulfonium hexafluorophosphate;
Diphenyliodonium hexafluoroarsenate, bis (p-tolyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate, bis (p-octylphenyl) iodonium hexafluoroarsenate, bis (p -Octadecylphenyl) iodonium hexafluoroarsenate, bis (p-octyloxyphenyl) iodonium hexafluoroarsenate, bis (p-octadecyloxyphenyl) iodonium hexafluoroarsenate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroarsenate Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate, methylnaphthyl iodonium Oxafluoroarsenate, ethyl naphthyl iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (p-tolyl) sulfonium hexafluoroarsenate, tris (p-isopropylphenyl) sulfonium hexafluoroarsenate, tris (2, 6-dimethylphenyl) sulfonium hexafluoroarsenate, tris (p-tert-butylphenyl) sulfonium hexafluoroarsenate, tris (p-cyanophenyl) sulfonium hexafluoroarsenate, tris (p-chlorophenyl) sulfonium hexafluoroarsenate , Dimethylnaphthylsulfonium hexafluoroarsenate, diethylnaphthylsulfonium hexafluoroarsenate Dimethyl (methoxy) sulfonium hexafluoroarsenate, dimethyl (ethoxy) sulfonium hexafluoroarsenate, dimethyl (propoxy) sulfonium hexafluoroarsenate, dimethyl (butoxy) sulfonium hexafluoroarsenate, dimethyl (octyloxy) sulfonium hexafluoroarsenate Dimethyl (octadecanoxy) sulfonium hexafluoroarsenate, dimethyl (isopropoxy) sulfonium hexafluoroarsenate, dimethyl (tert-butoxy) sulfonium hexafluoroarsenate, dimethyl (cyclopentyloxy) sulfonium hexafluoroarsenate, dimethyl (cyclohexyloxy) ) Sulfonium hexafluoroarsenate, dimethyl (Fluoromethoxy) sulfonium hexafluoroarsenate, dimethyl (2-chloroethoxy) sulfonium hexafluoroarsenate, dimethyl (3-bromopropoxy) sulfonium hexafluoroarsenate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroarsenate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroarsenate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroarsenate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroarsenate, dimethyl (tris (trichloromethyl) Methyl) sulfonium hexafluoroarsenate;
Diphenyliodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, bis (p-octylphenyl) iodonium hexafluoroantimonate, bis (p -Octadecylphenyl) iodonium hexafluoroantimonate, bis (p-octyloxyphenyl) iodonium hexafluoroantimonate, bis (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroantimonate Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, methyl naphthalate Tyl iodonium hexafluoroantimonate, ethyl naphthyl iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tolyl) sulfonium hexafluoroantimonate, tris (p-isopropylphenyl) sulfonium hexafluoroantimonate, tris ( 2,6-dimethylphenyl) sulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, tris (p-cyanophenyl) sulfonium hexafluoroantimonate, tris (p-chlorophenyl) sulfonium hexafluoro Antimonate, dimethyl naphthylsulfonium hexafluoroantimonate, diethyl naphthyl Rufonium hexafluoroantimonate, dimethyl (methoxy) sulfonium hexafluoroantimonate, dimethyl (ethoxy) sulfonium hexafluoroantimonate, dimethyl (propoxy) sulfonium hexafluoroantimonate, dimethyl (butoxy) sulfonium hexafluoroantimonate, dimethyl (octyl) Oxy) sulfonium hexafluoroantimonate, dimethyl (octadecanoxy) sulfonium hexafluoroantimonate, dimethyl (isopropoxy) sulfonium hexafluoroantimonate, dimethyl (tert-butoxy) sulfonium hexafluoroantimonate, dimethyl (cyclopentyloxy) sulfonium hexafluoro Antimonate, dimethyl (cyclohexyl) Ruoxy) sulfonium hexafluoroantimonate, dimethyl (fluoromethoxy) sulfonium hexafluoroantimonate, dimethyl (2-chloroethoxy) sulfonium hexafluoroantimonate, dimethyl (3-bromopropoxy) sulfonium hexafluoroantimonate, dimethyl (4-cyano Butoxy) sulfonium hexafluoroantimonate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroantimonate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroantimonate , Dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoro Nchimoneto;
Diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (p-tolyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (p-octylphenyl) Iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecyloxyphenyl) Iodonium tetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodonium tetrakis Pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, methylnaphthyliodonium tetrakis (pentafluorophenyl) borate, ethylnaphthyliodonium tetrakis (pentafluorophenyl) borate, triphenyl Sulfonium tetrakis (pentafluorophenyl) borate, tris (p-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-isopropylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (2,6-dimethylphenyl) sulfonium Tetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfonium teto Kiss (pentafluorophenyl) borate, tris (p-cyanophenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-chlorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, Diethyl naphthylsulfonium tetrakis (pentafluorophenyl) borate, dimethyl (methoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (ethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (propoxy) sulfonium tetrakis (pentafluorophenyl) borate, Dimethyl (butoxy) sulfonium tetrakis (pentafluorophenyl) bo Dimethyl (octyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (octadecanoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (isopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tert-butoxy) Sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclopentyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclohexyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (fluoromethoxy) sulfonium tetrakis (pentafluorophenyl) borate , Dimethyl (2-chloroethoxy) sulfonium tetra (Pentafluorophenyl) borate, dimethyl (3-bromopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (4-cyanobutoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (8-nitrooctyloxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (2-hydroxyisopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tris (trichloromethyl) Methyl) sulfonium tetrakis (pentafluorophenyl) borate and the like, preferably bis (p-tolyl) Donium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tert- Butylphenyl) sulfonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroarsenate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarcete Nate, triphenylsulfonium hexafluoroarsenate, tris (pt-butylphenyl) sulfonium hexafluoroarsenate, Bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate Nates, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) Borate, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (pt rt-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate and the like, more preferably bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, Bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) ) Borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert-butyl) Phenyl) iodonium tetrakis (pentafluorophenyl) borate, triphenyl sulfonium tetrakis (pentafluorophenyl) borate, or tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate.

In addition, the photopolymerization initiator can be used in combination with the photopolymerization initiation assistant (C-1), and the photopolymerization initiation assistant can be used in a plurality of combinations.
Examples of the photopolymerization initiation assistant include amine compounds, carboxylic acid compounds, polyfunctional thiol compounds, and compounds represented by the formula (III). As said amine compound, an aromatic amine compound is preferable. As the photopolymerization initiator, amine compounds, polyfunctional thiols, and compounds represented by the formula (III) are preferable.

Examples of the photopolymerization initiation assistant (C-1) include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4 Aromatic amine compounds such as 4,4′-bis (diethylamino) benzophenone;
Phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, Carboxylic acid compounds such as aromatic heteroacetic acids such as naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid;
Hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropio , Trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, pentaerythritol tetrakis (3-mercapto Butyrate), 1,4-bis (3-mercaptobutyryloxy) butane and other polyfunctional thiol compounds;
Examples thereof include compounds represented by the following formula (III).

In formula (III), the dotted line represented by X represents an aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom.
Y represents an oxygen atom or a sulfur atom.
R ¹ represents an alkyl group having 1 to 6 carbon atoms.
R ² represents an alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom or an aryl group which may be substituted with a halogen atom.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the aromatic ring having 6 to 12 carbon atoms include a benzene ring and a naphthalene ring.

  Examples of the aromatic ring having 6 to 12 carbon atoms that may be substituted with a halogen atom include a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, a pentylbenzene ring, and a hexylbenzene ring. Cyclohexylbenzene ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene ring, and the like.

  Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2-methyl-n-propyl group, tert- Butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2- Examples include dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group and the like.

  Examples of the alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2- Methyl-n-propyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl- n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group, 1-chloro-n-butyl group, 2-chloro-n- A butyl group, 3-chloro-n-butyl group, etc. are mentioned.

  The aryl group which may be substituted with a halogen atom includes a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorobromophenyl group, a biphenyl group, a chlorobiphenyl group, a dichlorobiphenyl group, and a bromophenyl group. , Dibromophenyl group, naphthyl group, chloronaphthyl group, dichloronaphthyl group, bromonaphthyl group, dibromonaphthyl group and the like.

As the compound represented by the formula (III), specifically,
2-benzoylmethylene-3-methyl-naphtho [2,1-d] thiazoline,
2-benzoylmethylene-3-methyl-naphtho [1,2-d] thiazoline,
2-benzoylmethylene-3-methyl-naphtho [2,3-d] thiazoline,
2- (2-naphthoylmethylene) -3-methylbenzothiazoline,
2- (1-naphthoylmethylene) -3-methylbenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-5-phenylbenzothiazoline,
2- (1-naphthoylmethylene) -3-methyl-5-phenylbenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-5-fluorobenzothiazoline,
2- (1-naphthoylmethylene) -3-methyl-5-fluorobenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-5-chlorobenzothiazoline,
2- (1-naphthoylmethylene) -3-methyl-5-chlorobenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-5-bromobenzothiazoline,
2- (1-naphthoylmethylene) -3-methyl-5-bromobenzothiazoline,
2- (4-biphenoylmethylene) -3-methylbenzothiazoline,
2- (4-biphenoylmethylene) -3-methyl-5-phenylbenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline,
2- (2-naphthoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline,
2- (4-biphenoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline,
2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline,
2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline,
2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline,
2-benzoylmethylene-3-methyl-naphtho [2,1-d] oxazoline,
2-benzoylmethylene-3-methyl-naphtho [1,2-d] oxazoline,
2-benzoylmethylene-3-methyl-naphtho [2,3-d] oxazoline,
2- (2-naphthoylmethylene) -3-methylbenzoxazoline,
2- (1-naphthoylmethylene) -3-methylbenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-5-phenylbenzoxazoline,
2- (1-naphthoylmethylene) -3-methyl-5-phenylbenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-5-fluorobenzoxazoline,
2- (1-naphthoylmethylene) -3-methyl-5-fluorobenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-5-chlorobenzoxazoline,
2- (1-naphthoylmethylene) -3-methyl-5-chlorobenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-5-bromobenzoxazoline,
2- (1-naphthoylmethylene) -3-methyl-5-bromobenzoxazoline,
2- (4-biphenoylmethylene) -3-methylbenzoxazoline,
2- (4-biphenoylmethylene) -3-methyl-5-phenylbenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline,
2- (2-naphthoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline,
2- (4-biphenoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline,
2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline,
2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline,
2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline,
Etc.

Among them, 2- (2-naphthoylmethylene) -3-methylbenzothiazoline represented by the formula (III-1), 2-benzoylmethylene-3-methyl-naphtho represented by the formula (III-2) [1,2 -D] thiazoline and 2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline represented by the formula (III-3) are preferred.

Content of a photoinitiator (C) is a mass fraction with respect to the total amount of binder resin (A) and a photopolymerizable compound (B), Preferably it is 0.1-40 mass%, More preferably, it is 1 -30 mass%.
The content of the photopolymerization initiation assistant (C-1) is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass, based on the same standard as described above.
When the total amount of the photopolymerization initiator (C) is in the above range, the photosensitive resin composition becomes highly sensitive, and the strength of the pixel portion formed using the photosensitive resin composition, This is preferable because smoothness on the surface tends to be good. In addition to the above, when the amount of the photopolymerization initiation assistant (C-1) is in the above range, the sensitivity of the obtained photosensitive resin composition is further increased, and the photosensitive resin composition is formed using the photosensitive resin composition. This is preferable because the productivity of the patterned substrate tends to be improved.

The photosensitive resin composition of the present invention contains a solvent (D). Examples of the solvent (D) include various organic solvents used in the field of photosensitive resin compositions, and specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl. Ethylene glycol monoalkyl ethers such as ether and ethylene glycol monobutyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate;
Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether, propylene glycol ethyl propyl ether, propylene glycol methyl ether propionate, propylene glycol ethyl ether Propylene glycol alkyl ether propionates such as propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate;
Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol, butoxybutyl alcohol;
Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, butoxybutyl acetate;
Butanediol monoalkyl ether propionates such as methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, butoxybutyl propionate;
Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether;
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;
Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxyethyl acetate, hydroxy Butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3-methylbutane Methyl acetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxyacetate, propoxy Ethyl acetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2- Butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxy Propyl propionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3- Methyl toxipropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxy Esters such as butyl propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate;
Cyclic ethers such as tetrahydrofuran and pyran;
and cyclic esters such as γ-butyrolactone.

Among the above solvents, from the viewpoints of coating properties and drying properties, an organic solvent having a boiling point of 100 ° C. to 200 ° C. is preferable among the above solvents, and more preferably alkylene glycol alkyl ether acetates, ketones, butane. Examples include diol alkyl ether acetates, butanediol monoalkyl ethers, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Examples include cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate.
These solvents (D) may be used alone or in combination of two or more.

  Content of the solvent (D) in the photosensitive resin composition of this invention is a mass fraction with respect to the photosensitive resin composition, Preferably it is 60-90 mass%, More preferably, it is 70-85 mass%. When the content of the solvent (D) is within the above range, when applied by a spin coater, slit & spin coater, slit coater (sometimes called a die coater or curtain flow coater), an ink jet or the like. It is preferable because the coating property is expected to be good.

Addition of a filler, other polymer compound, a leveling agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation material, a chain transfer agent, etc., to the photosensitive resin composition of the present invention as necessary. Agent (F) can also be used in combination.
Specific examples of the filler include glass, silica, and alumina.

  Specific examples of other polymer compounds include curable 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.

  As the leveling agent, a commercially available surfactant can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, and amphoteric surfactants. Two or more kinds may be used in combination. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFuck (manufactured by Dainippon Ink & Chemicals, Inc.) ), FLORARD (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by GENEKA Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS), PB821 (manufactured by Ajinomoto Co., Inc.) ) And the like.

  As the adhesion promoter, silane compounds are preferable, and specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyl. Dimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

  Specific examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy- 3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy]- 2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 3,9-bis [2- {3- (3-tert-butyl-4 -Hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2′-methyle Bis (6-tert-butyl-4-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (2-tert-butyl-5-methylphenol) ), 2,2′-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′- Thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine -2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', ''-(Mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di -Tert-butyl-4-methylphenol and the like.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.
Specific examples of the aggregation inhibitor include sodium polyacrylate.
Examples of the chain transfer agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

  For example, the photosensitive resin composition can be applied onto a substrate as described below, and can be photocured and developed to form a pattern. First, this composition is applied onto a substrate (usually glass) or a layer made of a solid content of a previously formed photosensitive resin composition, and prebaked from the applied photosensitive resin composition layer to obtain a solvent or the like. The volatile components are removed to obtain a smooth coating film. The thickness of the coating film at this time is usually about 1 to 6 μm. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so that the entire exposed portion is uniformly irradiated with parallel light rays and the mask and the substrate are accurately aligned. Thereafter, the cured coating film is brought into contact with an alkaline aqueous solution to dissolve the non-exposed portion and developed, whereby the intended pattern shape is obtained. The developing method may be any of a liquid piling method, a dipping method, a spray method, and the like. Further, the substrate may be tilted at an arbitrary angle during development.

Examples of the coating method include spin coating, casting coating, roll coating, slit and spin coating, and slit coating. After application, the photosensitive resin composition layer is formed by volatilizing volatile components such as a solvent by heating after drying (pre-baking) or drying under reduced pressure. Here, the temperature of heating is 70-200 degreeC normally, Preferably it is 80-130 degreeC. The photosensitive resin composition layer contains almost no volatile component. Moreover, the thickness of the said photosensitive resin composition layer is about 1.5-8 micrometers normally.
The developer used for development after patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant.

  The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, Examples thereof include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia.

  Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Etc. These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The surfactant in the alkali developer may be any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.
Specific examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Examples thereof include oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.

Specific examples of anionic surfactants include higher alcohol sulfate salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.
Specific examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride.
These surfactants may be used alone or in combination of two or more.

  The concentration of the surfactant in the alkali developer is preferably in the range of 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and still more preferably 0.1 to 5% by mass.

  After development, it is washed with water, and if necessary, post-baking at 150 to 230 ° C. for 10 to 60 minutes can also be performed.

  By using the photosensitive resin composition of the present invention, a pattern can be formed on the substrate or the color filter substrate through the above steps. This pattern is useful as a photospacer used in a liquid crystal display device. Moreover, if a photomask for hole formation is used in patterning exposure to a dry coating film, a hole can be formed and it is useful as an interlayer insulation film. Furthermore, when exposing to a dry coating film, a transparent film can be formed only by full exposure and heat curing, or heat curing without using a photomask, and this transparent film is useful as an overcoat, It can also be used for a touch panel.

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

  The photosensitive resin composition of the present invention has a small viscosity change during storage, can be resolved to a fine pattern, and can form a pattern or a coating film excellent in solvent resistance and heat resistance.

  The photosensitive resin composition of the present invention is, for example, a transparent film constituting a part of a color filter such as an overcoat, a photo spacer, an insulating film, a liquid crystal alignment control protrusion, and a coat layer for adjusting the thickness of a colored pattern. It is used suitably as a material for forming.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, it cannot be overemphasized that this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

Synthesis example 1
In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added. And heated to 70 ° C. with stirring. Next, 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) (Mix ratio of the compound to be prepared is a 50:50 mixture.) A solution is prepared by dissolving 240 parts by mass in 140 parts by mass of 3-methoxybutyl acetate, and the resulting solution is added over 4 hours using a dropping funnel. And dropped in a flask kept at 70 ° C. On the other hand, a solution in which 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of 3-methoxybutyl acetate was added to a flask over another 4 hours using another dropping funnel. It was dripped in. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature, so that the solid content was 32.6% by mass and the acid value was 110 mg-KOH / g (solid content conversion). A solution of the polymer (resin Aa) was obtained. The obtained resin Aa had a weight average molecular weight Mw of 13,400 and a dispersity of 2.50.

Synthesis example 2
In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added. And heated to 70 ° C. with stirring. Subsequently, 55 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) A mixture of the compound to be prepared in a molar ratio of 50:50.) A solution was prepared by dissolving 175 parts by mass and 70 parts by mass of N-cyclohexylmaleimide in 140 parts by mass of 3-methoxybutyl acetate. It dropped in the flask kept at 70 degreeC using the dropping funnel over 4 hours. On the other hand, a solution in which 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of 3-methoxybutyl acetate was added to a flask over another 4 hours using another dropping funnel. It was dripped in. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature, and the copolymer (resin Ab) having a solid content of 32.6% by mass and an acid value of 105 mg-KOH / g ) Was obtained. The obtained resin Ab had a weight average molecular weight Mw of 13,600 and a dispersity of 2.54.

Synthesis example 3
As in Synthesis Example 1 of JP-A-11-133600, in a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile), 200 parts by mass of diethylene glycol dimethyl ether Was charged. Subsequently, after 30 parts by mass of styrene, 20 parts by mass of methacrylic acid, and 50 parts by mass of glycidyl methacrylate were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the resin Ac. The obtained resin Ac had a polystyrene equivalent weight average molecular weight of 24,000.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the binder polymer were measured using the GPC method under the following conditions.
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
The ratio of the weight average molecular weight and the number average molecular weight obtained in the above-mentioned manner as polystyrene was defined as the dispersity (Mw / Mn).

Example 1
169 parts of resin solution (A) containing resin Aa obtained in Synthesis Example 1 (55 parts in terms of solid content), 45 parts of dipentaerythritol hexaacrylate (B), 2,2′-bis (2-chlorophenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole (C) 4 parts, 2- (2-naphthoylmethylene) -3-methylbenzothiazoline (C-1) 0.5 part, pentaerythritol tetrakisthiopropio 3 parts of Nate (C-1), IRGANOX 3114 (manufactured by Ciba Specialty Chemicals) (F) 0.8 part, 58 parts of propylene glycol monomethyl ether acetate, 42 parts of 3-ethoxyethyl propionate, 3-methoxy 1-butanol 3 Part and 3-methoxybutyl acetate 2 parts were mixed to obtain photosensitive resin composition 1.

<Pattern formation>
A 2-inch square glass substrate (Eagle 2000; manufactured by Corning) was sequentially washed with a neutral detergent, water, and alcohol, and then dried. On this glass substrate, the photosensitive resin composition 1 is exposed at an exposure amount (405 nm) of 100 mJ / cm ² and spin-coated so that the film thickness becomes 3.0 μm when developed, washed with water, and post-baked. And then pre-baked in a clean oven at 90 ° C. for 3 minutes. After cooling, the distance between the substrate coated with the photosensitive resin composition and the photomask made of quartz glass was set to 10 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Corporation) was used, and 100 mJ / It was irradiated with light at an exposure amount of cm ² (405 nm reference). In addition, the irradiation to the polymerizable resin composition at this time was performed by passing the light emitted from the ultra-high pressure mercury lamp through an optical filter (LU0400; manufactured by Asahi Spectrometer Co., Ltd.) and cutting light of 400 nm or less.

  As the photomask, a photomask having the following pattern formed on the same plane was used.

-It has a square light transmission part (pattern) whose one side is 10 μm, and the interval between the squares is 100 μm.
-It has a square translucent part (pattern) whose one side is 15 μm, and the interval between the squares is 100 μm.

  After light irradiation, the substrate was developed by immersing the coating film in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 100 seconds, washed with water, Post-baking was performed in an oven at 220 ° C. for 20 minutes. After cooling, the thickness of the cured film obtained was 3.0 μm as measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

<Storage stability>
The viscosity of the photosensitive resin composition 1 obtained above was measured. Then, the photosensitive resin composition 1 was sealed in a light shielding container, and the container was stored in a thermostatic bath at 23 ° C. for 2 weeks.
The viscosity of the photosensitive resin composition 1 after storage was measured. The viscosity change obtained based on the following formula was 100%.

[Viscosity of photosensitive resin composition after storage at 23 ° C. for 2 weeks]
Viscosity change = --------------------- x100 (%)
[Viscosity of photosensitive resin composition before storage]

The smaller the change in viscosity, the better, for example, in the range of 100 to 103%. The viscosity was measured as follows.
The viscosity was measured at 23 ° C. using a viscometer (VISCOMETER TV-30; manufactured by Toki Sangyo Co., Ltd.).

<Line width, cross-sectional shape>
The obtained cured film was observed and measured for line width and shape (cross section) using a scanning electron microscope (S-4000; manufactured by Hitachi, Ltd.).
The line width measured in the pattern corresponding to the 10 μm pattern on the photomask was 10.0 μm.
The cross-sectional shape was a forward taper with the pattern angle with respect to the substrate being less than 90 degrees. In addition, the case where the angle of the pattern with respect to a board | substrate was 90 degree | times or more was judged as reverse taper.
A forward taper is preferred because the ITO wiring is less likely to break during the formation of the liquid crystal display device.

<Mechanical properties> (Total displacement and recovery rate)
The obtained cured film was measured for its total displacement (μm) and elastic displacement (μm) using a dynamic ultra-micro hardness meter (DUH-W201; manufactured by Shimadzu Corporation). From these figures, the recovery rate (%) was obtained. The total displacement was 0.57 μm, and the recovery rate was 92.9%.

-Measurement conditions-
Test mode; load-unload test test force; 5 gf [SI unit converted value; 49.0 mN]
Load speed: 0.45 gf / sec [SI unit converted value; 4.41 mN / sec]
Holding time: 5 sec
Indenter: truncated cone indenter (diameter 50 μm)
Recovery rate (%); [elastic displacement (μm)] / [total displacement (μm)] × 100

<Solvent resistance>
In the exposure step, the same operation was performed except that a photomask was not used, a coating film was prepared, and the film thickness was measured. The obtained coating film was immersed for 40 minutes in 40 degreeC N-methylpyrrolidone, and the film thickness after immersion was measured. The change in film thickness was determined according to the following formula, and this was used as an index of solvent resistance. The value obtained was 103.9%.

  Change in film thickness (%); [film thickness after immersion (μm)] / [film thickness before immersion (μm)] × 100

  The film thickness change is preferably 104% or less.

<Heat resistance>
In the exposure step, the same operation was performed except that no photomask was used, and a coating film was produced. The prepared coating film was allowed to stand in a clean oven at 240 ° C. for 1 hour, the film thickness before and after heating was measured, and the change in film thickness was determined according to the following formula, which was used as an index of heat resistance. The value obtained was 98.2%.

  Change in film thickness (%); [film thickness after heating (μm)] / [film thickness before heating (μm)] × 100

  The film thickness change is preferably 97% or more.

Example 2
The photosensitive resin composition 2 was obtained so that it might become a composition shown in Table 1, and the evaluation was performed like Example 1. FIG. The results are shown in Table 2.

Example 3
The photosensitive resin composition 3 was obtained so that it might become a composition shown in Table 1, and it evaluated in the same manner as Example 1. The results are shown in Table 2.

Comparative Example 1
The photosensitive resin composition 4 was obtained so that it might become a composition shown in Table 1, and it evaluated in the same manner as Example 1. The results are shown in Table 2.

Comparative Example 2
The photosensitive resin composition 5 was obtained so that it might become a composition shown in Table 1. When the storage stability was measured in the same manner as in Example 1, the viscosity was increased and the evaluation was stopped.

Example 4
The photosensitive resin composition 6 was obtained so that it might become a composition shown in Table 3.
<Pattern formation>
A 2-inch square glass substrate (Eagle 2000; manufactured by Corning) was sequentially washed with a neutral detergent, water, and alcohol, and then dried. On this glass substrate, the photosensitive resin composition 1 is exposed at an exposure amount (365 nm) of 40 mJ / cm ² , spin-coated so that the film thickness becomes 3.0 μm when it is developed, washed with water, and post-baked. And then pre-baked in a clean oven at 85 ° C. for 3 minutes. After cooling, the distance between the substrate coated with the photosensitive resin composition and the photomask made of quartz glass was set to 10 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used. Light irradiation was performed with an exposure amount of cm ² (based on 365 nm). In addition, irradiation to the polymerizable resin composition at this time made the radiated light from an ultrahigh pressure mercury lamp pass through the optical filter (UV-31; made by Asahi Spectroscopic Co., Ltd.).
As the photomask, a photomask having the following pattern formed on the same plane was used.

-It has a square light transmission part (pattern) whose one side is 10 μm, and the interval between the squares is 100 μm.
-It has a square translucent part (pattern) whose one side is 15 μm, and the interval between the squares is 100 μm.

After light irradiation, the substrate was developed by immersing the coating film in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23 ° C. for 40 seconds, washed with water, Post-baking was performed in an oven at 220 ° C. for 20 minutes. After cooling, the thickness of the cured film obtained was 3.0 μm as measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).
Evaluation after pattern formation was performed in the same manner as in Example 1.

Comparative Example 3
The photosensitive resin composition 7 was obtained so that it might become a composition shown in Table 3. Evaluation was performed in the same manner as in Example 4.

  From the results of Examples 1 to 3 shown in Table 2, the photosensitive resin composition of the present invention containing a binder resin containing an aliphatic polycyclic epoxy compound is excellent in storage stability. Moreover, when the photosensitive resin composition of this invention is used, it turns out that a pattern and a coating film with good pattern shape, mechanical characteristics, solvent resistance, and heat resistance are obtained. In addition, it can be seen that a fine pattern can be resolved as compared with Comparative Example 1.

  Moreover, from the result of Example 4 shown in Table 4, the photosensitive resin composition of this invention containing the binder resin containing an aliphatic polycyclic epoxy compound is excellent in storage stability. Moreover, when the photosensitive resin composition of this invention is used, it turns out that a pattern and a coating film with a favorable pattern shape are obtained. In addition, it can be seen that a fine pattern can be resolved as compared with Comparative Example 3.

  The photosensitive resin composition of the present invention is excellent in storage stability, and can form a pattern and a coating film excellent in pattern shape, surface smoothness, mechanical properties, heat resistance, and solvent resistance, It can be suitably used for forming a film used for a display device such as an overcoat, a photo spacer, an insulating film, a liquid crystal alignment control protrusion, and a coating layer for adjusting the thickness of a colored pattern.

Claims (7)

  Binder resin (A), photopolymerizable compound (B), photopolymerization initiator (C) and solvent (D) are contained, and binder resin (A) is unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride. The photosensitive resin composition which is a copolymer which consists only of (A1) and an aliphatic polycyclic epoxy compound (A2).   The photosensitive resin composition according to claim 1, wherein the aliphatic polycyclic epoxy compound (A2) is a compound having an epoxy group on the ring of the aliphatic polycyclic compound and having an unsaturated bond. The monomer (A2) having an aliphatic polycyclic epoxy group is at least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II). Item 3. The photosensitive resin composition according to Item 1 or 2.

[In the formulas (I) and (II), each R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group, and each X independently represents a single bond. Alternatively, it represents a C 1-6 alkylene group which may contain a hetero atom. ]   The content of the photopolymerization initiator (C) is 0.1 to 40 mass% with respect to the total amount of the binder resin (A) and the photopolymerizable compound (B). Photosensitive resin composition. The photosensitive resin composition in any one of Claims 1-4 in which a photopolymerizable compound (B) contains a polyfunctional monomer more than trifunctional.   The pattern formed using the photosensitive resin composition in any one of Claims 1-5.   A liquid crystal display device comprising the pattern according to claim 6.