TW201546542A - Photosensitive resin composition - Google Patents

Abstract

A photosensitive resin composition containing (A), (B), (C), and (D), the amount of (A) being 45-80% by mass in relation to the total amount of (A) and (C): (A) a polymer that contains a structural unit derived from an aromatic carboxylic acid having an ethylenically unsaturated bond and a structural unit derived from an unsaturated compound having a C2-4 cyclic ether structure, said polymer having no structural units that have a C4-6 perfluoroalkyl group; (B) a polymer containing structural unit that has a C4-6 perfluoroalkyl group; (C) a polymeric compound; and (D) a polymerization initiator.

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition.

In recent years, display devices and the like have produced color filters, ITO electrodes for liquid crystal display elements, organic EL display elements, circuit wiring boards, and the like by an inkjet method. Further, in the inkjet method, a partition wall formed using a photosensitive resin composition is used.

A photosensitive resin composition containing a copolymer of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate as a resin is known as the photosensitive resin composition (Patent Document 1).

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 2012-73603

When the ink containing the functional material of the machine is applied to the recessed portion formed by the partition wall formed on the substrate and the substrate by using the ink jet device, the ink is completely coated on the surface of the concave substrate, and the wettability of the ink on the surface of the substrate is better. High, and preferably, the ink has low wettability (high liquid repellency) on the partition wall for preventing leakage outside the target area. However, the wettability of the partition wall formed by using the photosensitive resin composition proposed in the past and the surface of the concave substrate into which the substrate is divided may not be satisfactory.

The present invention provides the following [1] to [6].

[1] A photosensitive resin composition containing (A), (B), (C), and (D), and the content of (A) is 45 mass% based on the total content of (A) and (C) 80% by mass or less, (A) includes a structural unit derived from an aromatic carboxylic acid having an ethylenically unsaturated bond, and a structural unit derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms, and a polymer having a structural unit having a perfluoroalkyl group having 4 to 6 carbon atoms, (B) a polymer having a structural unit having a perfluoroalkyl group having 4 to 6 carbon atoms, (C) a polymerizable compound, (D) a polymerization initiator.

[2] The photosensitive resin composition according to [1], wherein (D) contains a polymerization initiation of at least one selected from the group consisting of a biimidazole compound, a phenyl ketone compound, and an O-mercapto fluorene compound. Agent.

[3] A pattern formed of the photosensitive resin composition described in [1] or [2].

[4] A partition wall for inkjet, comprising the photosensitive resin composition according to [1] or [2].

[5] A display device comprising the pattern described in [3].

[6] A display device comprising the partition wall for inkjet according to [4].

According to the photosensitive resin composition of the present invention, a pattern excellent in wettability can be obtained, that is, the wettability of the surface of the concave substrate divided by the partition wall and the substrate is high, and the liquid repellency on the partition wall is high. .

1‧‧‧ display device

2‧‧‧Support substrate

3‧‧‧ partition wall

4‧‧‧Organic EL components

5‧‧‧ recess

6‧‧‧1st electrode

7‧‧‧1st organic EL layer (hole injection layer)

9‧‧‧2nd organic EL layer (light-emitting layer)

10‧‧‧2nd electrode

Fig. 1 is a cross-sectional view showing a portion of the display device 1 in an enlarged and schematic manner.

Fig. 2 is a plan view showing a part of the display device 1 according to the embodiment of the present invention in an enlarged manner.

The photosensitive resin composition of the present invention contains the photosensitive resin compositions of (A), (B), (C) and (D).

(A) a structural unit containing a structural unit derived from an aromatic carboxylic acid having an ethylenically unsaturated bond, and an unsaturated compound derived from a cyclic ether structure having a carbon number of 2 to 4, and having no carbon number 4~ a polymer of a structural unit of a perfluoroalkyl group of 6 (hereinafter sometimes referred to as "resin (A)")

(B) a polymer containing a structural unit having a perfluoroalkyl group having 4 to 6 carbon atoms (hereinafter sometimes referred to as "resin (B)")

(C) polymerizable compound

(D) A polymerization initiator.

Further, the photosensitive resin composition of the present invention preferably contains a solvent (E).

The photosensitive resin composition of the present invention may contain a resin other than the resin (A) and the resin (B) (hereinafter sometimes referred to as "resin (A1)"), a polymerization initiation aid (D1), and a polyfunctional sulfur. At least one selected from the group consisting of an alcohol compound (T) and a surfactant (F).

Further, in the present specification, the compounds exemplified as the respective components may be used singly or in combination unless otherwise specified.

The resin (A) contained in the photosensitive resin composition of the present invention is exemplified by a resin (A-1) containing an aromatic carboxylic acid (a) derived from an ethylenically unsaturated bond (hereinafter sometimes referred to as "( a structural unit of a)"), a polymer derived from a structural unit derived from an unsaturated compound (b) having a cyclic ether structure having 2 to 4 carbon atoms (hereinafter sometimes referred to as "(b)"), a resin ( A-2): a monomer (c) (hereinafter sometimes referred to as "(c)"), (a sometimes referred to as "(c)"), which is polymerizable with (a) and (b) and has no cyclic ether structure of 2 to 4 carbon atoms. And polymer synthesized by (b). However, none of (a), (b) and (c) has a perfluoroalkyl group having 4 to 6 carbon atoms.

(a) at least one monomer selected from the group consisting of an aromatic carboxylic acid having an ethylenically unsaturated bond and an aromatic carboxylic anhydride having an ethylenically unsaturated bond, specifically, o-vinylbenzene Aromatic carboxylic acids such as formic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, 3-vinylphthalic acid, 4-vinylphthalic acid; 3-vinylphthalic anhydride, 4 An aromatic carboxylic acid anhydride such as vinyl phthalic anhydride.

(b) a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring), preferably The monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated double bond is more preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloxy group.

In the present specification, the term "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth)acrylonitrile" and "(meth)acrylate" have the same meaning.

(b) For example, a monomer (b1) having an epoxy group (hereinafter sometimes referred to as "(b1)") or a monomer (b2) having an oxetanyl group (hereinafter sometimes referred to as "( B2)"), a monomer (b3) having a tetrahydroindenyl group (hereinafter sometimes referred to as "(b3)") or the like.

(b1) is exemplified by a monomer (b1-1) having an epoxidized structure of an unsaturated aliphatic hydrocarbon group (hereinafter sometimes referred to as "(b1-1)"), and having an epoxidized unsaturated alicyclic hydrocarbon. The monomer (b1-2) of the structure (hereinafter sometimes referred to as "(b1-2)").

(b1) is preferably a monomer having an epoxyethyl group and a (meth)acryloxy group, more preferably a structure having an epoxidized structure of an unsaturated alicyclic hydrocarbon and a (meth)acryloxy group. body. When it is such a preferable monomer, the photosensitive resin composition is excellent in storage stability.

(b1-1) is specifically exemplified by glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl Oleic ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2, 3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6- Bis(glycidoxymethyl)styrene, 2,3,4-cis (glycidoxymethyl)styrene, 2,3,5-gin (glycidoxymethyl)styrene, 2, 3,6-gin (glycidoxymethyl)styrene, 3,4,5-gin (glycidoxymethyl)styrene, 2,4,6-gin (glycidoxymethyl)benzene A compound or the like described in JP-A-H07-248625.

(b1-2) is exemplified by vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE (registered trademark) 2000; manufactured by DAICEL Chemical Industry Co., Ltd.), 3,4-Epoxycyclohexylmethyl acrylate (for example, CYCLOMER (registered trademark) A400; manufactured by DAICEL Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, CYCLOMER ( Registered trademark) M100; DAICEL Chemical Industry Co., Ltd.), a compound represented by the formula (I), a compound represented by the formula (II), and the like.

[In the formulae (I) and (II), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group, X ¹ and X ² each independently represents a single ^{bond, * - R 3 -, *} - R3-O -, * - R 3 -S-, or * -R ³ -NH-, R ³ represents alkyl having 1 to 6 carbon atoms, bis-yl , * indicates the key with O.].

The alkyl group having 1 to 4 carbon atoms represented by R ¹ and R ² is exemplified by a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, a t-butyl group or the like.

The alkyl group substituted by a hydroxy group is hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methyl Ethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

R ¹ and R ^{2 are} preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

The alkanediyl group represented by R ³ is exemplified by methylene, ethyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1. , 5-diyl, hexane-1,6-diyl, and the like.

X ¹ and X ^{2 are} preferably a single bond, a methylene group, an extended ethyl group, a *-CH ₂ -O- (* represents a bond with O), and a *-CH ₂ CH ₂ -O- group. More preferably, it is a single bond, *-CH ₂ CH ₂ -O- group.

The compound represented by the formula (I) is exemplified by the compound represented by the formula (I-1) to the formula (I-15). Among them, it is preferred to formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to I-15) representation of the combination More preferably, it is a compound represented by the formula (I-1), the formula (I-7), the formula (I-9) or the formula (I-15).

The compound represented by the formula (II) is exemplified by the compound represented by the formula (II-1) to the formula (II-15), and among them, the formula (II-1), the formula (II-3), and the formula are preferred. (II-5), a compound represented by the formula (II-7), the formula (II-9) or the formula (II-11) to the formula (II-15), more preferably a formula (II-1), a formula (II) A compound represented by II-7), formula (II-9) or formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) may be used singly or in combination of two or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used, the content ratio [the compound represented by the formula (I): the compound represented by the formula (II)] is based on the molar ratio. It is preferably 5:95 to 95:5, more preferably 20:80 to 80:20.

(b2) is preferably a monomer having an oxetanyl group and a (meth) acryloxy group. (b2) is exemplified by, for example, 3-methyl-3-(methyl)propenyloxymethyloxetane, 3-ethyl-3-(methyl)propenyloxymethyloxetane Alkyl, 3-methyl-3-(methyl)propenyloxyethyloxetane, 3-ethyl-3-(methyl)propenyloxyethyloxetane, and the like.

The (b3) is preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group.

Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, VISCOTE V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

(c) Listed as (meth) acrylates, N-substituted maleimide, unsaturated dicarboxylic acid diesters, alicyclic unsaturated compounds, unsaturated carboxylic acids, unsaturated carboxylic acids Anhydrides, styrenes, other vinyl compounds, and the like.

The (meth) acrylates are exemplified by methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Alkyl esters such as tributyl ester; cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.1.0 ^2,6 ]癸-8-yl (meth)acrylate Esters (commonly known in the art as dicyclopentyl (meth)acrylate), dicyclopentyloxyethyl (meth)acrylate, tricyclo(methyl)acrylate [5.2.1.0 ^2,6 ]癸Alkenyl-8-yl ester (a customary name in the art is "dicyclopentenyl (meth)acrylate)", a cycloalkyl ester such as isobornyl (meth)acrylate; (meth)acrylic acid 2- Hydroxyalkyl esters such as hydroxyethyl ester and 2-hydroxypropyl (meth)acrylate; aryl groups such as phenyl (meth)acrylate and benzyl (meth)acrylate; and aralkyl esters.

N-substituted maleimide is exemplified by N-phenylmaleimide, N-cyclohexylmaleimide, N-benzyl maleimide, N-amber 醯imino-3-maleimide benzoate, N-amber succinimide-4-maleimide butyrate, N-succinimide-6-Malaysia Aminohexanoate, N-succinimide-3-maleimide propionate, N-(9-acridinyl)maleimide, and the like.

The unsaturated dicarboxylic acid diesters are exemplified by maleic acid diester, fumaric acid diester, itaconic acid diester, and the like.

The alicyclic unsaturated compounds are exemplified by bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] g-2 - alkene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1 Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2 .1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1] Hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy- 5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2. 1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-benzene Oxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxy) A carbonyl group) a bicyclic unsaturated compound such as a bicyclo[2.2.1]hept-2-ene or the like.

The unsaturated carboxylic acids are listed as unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3, 4, 5 ,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid Unsaturated dicarboxylic acid such as acid, dimethyltetrahydrophthalic acid or 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] Hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5 -carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2 .1] a carboxyl group-containing bicyclic unsaturated compound such as hept-2-ene; succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) propylene] An unsaturated mono[2-(methyl)acryloxyalkylene] ester of a polyvalent carboxylic acid having two or more members such as a methoxyethyl]ester; and the same molecule such as α-(hydroxymethyl)acrylic acid Unsaturated (meth) acrylates such as hydroxyl groups and carboxyl groups.

The unsaturated carboxylic anhydrides are exemplified by maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydroortene. Phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride An unsaturated diacid anhydride or the like.

The styrenes are exemplified by styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and the like.

Other ethylene compounds are exemplified by (meth)acrylonitrile, vinyl chloride, vinylidene chloride, (meth)acrylamide, vinyl acetate, 1,3-butadiene, isoprene and 2,3-dimethyl Base-1,3-butadiene and the like.

As (c), it is preferred from the viewpoints of polymerization reactivity and alkali solubility. Examples of styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo[2.2.1]hept-2-ene.

In the resin (A-1), the ratio of the structural unit derived from each monomer to the total number of moles of the structural unit constituting the resin (A-1) is preferably in the following range.

The structural unit derived from (a): 5 to 60 mol% (more preferably 10 to 50 mol%)

Structural unit derived from (b): 40 to 95 mol% (more preferably 50 to 90 mol%)

When the ratio of the structural unit of the resin (A-1) is in the above range, the storage stability of the photosensitive resin composition, the development property when the pattern is formed from the photosensitive resin composition, and the obtained coating film and pattern are The solvent resistance, heat resistance, and mechanical strength tend to be good.

The resin (A-1) is preferably a resin (A-1) of (b1), more preferably (b) a resin (A-1) of (b1-2).

For the resin (A-1), for example, the method described in the literature "Experimental method for polymer synthesis" (Otsuka Ryo, Chemical Co., Ltd., 1st edition, 1st brush, issued on March 1, 1972) The cited documents described in the literature are manufactured.

Specifically, it is exemplified that a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are fed into a reaction container, and oxygen in the atmosphere is replaced with, for example, nitrogen gas, thereby forming a deoxidizing atmosphere and stirring. Heating and insulation methods. Further, the polymerization initiator, solvent and the like used herein are not particularly limited, and any of the usual users in the field can be used. For example, as an aggregation The initiators are listed as azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides (benzamide). The solvent (such as a base peroxide) may be used as a solvent (E) as a photosensitive resin composition, as long as it can dissolve each monomer. In order to adjust the molecular weight of the obtained resin, a chain transfer agent may also be added during the polymerization reaction. Chain transfer agents are listed as n-butane thiol, third butane thiol, n-dodecyl mercaptan, 2-mercaptoethanol, thioglycolic acid, ethyl thioglycolate, 2-ethyl thioglycolate Thiols such as hexyl ester, methoxybutyl thioglycolate, 3-alkylthiopropionic acid, polysulfonium oxide containing an alkylthio group (KF-2001: manufactured by Shin-Etsu Chemical Co., Ltd.); chloroform, carbon tetrachloride, Halogenated alkane such as carbon tetrabromide.

Further, as the obtained polymer, the solution after the reaction may be used as it is, or a solution which is concentrated or diluted may be used, or a solid (powder) may be taken out by a method such as reprecipitation. In particular, by using the same solvent as the solvent (E) to be described later as the solvent in the polymerization, the solution after the reaction can be used as it is, and the production steps can be simplified.

In the resin (A-2), the ratio of the structural unit derived from each monomer to the total number of moles of all the structural units constituting the resin (A-2) is preferably in the following range.

Structural unit derived from (a): 2 to 40 mol% (more preferably 5 to 35 mol%)

The structural unit derived from (c): 1 to 65 mol% (more preferably 1 to 60 mol%)

The structural unit derived from (b): 2 to 95 mol% (more preferably 5 to 80 mol%)

When the ratio of the structural unit of the resin (A-2) is in the above range, the storage stability of the photosensitive resin composition, the development property when the pattern is formed from the photosensitive resin composition, and the obtained coating film and pattern are The solvent resistance, heat resistance, and mechanical strength tend to be good.

The resin (A-2) is preferably a resin (A-2) of (b1), more preferably (b) is a resin (A-2) of (b1-2).

The resin (A-2) can be produced by the same method as the resin (A-1).

The polystyrene-equivalent weight average molecular weight of the resin (A) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000. When the weight average molecular weight of the resin (A) is in the above range, the coating property tends to be excellent, and film formation at the exposed portion is less likely to occur during development, and the non-exposed portion can be easily removed by development.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A) is preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0. When the molecular weight distribution is in the above preferred range, the developing property tends to be excellent.

The acid value of the resin (A) is usually from 20 to 150 mgKOH/g, preferably from 40 to 135 mgKOH/g, more preferably from 50 to 135 mgKOH/g. Here, the acid value is a value obtained by measuring the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined by titration with an aqueous potassium hydroxide solution.

The content of the resin (A) is 45% by mass or more and 80% by mass or less based on the total content of the resin (A) and the polymerizable compound (C), preferably 48% by mass or more and 75% by mass or less, more preferably 50% by mass. The above 70% by mass or less.

The content of the resin (A) is relative to the combination of the resin (A) and the polymerizable compound (C) When the content is more than 80% by mass, the development time when the coating film formed from the photosensitive resin composition is developed tends to be long.

When the content of the resin (A) is in the above preferred range, the wettability of the patterned surface of the substrate formed by the photosensitive resin composition is good.

The photosensitive resin composition of the present invention contains a resin (B). The resin (B) is a polymer containing a structural unit derived from an unsaturated compound (d) (hereinafter sometimes referred to as "(d)") having a perfluoroalkyl group having 4 to 6 carbon atoms.

As (d), a compound represented by the formula (d-0) is listed.

[In the formula (d-0), R ^f represents a perfluoroalkyl group having 4 to 6 carbon atoms, and R ^d represents a hydrogen atom, a halogen atom, a cyano group, a phenyl group, a benzyl group or an alkyl group having 1 to 21 carbon atoms; The hydrogen atom contained in the alkyl group may be substituted by a halogen atom or a hydroxyl group, and X ^d represents a single bond, a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a carbon number. a 6- to 12-valent aromatic hydrocarbon group, and the aliphatic hydrocarbon group and -CH ₂ - contained in the alicyclic hydrocarbon group may also be -O-, -CO-, -NR ^e -, -S- or -SO ₂ - substituted].

R ^f is a perfluoroalkyl group having 4 to 6 carbon atoms, preferably perfluorobutyl group and perfluorohexyl group.

The alkyl group having 1 to 21 carbon atoms in R ^d is exemplified by methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group and n-decyl group. Iso-linear alkyl; isopropyl, isobutyl, t-butyl, isopentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl Base, 1-ethylbutyl, 2-ethylbutyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethyl Pentyl, 2-ethylpentyl, 3-ethylpentyl, 1-propylbutyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl , 5-methylheptyl, 6-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-propylpentyl, 1-butyl Butyl, 1-butyl-2-methylbutyl, 1-butyl-3-methylbutyl, tert-butyl, 1,1-dimethylpropyl, 1,1-dimethyl Butyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethyl-2-methylpropyl, 1,1-di Methylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 2,2-dimethylpentyl, 2,3-di Pentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3,4-dimethylpentyl, 1-ethyl-1-methylbutyl, 2-ethyl a branched alkyl group such as -3-methylbutyl group.

R ^{d is} preferably a hydrogen atom, a halogen atom or a methyl group.

The divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms in X ^d is exemplified by methylene, ethyl, propyl-1,3-diyl, propyl-1,2-diyl, butane-1,4-di Base, butyl-1,3-diyl, butyl-1,2-diyl, pent-1,5-diyl, hex-1,6-diyl, hept-1,7-diyl, octane-1 , 8-diyl and the like alkanediyl.

The divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms in X ^d is exemplified by a cyclopropyldiyl group, a cyclobutanediyl group, a cyclopentadienyl group, a cyclohexanediyl group, a cycloheptyl group, a cyclodecanediyl group and the like.

The divalent aromatic hydrocarbon group having 6 to 12 carbon atoms in X ^d is exemplified by a phenylene group, a naphthalene diyl group and the like.

The 2-valent alicyclic hydrocarbon group having 1 to 10 carbon atoms and the -CH ₂ - contained in the 3 to 10 valent alicyclic hydrocarbon group having 3 to 10 are -O-, -CO-, -NR ^e -, -S- The X ^d substituted by -SO ₂ - is, for example, a group represented by the formula (xd-1) to the formula (xd-10).

X ^{d is} preferably an alkanediyl group having 1 to 6 carbon atoms, more preferably an ethyl group.

(d) is preferably a compound represented by the formula (d-0').

[In the formula (d-0'), R ^h represents a perfluoroalkyl group having 4 to 6 carbon atoms, and R ^g represents a hydrogen atom, a halogen atom or a methyl group].

The compound represented by the formula (d-0) is exemplified by, for example, the compound (d-1) to the compound (d-94). In the table, the formula number shown in the column of X ^d indicates the formula number of the above-exemplified base. Further, for example, the compound (d-1) is a compound represented by the following formula (d-1).

The resin (B) preferably contains a structural unit derived from (d), a structural unit derived from the above (a), and an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride (e) (but, a) at least one selected from the group consisting of structural units (hereinafter sometimes referred to as "(e)"), preferably containing a structural unit derived from (d) and a structure derived from (e) The resin of the unit is preferably a structural unit derived from (d) and a structural unit derived from (e) and a structural sheet derived from (b) Bit of resin. When the resin (B) contains the structural unit derived from (a) and/or (e), it is excellent in developability, and thus tends to suppress unevenness due to residue or development. When the resin (B) contains the structural unit derived from (b), the solvent resistance tends to be excellent. Further, the resin (B) may contain other structural units. The monomer introduced into another structural unit (hereinafter sometimes referred to as "(c')") is, for example, a monomer other than the unsaturated carboxylic acid and the unsaturated carboxylic anhydride, in addition to the above (c).

When the resin (B) is a polymer of (a) and/or (e) and (d), the ratio of the structural unit derived from each monomer to the total number of moles of the structural unit constituting the resin (B) is Good for the following range.

The structural unit derived from (a) and/or (e): 5 to 40% by mass (more preferably 10 to 30% by mass)

The structural unit derived from (d): 60 to 95% by mass (more preferably 70 to 90% by mass)

When the resin (B) is a polymer of (a) and/or (e), (b) or (d), the ratio of the ratio of the structural unit derived from each monomer to the structural unit constituting the resin (B) The molar number is preferably in the range below.

The structural unit derived from (a) and/or (e): 5 to 40% by mass (more preferably 10 to 30% by mass)

The structural unit derived from (b): 5 to 80% by mass (more preferably 10 to 70% by mass)

The structural unit derived from (d): 10 to 80% by mass (more preferably 20 to 70% by mass)

Resin (B) is an aggregation of (a) and / or (e), (b), (c') and (d) In the case of the material, the ratio of the structural unit derived from each monomer to the total number of structural units constituting the resin (B) is preferably in the following range.

The structural unit derived from (a) and/or (e): 5 to 40% by mass (more preferably 10 to 30% by mass)

The structural unit derived from (b): 5 to 70% by mass (more preferably 10 to 60% by mass)

The structural unit derived from (c'): 10 to 50% by mass (more preferably 20 to 40% by mass)

The structural unit derived from (d): 10 to 80% by mass (more preferably 20 to 70% by mass)

When the ratio of each structural unit is in the above range, the liquid repellency and the development property tend to be excellent.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably from 3,000 to 20,000, more preferably from 5,000 to 15,000. When the weight average molecular weight of the resin (B) is in the above preferred range, the coating property tends to be excellent, and film formation in the exposed portion is less likely to occur during development, and the non-exposed portion can be easily removed by development.

The acid value of the resin (B) is 20 to 200 mgKOH/g, preferably 40 to 150 mgKOH/g.

The content of the resin (B) is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the total of the resin (A), the resin (A1) and the polymerizable compound (C). When the content of the resin (B) is in the above preferred range, the image forming property at the time of pattern formation is excellent, and the liquid repellency of the obtained pattern tends to be excellent.

The photosensitive resin composition of the present invention may further contain a resin (A1). The resin (A1) is exemplified by the following resins and the like:

Resin (A1-1): a polymer obtained by polymerizing (e) and (b)

Resin (A1-2): a polymer obtained by polymerizing (e) and (b) and (c')

Resin (A1-3): a polymer obtained by polymerizing (e) and (c')

Resin (A1-4): a resin obtained by reacting (b) with a polymer obtained by polymerizing (e) and (c')

Resin (A1-5): a resin obtained by reacting (a) and/or (e) with a polymer obtained by polymerizing (b) and (c').

In the resin (A1-1), the ratio of the structural unit derived from each monomer to the total number of structural units of all the structural units constituting the resin (A1-1) is preferably in the following range.

Structural unit derived from (e): 5 to 60 mol% (more preferably 10 to 50 mol%)

Structural unit derived from (b): 40 to 95 mol% (more preferably 50 to 90 mol%)

When the ratio of the structural unit of the resin (A1-1) is in the above range, the storage stability of the photosensitive resin composition, the development property when the photosensitive resin composition forms a pattern, and the obtained coating film and pattern are The tendency to have good solvent resistance.

In the resin (A1-2), the ratio of the structural unit derived from each monomer to the total structural unit of all the structural units constituting the resin (A1-2) is preferably in the following range.

Structural unit derived from (e): 2 to 45 mol% (more preferably 5 to 40 m) %)

The structural unit derived from (b): 2 to 95 mol% (more preferably 5 to 80 mol%)

Structural unit derived from (c'): 1 to 65 mol% (more preferably 5 to 60 mol%)

When the ratio of the structural unit of the resin (A1-2) is in the above range, the storage stability of the photosensitive resin composition, the development property when the photosensitive resin composition forms a pattern, and the obtained coating film and pattern are The tendency to have good solvent resistance.

In the resin (A1-3), the ratio of the structural unit derived from each monomer to the total number of structural units of all the structural units constituting the resin (A1-3) is preferably in the following range.

Structural unit derived from (e): 2 to 40 mol% (more preferably 5 to 35 mol%)

Structural unit derived from (c'): 60 to 98 mol% (more preferably 65 to 95 mol%)

When the ratio of the structural unit of the resin (A1-1) is in the above range, the storage stability of the photosensitive resin composition, the development property when the photosensitive resin composition forms a pattern, and the obtained coating film and pattern are The tendency to have good solvent resistance.

The resin (A1-4) is a resin obtained by reacting the polymer of (e) and (c') with (b).

The resin (A1-4) can be produced, for example, by a two-stage process. In this case, you can also refer to the above-mentioned document "Experimental Method for Polymer Synthesis" (Otsu Takayuki) It is produced by the method described in Japanese Laid-Open Patent Publication No. 2001-89533, and the method described in the Japanese Patent Publication No. 2001-89533.

First, the first stage is the same as the above-described method for producing the resin (A-1), and the polymers of (e) and (c') are obtained.

In this case, as described above, the obtained polymer may be used as it is, or a solution obtained by concentration or dilution may be used as a solid (powder) extractor. Further, the weight average molecular weight and molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] in terms of polystyrene equivalent to the above are preferable.

However, the ratio of the structural unit derived from (e) and (c') to the total number of moles constituting all the structural units of the polymer is preferably in the following range.

Structural unit derived from (e): 5 to 50 mol% (more preferably 10 to 45 mol%)

Structural unit derived from (c'): 50 to 95 mol% (more preferably 55 to 90 mol%)

Next, in the second stage, a part of the carboxylic acid and the carboxylic anhydride derived from the (e) of the obtained polymer is reacted with the cyclic ether of the above (b). Since the cyclic ether has high reactivity and does not easily remain unreacted (b), the (b) used for the resin (A1-2) is preferably (b1) or (b2), more preferably (b1-1).

Specifically, in the above, the ambient atmosphere in the flask can be changed from nitrogen to air, and the number of moles in the flask relative to (e) is 5 to 80 mol% (b), relative to The total amount of e), (b) and (c') is 0.001~5 The reaction catalyst of the carboxyl group and the cyclic ether (for example, dimethylaminomethyl phenol), and the total amount of (a), (b), and (c) is 0.001 to 5% by mass. The polymerization inhibitor (for example, hydroquinone or the like) is reacted at 60 to 130 ° C for 1 to 10 hours to obtain a resin (A1-4). Further, in the same manner as the polymerization conditions, the feeding method or the reaction temperature can be appropriately adjusted in consideration of the production equipment or the calorific value of the polymerization.

Further, in this case, the number of moles of (b) relative to the number of moles of (e) is preferably from 10 to 75 mol%, more preferably from 15 to 70 mol%. By the above-mentioned preferable range, the storage stability of the photosensitive resin composition, the development property when the pattern is formed from the photosensitive resin composition, and the solvent resistance, heat resistance, and mechanical properties of the obtained coating film and pattern are obtained. The tendency to balance the strength and sensitivity.

The resin (A1-5) is the first stage, and the polymers of (b) and (c') are obtained in the same manner as in the production method of the above resin (A-1).

In this case, as in the above, the obtained polymer may be directly used as a solution after the reaction, or a concentrated or diluted solution may be used, or a solid (powder) extractor may be used by a method such as reprecipitation.

The ratio of the structural unit derived from (b) and (c') to the total number of structural units constituting the entire structural unit of the polymer is preferably in the following range.

Structural unit derived from (b): 5 to 95 mol% (more preferably 10 to 90 mol%)

Structural unit derived from (c'): 5 to 95 mol% (more preferably 10 to 90 mol%)

Further, in the same manner as in the production method of the resin (A1-4), the cyclic ether derived from (b) in the polymers of (b) and (c') can be obtained by having (a) and / Or obtained by reacting a carboxylic acid or a carboxylic anhydride of (e). The hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride can also be further reacted with a carboxylic acid anhydride.

The amount of (a) and/or (e) used in the reaction of the polymer is preferably from 5 to 80 mol% based on the number of moles of (b). Since the cyclic ether has high reactivity and does not easily remain unreacted (b), (b) is preferably (b1), more preferably (b1-1).

The polystyrene-equivalent weight average molecular weight of the resin (A1) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000. When the weight average molecular weight of the resin (A) is in the above preferred range, the coating property tends to be excellent, and film formation at the exposed portion is less likely to occur during development, and the non-exposed portion can be easily removed by development.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A1) is preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0. When the molecular weight distribution is in the above preferred range, the developing property tends to be excellent.

The acid value of the resin (A1) is usually from 20 to 150 mgKOH/g, preferably from 40 to 135 mgKOH/g, more preferably from 50 to 135 mgKOH/g.

When the resin (A1) is contained, the content thereof is preferably from 1 to 80% by mass, more preferably from 1 to 50% by mass, based on the total amount of the resin (A) and the resin (A1). When the content of the resin (A1) is in the above preferred range, the pattern can be formed with high sensitivity and the image forming property is excellent.

The polymerizable compound (C) is a compound which is polymerized by an active radical generated from the polymerization initiator (D), and is, for example, a compound having an ethylenically unsaturated bond, and is preferably a (meth) acrylate compound.

The polymerizable compound (C) having one ethylenically unsaturated bond is the same as those exemplified as the above-mentioned (a), (b), and (c). Among them, (meth) acrylates are preferred.

The polymerizable compound (C) having two ethylenically unsaturated bonds is exemplified by 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, 1,6- Hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol Di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bisphenol A bis(acryloxyethyl)ether, ethoxylated bisphenol A II Methyl) acrylate, propoxy neopentyl glycol di(meth) acrylate, ethoxylated neopentyl glycol di(meth) acrylate, 3-methyl pentanediol di(meth) acrylate, and the like.

The polymerizable compound (C) having three or more ethylenically unsaturated bonds is exemplified by trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and stilbene (2-hydroxyethyl)isocyanate. Uric acid tris(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, a reaction of tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri(meth) acrylate with an acid anhydride, dipentaerythritol penta (meth) acrylate and an acid anhydride, three a reaction of pentaerythritol hepta (meth) acrylate with an acid anhydride, a caprolactone-modified trimethylolpropane tri(meth) acrylate, a caprolactone-modified pentaerythritol tri(meth) acrylate, or the like Ester-modified ginseng (2-hydroxyethyl) isocyanurate three ( Methyl) propyl Ethyl ester, caprolactone modified pentaerythritol tetra(meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate , caprolactone modified tripentaerythritol tetra (meth) acrylate, caprolactone modified trimellititol penta (meth) acrylate, caprolactone modified triptyp pentaerythritol hexa (meth) acrylate, Reaction of lactone modified trimellititol seven (meth) acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, caprolactone modified pentaerythritol tri(meth) acrylate and anhydride a reaction of a caprolactone-modified dipentaerythritol penta (meth) acrylate with an acid anhydride, a reaction of caprolactone-modified tripentaerythritol hepta (meth) acrylate with an acid anhydride, and the like. Among them, a polymerizable compound (C) having three or more ethylenically unsaturated bonds is preferred, and more preferably dipentaerythritol hexa(meth)acrylate or trimethylolpropane tri(meth)acrylate. Pentaerythritol tri(meth)acrylate.

The content of the polymerizable compound (C) is preferably from 20 to 55% by mass, more preferably from 30 to 45% by mass, based on the total of the resin (A), the resin (A1) and the polymerizable compound (C). When the content of the polymerizable compound (C) is in the above range, the sensitivity, the smoothness, and the reliability of the obtained pattern tend to be good.

The photosensitive resin composition of the present invention contains a polymerization initiator (D). The polymerization initiator (D) is not particularly limited as long as it is a compound which starts polymerization by the action of light or heat, and a conventional polymerization initiator can be used.

The polymerization initiator (D) is exemplified by, for example, an alkylphenol compound, a biimidazole compound, a triazine compound, a mercaptophosphine oxide compound, or an O-indenylphosphonium compound. Further, it is also possible to use the Japanese Patent Publication No. 2008-181087. Light and/or thermal cationic polymerization initiator (for example, composed of a phosphonium cation and an anion derived from a Lewis acid). Among them, at least one selected from the group consisting of a biimidazole compound, a phenylalkanone compound and an O-indenyl ruthenium compound is preferred, and a phenyl ketone compound is preferred. In the case of a polymerization initiator containing these compounds, it is particularly preferred to have a high sensitivity.

The aforementioned O-indenyl ruthenium compound has a compound having a partial structure represented by the formula (d1). Hereinafter, * indicates a keying key.

The above O-indenyl ruthenium compound is exemplified by, for example, N-benzylideneoxy-1-(4-phenylmercaptophenyl)butan-1-one-2-imine, N-benzylideneoxy-1- (4-phenylmercaptophenyl)oct-1-one-2-imine, N-benzylideneoxy-1-(4-phenylmercaptophenyl)-3-cyclopentylpropan-1-one -2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethane-1-imine , N-Ethyloxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolylmethyloxy) Benzamethylene}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-(2-methylbenzhydryl) -9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylideneoxy-1-[9-ethyl-6-(2-methylbenzhydryl) )-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as IRGACURE (registered trademark) OXE01, OXE02 (above, BASF) and N-1919 (made by ADEKA) can also be used.

The phenylalkanone compound has a partial structure represented by the formula (d2) or a compound having a partial structure represented by the formula (d3). In these partial structures, the benzene ring may also have a substituent.

A compound having a partial structure represented by the formula (d2) is exemplified by, for example, 2-methyl-2-morpholine-1-(4-methylmercaptophenyl)propan-1-one, 2-dimethylamino-1 -(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4 -(4-morpholinyl)phenyl]butan-1-one and the like. Commercial products such as IRGACURE (registered trademark) 369, 907, and 379 (manufactured by BASF Corporation) can also be used.

The compound having a partial structure represented by the formula (d3) is exemplified by, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2) -hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one Oligomer, α,α-diethoxyacetophenone, benzyldimethylketal, and the like.

From the viewpoint of sensitivity, the phenylalkanone compound is preferably a compound having a partial structure represented by the formula (d2).

The biimidazole compound is exemplified by 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorobenzene). (4) 4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Laid-Open Patent Publication No. Hei 6-75372, JP-A-6-75373, etc.), 2, 2'-double (2) -chlorophenyl)- 4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(alkoxyphenyl)biimidazole , 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl) -4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. Sho 48-38403, JP-A-62-174204, etc.), 4, 4 The imidazole compound in which the phenyl group at the 5, 5'-position is substituted with a carbonyl alkoxy group (for example, refer to JP-A-7-10913, etc.). Preferred is 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)- 4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole.

The above triazine-based compounds are exemplified by 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis(trichloromethyl). - 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-indolyl-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)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethylene 1,1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1, 3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

The above fluorenylphosphine oxide compound is exemplified by 2,4,6-trimethylbenzimidyldiphenylphosphine oxide.

Further, the polymerization initiator (D) is exemplified by a benzoin compound such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzoin isobutyl ether; Benzophenone, methyl o-benzhydrylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, a benzophenone compound such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone or 2,4,6-trimethylbenzophenone; 9,10- Anthraquinone compounds such as phenanthraquinone, 2-ethylhydrazine, camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, Titanocene compounds and the like. These are preferably used in combination with a polymerization initiation aid (D1) to be described later.

As the polymerization initiator having a group which causes chain transfer, a polymerization initiator described in JP-A-2002-544205 can also be used.

The above polymerization initiator having a group which causes chain transfer can also be used as the component (c) constituting the resin (A).

In the photosensitive resin composition of the present invention, a polymerization initiation aid (D1) can be used together with the above polymerization initiator (D). The polymerization initiation aid (D1) is used in combination with a polymerization initiator (D) to promote a compound used for polymerization of a polymerizable compound which starts polymerization by a polymerization initiator, or a sensitizer. The polymerization initiation aid (D1) is exemplified by a thioxanthone compound, an amine compound, a carboxylic acid compound, a compound described in JP-A-2008-65319, and JP-A-2009-139932.

The thioxanthone compounds are exemplified by, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-propoxythioxanthone and the like.

The amine compound is exemplified by an aliphatic amine compound such as triethanolamine, methyldiethanolamine or triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-di Isoamyl methyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylamino B benzoate Ester, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (general name; Michler's ketone) or 4,4'-bis (diethylamine) An aromatic amine compound such as benzophenone.

The carboxylic acid compound is exemplified by phenylmercaptoacetic acid, methylphenylmercaptoacetic acid, ethylphenylmercaptoacetic acid, methylethylphenylmercaptoacetic acid, dimethylphenylmercaptoacetic acid, methoxyphenylmercaptoacetic acid, and Methoxyphenylmercaptoacetic acid, chlorophenylmercaptoacetic acid, dichlorophenylmercaptoacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxy An aromatic heteroacetic acid such as acetic acid.

The combination of the polymerization initiator (D) and the polymerization initiation aid (D1) is exemplified by a benzene ketone compound and a thioxanthone compound, a phenyl ketone compound and an aromatic amine compound, and specifically exemplified is 2-methyl-2- Morpholinyl-1-(4-methylmercaptophenyl)propan-1-one with 2,4-diethylthioxanthone, 2-dimethylamino-2-benzyl-1-(4-? Phenylphenyl)butan-1-one with 2,4-diethylthioxanthone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinylphenyl ) butan-1-one with 2,4-diethylthioxanthone, 2-morpholinyl-1-(4-methyldecylphenyl)-2-methylpropan-1-one and 2-isopropyl Thiophenone and 4-isopropylthioxanthone, 2-morpholinyl-1-(4-methylnonylphenyl)-2-methylpropan-1-one and 4,4'-bis (two Ethylamino)benzophenone, 2-dimethylamino-2-benzyl-1-(4-morpholinylphenyl)butan-1-one and 4,4'-bis(diethylamino) Benzophenone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinylphenyl)butan-1-one and 4,4'-bis(diethylamine) Base) benzophenone and the like.

Wherein, a combination of a phenylalkanone compound and a thioxanthone compound is preferred, more preferably 2-methyl-2-morpholinyl-1-(4-methylnonylphenyl)propan-1-one and 2, 4-Diethylthioxanthone, 2-methyl-2-morpholinyl-1-(4-methylindole Phenyl phenyl) propan-1-one with 2-isopropyl thioxanthone and 4-isopropyl thioxanthone. In the case of these combinations, a pattern having high sensitivity and high visible light transmittance is obtained.

The content of the polymerization initiator (D) is preferably from 0.5 to 30 parts by mass, more preferably from 1 to 20% by mass based on 100 parts by mass of the total of the resin (A), the resin (A1) and the polymerizable compound (C). It is preferably 1 to 10 parts by mass. When the content of the polymerization initiator (D) is in the above preferred range, the pattern can be obtained with high sensitivity.

The amount of use of the polymerization initiator (D1) is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 100 parts by mass based on the total amount of the resin (A), the resin (A1) and the polymerizable compound (C). 7 parts by mass. When the content of the polymerization initiation aid (D1) is in the above preferred range, the pattern can be obtained with high sensitivity, and the shape of the obtained pattern is good.

The photosensitive resin composition of the present invention may further contain a solvent (E).

As the solvent which can be used in the present invention, for example, an ester solvent (-COO-containing in the molecule, a solvent containing no -O-), an ether solvent (a solvent containing -O- in the molecule, a solvent containing no -COO-), an ether ester solvent can be used. (The solvent containing -COO- and -O- in the molecule), the ketone solvent (the solvent containing -CO-, the solvent containing no -COO-), the alcohol solvent, the aromatic hydrocarbon solvent, the guanamine solvent, the dimethylene Among those selected from the group.

The ester solvent is exemplified by methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, propionic acid. Butyl ester, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, pyruvic acid Propyl ester, methyl acetoxyacetate, ethyl acetoxyacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

The ether solvent is exemplified by ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol single Ethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3- Methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl Ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, methyl anisole, and the like.

The ether ester solvent is exemplified by methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropanoate, 2-ethoxyl Ethyl 2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl Ethyl ether acetate and the like.

The ketone solvent is exemplified by 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, Cyclopentanone, cyclohexanone, isophorone, and the like.

The alcohol solvent is exemplified by methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin or the like.

The aromatic hydrocarbon solvent is exemplified by benzene, toluene, xylene, mesitylene, etc., and the guanamine solvent is exemplified by N,N-dimethylformamide, N,N-dimethylacetamide, N- Methyl pyrrolidone and the like.

These solvents may be used alone or in combination of two or more.

Among the above solvents, from the viewpoint of coatability and drying property, an organic solvent having a boiling point of from 1 to 10 at from 120 ° C to 180 ° C is preferred. Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-ethoxypropionic acid ethyl ester, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 3-methyl Oxy-1-butanol or the like is preferred. When the solvent (E) is a preferred solvent, unevenness in coating can be suppressed, and flatness of the coating film can be improved.

The content of the solvent (E) in the photosensitive resin composition of the present invention is preferably from 60 to 95% by mass, more preferably from 70 to 90% by mass, based on the total mass of the photosensitive resin composition.

In other words, the solid content of the photosensitive resin composition is preferably from 5 to 40% by mass, more preferably from 10 to 30% by mass. When the content of the solvent (E) is in the above preferred range, the film obtained by applying the photosensitive resin composition tends to have high flatness. Here, the solid content means the amount by which the solvent (E) is removed from the photosensitive resin composition.

Further, the photosensitive resin composition of the present invention may further contain a polyfunctional thiol compound (T). The so-called polyfunctional thiol compound (T) is a point A compound having two or more thiol groups (-SH) in the subunit. In particular, when a compound having two or more mercapto groups bonded to a carbon atom derived from an aliphatic hydrocarbon group is used, the sensitivity of the photosensitive resin composition of the present invention tends to be high.

The polyfunctional thiol compound (T) is specifically exemplified by hexanedithiol, decanedithiol, 1,4-bis(methylindenyl)benzene, butyl dithiol bis(3-mercaptopropionate), butadiene disulfide. Alcohol bis(3-mercaptoacetate), ethylene glycol bis(3-mercaptoacetate), trimethylolpropane ginseng (3-mercaptoacetate), butyl dithiol bis(3-mercaptopropionic acid) Ester), trimethylolpropane ginseng (3-mercaptopropionate), trimethylolpropane ginseng (3-mercaptoacetate), pentaerythritol ruthenium (3-mercaptopropionate), pentaerythritol ruthenium (3-mercapto) Acetate), hydroxyethyl ginseng (3-mercaptopropionate), pentaerythritol ruthenium (3-mercaptobutyrate), 1,4-bis(3-mercaptobutoxy)butane, and the like.

The content of the polyfunctional thiol compound (T) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, per 100 parts by mass of the polymerization initiator (D). When the content of the polyfunctional thiol compound (T) is in the above preferred range, the sensitivity of the photosensitive resin composition tends to be high, and the developing property tends to be good.

The photosensitive resin composition of the present invention may contain a surfactant (F) (except for the resin (B)). The surfactant is exemplified by, for example, a polyfluorene-based surfactant, a fluorine-based surfactant, a polyfluorene-based surfactant having a fluorine atom, and the like.

The polyoxygenated surfactant is exemplified by a surfactant having a decane bond. Specifically listed as TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, polyether modified oxygenated oil SH8400 (trade name; TORAY‧DOW CONNING (share) system), KP321, KP322, KP323, KP324, KP326, KP340 KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (made by Japan Momentive Performance Materials Co., Ltd.).

The fluorine-based surfactant is exemplified by a surfactant having a fluorocarbon chain. Specifically, FLUORINERT (registered trademark) FC430, FLUORINERT FC431 (Sumitomo 3M (share) system), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC R30 (DIC) EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (Mitsubishi Materials Electronics Co., Ltd.), SURFLON (registered trademark) S381, SURFLON S382, SURFLON SC101, SURFLON SC105 (Asahi Glass Co., Ltd.) ), E5844 (Daikin Institute of Precision Chemistry (stock) system).

The polyfluorene-based surfactant having a fluorine atom is exemplified by a surfactant having a siloxane chain and a fluorocarbon chain. Specifically, it is MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, MEGAFAC F443 (made by DIC). Preferred is MEGAFAC (registered trademark) F475.

The content of the surfactant (F) is relative to the composition of the photosensitive resin The total amount of the material is 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, more preferably 0.01% by mass or more and 0.05% by mass or less. By containing the surfactant in the range of 0.001% by mass or more and 0.2% by mass or less, the flatness of the coating film can be improved.

The photosensitive resin composition of the present invention may optionally contain various additives such as a filler, another polymer compound, an adhesion promoter, an antioxidant, an ultraviolet absorber, a photosetter, and a chain transfer agent.

The adhesion promoter is exemplified by vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, 3-glycidoxy propyl trimethoxy decane, and 3 - glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 2-( 3,4-Epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyl Trimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, N-2-(aminoethyl)-3-amine Propylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxydecane, N-2-(aminoethyl)-3-amine Propyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyl Triethoxy decane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxy Decane and so on.

The photosensitive resin composition of the present invention contains substantially no coloring agent such as a pigment or a dye. That is, in the photosensitive resin composition of the present invention, The coloring agent content with respect to the entire composition is, for example, preferably less than 1% by mass, more preferably less than 0.5% by mass.

The photosensitive resin composition of the present invention is filled in a quartz cell having a light path length of 1 cm, and the average transmittance when the transmittance is measured at a measurement wavelength of 400 to 700 nm using a spectrophotometer is preferably 70% or more. More preferably 80% or more.

When the photosensitive resin composition of the present invention is used as a coating film, the average transmittance of the coating film is preferably 90% or more, more preferably 95% or more. The average transmittance is a coating film having a thickness of 3 μm after heat curing (for example, hardening at 100 to 250 ° C for 5 minutes to 3 hours), and measuring at a measurement wavelength of 400 to 700 nm using a spectrophotometer. The average of the time. According to this, it is possible to provide a coating film excellent in transparency in the visible light region.

The photosensitive resin composition of the present invention can be applied to a substrate such as glass, metal, plastic, or the like, or a substrate on which a color filter, various insulating or conductive films, a driving circuit, or the like is formed, and patterned into a desired shape. Form a pattern. Further, the pattern may be formed as part of a component of a display device or the like.

First, the photosensitive resin composition of the present invention is applied onto a substrate.

As described above, the coating system can be carried out by various coating apparatuses such as spin coating, slit and spin coating, slit coating, inkjet, roll coating, and dip coating.

Next, it is preferred to remove the volatile component such as a solvent by drying or prebaking. According to this, a smooth unhardened coating film can be obtained.

The film thickness of the coating film at this time is not particularly limited, and may be appropriately adjusted depending on the material to be used, the use, and the like, and is exemplified as about 1 to 6 μm.

Next, the obtained uncured coating film is irradiated with light such as ultraviolet light generated by a mercury lamp, a light-emitting diode or the like through a photomask for forming a target pattern. The shape of the mask is not particularly limited at this time, and the shape or size can be selected depending on the use of the pattern.

In recent years, exposure machines have used a filter that cuts off the wavelength region of light up to 350 nm to cut off light in this wavelength region, and are selectively selected using a band pass filter that sweeps light near 436 nm, near 408 nm, and near 365 nm. The light of the wavelength regions is taken out to uniformly illuminate the entire exposed surface with a slightly parallel light. If a device such as a reticle aligner or a stepper is used, the position of the reticle and the substrate at this time can be correctly aligned.

By bringing the exposed coating film into contact with the developing liquid, a specific portion such as an unexposed portion (i.e., a non-pixel portion) is dissolved and developed, and a target pattern shape can be obtained.

The development method may be any one of a discharge method, a dipping method, a spray method, and the like. In addition, the substrate can be tilted at any angle during development.

The developing solution used for development is preferably an aqueous solution of a basic compound.

The basic compound is any one of an inorganic or organic basic compound.

Specific examples of the inorganic basic compound are sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, potassium citrate, Sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, and the like.

The organic basic compound is exemplified by tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, and single Isopropylamine, diisopropylamine, ethanolamine, and the like.

The concentration of the inorganic and organic basic compounds in the aqueous solution is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass.

The aforementioned developing solution may also contain a surfactant.

The surfactant may be any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.

Nonionic surfactants are exemplified by, for example, polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymers, Sorbitol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. .

The anionic surfactants are listed as higher alcohol sulfate salts such as sodium lauryl sulfate or oleyl sulfate, alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate, and dodecylbenzenesulfonic acid. An alkyl aryl sulfonate such as sodium or sodium dodecyl naphthalene sulfonate.

The cationic surfactant is exemplified by an amine salt such as stearylamine hydrochloride or lauryl trimethylammonium chloride or a quaternary ammonium salt.

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

After the development, the pattern can be obtained by washing with water, and then post-baking can be performed as needed. The post-baking is preferably carried out at a temperature ranging from, for example, 150 to 240 ° C for 10 to 180 minutes.

When the uncured coating film is exposed, the mask which forms the pattern is not used, and illuminating and/or developing the entire surface is omitted, and a coating film having no pattern can be obtained.

An example of the display device of the present invention is described below with respect to an organic EL (electroluminescence) display device.

Fig. 1 is a cross-sectional view schematically showing a part of a display device 1 as an example of a display device of the present invention. Fig. 2 is a plan view showing a part of the display device 1 of an example of the display device of the present invention in an enlarged manner. The display device 1 mainly includes a partition wall 3 including a support substrate 2, a section in which a predetermined section is formed on the support substrate 2, and a plurality of organic EL elements 4 provided in a section partitioned by the partition wall 3. The partition wall 3 corresponds to the partition wall for inkjet of the present invention.

The partition wall 3 is formed, for example, in a lattice shape or a strip shape on the support substrate 2. 2 shows a display device 1 in which the grid-shaped partition walls 3 are provided as one embodiment. In the figure, the area where the partition wall 3 is provided is punched.

A plurality of recesses 5 defined by the partition wall 3 and the support substrate 2 are set on the support substrate 2. This recess 5 corresponds to a section divided by the partition wall 3.

The partition wall 3 in the display device 1 is formed in a lattice shape. Therefore, viewed from one of the thickness directions Z of the support substrate 2 (hereinafter sometimes referred to as "plan view"), the plurality of recesses 5 are arranged in a matrix. That is, the recess 5 A certain interval is left in the row direction X, and a certain interval is also left in the column direction Y to be arranged neatly. The shape of each recessed portion 5 in plan view is not limited to this. For example, the concave portion 5 may have a shape such as a substantially rectangular shape, a slightly elliptical shape, or a long elliptical shape in plan view. This embodiment is a recessed portion 5 having a substantially rectangular shape in plan view. In the present specification, the row direction X and the column direction Y refer to a direction perpendicular to the thickness direction Z of the support substrate and perpendicular to each other.

Further, in another embodiment, when the strip-shaped partition wall is provided, the partition wall is configured such that a plurality of partition wall members extending in the row direction X are disposed at a predetermined interval in the column direction Y. In this form, a strip-shaped recess is defined by the strip-shaped partition wall and the support substrate.

The partition wall is formed to be narrowed as it is away from the support substrate. For example, when the partition wall extending in the column direction Y is cut in a plane perpendicular to the extending direction (column direction Y), the cross-sectional shape is formed to be narrower as it goes away from the support substrate. The partition wall of the equilateral trapezoidal shape is shown in Fig. 1. When the upper bottom is compared with the lower bottom of the support substrate side, the lower bottom is wider than the upper base. Further, the cross section of the partition wall actually formed does not necessarily have to have a trapezoidal shape, and the straight portion and the corner portion of the trapezoidal shape may be rounded.

The top surface of the partition wall 3 preferably exhibits liquid repellency. The term "top surface" means a plane existing in the surface of the partition wall 3 which is the farthest from the support substrate 2. By displaying the liquid repellency on the top surface of the partition wall 3, it is possible to prevent the ink supplied to the region (the recess 5) surrounded by the partition wall 3 from being transmitted to the top surface of the partition wall 3 and overflowing to the adjacent region.

The organic EL element 4 is provided in a section (i.e., the recess 5) partitioned by the partition wall 3. A grid-shaped partition wall 3 in the display device 1 is provided At this time, each of the organic EL elements 4 is provided in each of the concave portions 5. In other words, the organic EL element 4 is arranged in a matrix shape in the same manner as each of the concave portions 5, and is spaced apart from each other in the row direction X on the support substrate 2, and is also arranged in a line at a predetermined interval in the column direction Y.

The shape and arrangement of the partition wall 3 are appropriately set depending on the specifications of the display device such as the number of pixels and the resolution, ease of manufacture, and the like. For example, the width of the partition wall 3 in the row direction X or the column direction Y is about 5 μm to 50 μm, the height of the partition wall 3 is about 0.5 μm to 5 μm, and the interval between the partition walls 3 adjacent to the row direction X or the column direction Y is That is, the width of the row direction X or the column direction Y of the concave portion 5 is about 10 μm to 200 μm. Further, the widths of the first electrode 6 in the row direction X or the column direction Y are each about 10 μm to 200 μm.

The partition wall 3 can be formed from the photosensitive resin composition of the present invention by the above-described pattern forming method.

When the strip-shaped partition wall is provided as another embodiment, the organic EL element 4 is disposed at a predetermined interval in each of the recesses extending in the row direction X.

The display device 1 is provided with three kinds of organic EL elements 4. That is, (1) a red organic EL element 4R that emits red light, (2) a green organic EL element 4G that emits green light, and (3) a blue organic EL element 4B that emits blue light.

The organic EL element 4 is formed by sequentially laminating a first electrode, an organic EL layer, and a second electrode from the side of the supporting substrate. In the present specification, one or a plurality of layers provided between the first electrode 6 and the second electrode 10 are also referred to as an organic EL layer. The organic EL element 4 is provided with at least one light emitting layer as Machine EL layer. Further, in addition to the one-layer light-emitting layer, the organic EL element may further include an organic EL layer different from the light-emitting layer. For example, a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, an electron injection layer, and the like are provided as an organic EL layer between the first electrode 6 and the second electrode 10. Further, two or more light-emitting layers may be provided between the first electrode 6 and the second electrode 10.

The organic EL element 4 includes the first electrode 6 and the second electrode 10 as a pair of electrodes formed by an anode and a cathode. One of the first electrode 6 and the second electrode 10 is an anode, and the other electrode is a cathode. The display device 1 is provided with a first electrode 6 that functions as an anode, a first organic EL layer 7 that functions as a hole injection layer, and a second organic EL layer 9 that functions as a light-emitting layer. The second electrode 10 functions as a cathode.

The first electrode 6 is provided on each of the organic EL elements 4. That is, the number of the first electrodes 6 equal to the number of the organic EL elements 4 is provided on the support substrate 2. The first electrodes 6 are provided in accordance with the arrangement of the organic EL elements 4, and are arranged in a matrix like the organic EL elements 4. Further, the partition wall 3 is formed in a lattice shape mainly in a region excluding the first electrode 6, but may be formed to cover the edge portion of the first electrode 6 (see FIG. 1).

The first organic EL layer 7 corresponding to the hole injection layer is provided on the first electrode 6 of the recess 5, respectively. The first organic EL layer 7 may be provided with a different material or film thickness for each organic EL element type as needed. Further, all of the first organic EL layers 7 can be formed of the same material and the same film thickness from the viewpoint of the simple formation step of the first organic EL layer 7.

The first organic EL layer 7 is supplied to the region (recessed portion 5) surrounded by the partition wall 3 by an inkjet method by ink which is a material of the first organic EL layer 7, and then dried, heated, and/or The light is formed by curing the ink.

The second organic EL layer 9 functioning as a light-emitting layer is provided on the first organic EL layer 7 of the concave portion 5. The above-mentioned light-emitting layer is provided in accordance with the kind of the organic EL element. Therefore, the red light-emitting layer 9R is provided in the concave portion 5 in which the red organic EL element 4R is provided, the green light-emitting layer 9G is provided in the concave portion 5 in which the green organic EL element 4G is provided, and the blue light-emitting layer 9B is provided in the blue organic layer. The recess 5 of the EL element 4B.

The second electrode 10 is formed over the entire display region where the organic EL element 4 is provided. In other words, the second electrode 10 is formed not only on the second organic EL layer 9, but also on the partition wall 3, and is formed continuously across the plurality of organic EL elements.

As described above, the organic EL display device can be manufactured by covering the plurality of organic EL elements 4 (not shown) formed on the support substrate 2 with the sealing layer and the sealing substrate.

The pattern obtained by the photosensitive resin composition of the present invention has a high wettability on the surface of the concave portion partitioned by the partition wall and the substrate, and has high liquid repellency on the partition wall, so that it can be used in particular as an ink jet method. A separator used for a filter, an ITO electrode of a liquid crystal display element, an organic EL display element, and a circuit wiring board. Further, for example, an optical spacer which is a part of a color filter substrate and/or an array substrate, a pattern overcoat layer, an interlayer insulating film, and a liquid crystal alignment control can be used. The protrusion, the microlens, the coating for adjusting the film thickness, and the like, the member for the touch panel, and the coating film having the pattern obtained as described above can be used as a part of the color filter substrate and/or the array substrate. Coating. The color filter substrate and the array substrate can be preferably used for a liquid crystal display device, an organic EL display device, electronic paper, or the like.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The "%" and "parts" in the examples are % by mass and parts by mass unless otherwise specified.

(Synthesis Example 1)

Nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer in an appropriate amount to replace the nitrogen gas atmosphere, and 166 parts of propylene glycol monomethyl ether acetate and 52 parts of methoxypropanol were fed, and the mixture was heated to 85 with stirring. °C. Next, 233 parts of a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]non-8-yl acrylate and/or 9-yl acrylate and p-vinylbenzoic acid were added dropwise over 4 hours. 77 parts, a mixed solution of 125 parts of propylene glycol monomethyl ether acetate and 115 parts of methoxypropanol. On the other hand, a mixed solution of 32 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 210 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 3 hours, and then cooled to room temperature to obtain a polymer (resin Aa) solution having a B-type viscosity (23 ° C) of 46 mPas, a solid content of 33.7%, and a solution acid value of 83 mgKOH/g. The obtained resin Aa had a weight average molecular weight Mw of 7.7 × 10 ³ and a molecular weight distribution of 1.90.

The resin Aa has the following structural unit.

(Synthesis Example 2)

Nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer at 0.02 L/min to make a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 3-methoxybutyl acetate were fed. 105 parts by mass, heated to 70 ° C while stirring. Next, 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (the compound represented by the formula (I-1) in a molar ratio of 50:50 and 240 parts by mass of the compound represented by the formula (II-1) was dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution was added dropwise at 70 hours using a dropping funnel over 4 hours. The flask was kept at °C.

On the other hand, using another dropping funnel, 30 parts by mass of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of acetic acid 3- in 4 hours. A solution of methoxybutyl ester was added dropwise to the flask. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a polymer (resin A1a) having a solid content of 32.6% by mass and an acid value of 110 mg KOH/g (in terms of solid content). Solution. The obtained resin A1a had a weight average molecular weight Mw of 1.3 × 10 ⁴ and a molecular weight distribution of 2.50. The resin A1a has the following structural unit.

(Synthesis Example 3)

Feeding 78 parts of α-chloroacrylic acid 3,3,4,4,5,5,6,6,6-nonafluorohexyl ester in a four-necked flask equipped with a reflux condenser, a nitrogen gas introduction tube, a thermometer and a stirring device, 19.5 parts of methacrylic acid, 19.5 parts of isobornyl methacrylate, 13 parts of glycidyl methacrylate, 12.7 parts of dodecanethiol, and 266 parts of propylene glycol monomethyl ether acetate, after heating to 70 ° C, Stir under a stream of nitrogen for 30 minutes. 1 part of azobisisobutyronitrile was added thereto, and polymerization was carried out for 18 hours to obtain a solid content of 33% by mass and an acid value of 68 mgKOH/g (solid A polymer (resin Ba) solution in terms of body composition. The weight average molecular weight of the obtained resin Ba was 7,500. The resin Ba has the following structural units.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example were measured by the GPC method under the following conditions.

Device; K2479 (Shimadzu Corporation (stock) system)

Pipe string; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ° C

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0mL/min

Detector; RI

The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained above was used as the molecular weight distribution.

(Examples 1 to 4 and Comparative Examples 1 to 3)

<Adjustment of photosensitive resin composition>

The components of Table 3 were separately mixed to obtain a photosensitive resin composition.

The components in Table 3 are as follows. The parts described in the column of the resin (A) and the resin (B) are mass parts in terms of solid content.

Resin (A); Aa: Resin Aa obtained in Synthesis Example 1.

Resin (A1); A1a: Resin A1a obtained in Synthesis Example 2.

Resin (B); Ba: resin Ba obtained in Synthesis Example 3.

Polymerizable compound (C); Ca: trimethylolpropane triacrylate (A-TMPT; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

Polymerizable compound (C): Cb: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D); Da: 2-methyl-2-morpholinyl-1-(4-methylmercaptophenyl)propan-1-one (Irgacure (registered trademark) 907; manufactured by BASF Corporation)

Polymerization initiator (D); Db: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-乙醯基肟) (Irgacure (Registrar) Standard) OXE02; made by BASF)

Polymerization initiation aid (D1); 4,4'-bis(diethylamino)benzophenone (EAB-F; manufactured by HODOGAYA Chemical Industry Co., Ltd.)

Solvent (E); Ea: propylene glycol monomethyl ether acetate

Solvent (E); Eb: ethyl 3-ethoxypropionate

Solvent (E); Ec: 3-methoxy 1-butanol

Solvent (E); Ed: 3-methoxybutyl acetate

In the solvent (E), the solid content of the photosensitive resin composition is mixed as in the "solid content (%)" of Table 3, and the value of the solvent (Ea) to (Ed) in the solvent (E) is expressed. The mass ratio in the solvent (E).

<Average transmittance of the composition>

For the photosensitive resin composition obtained above, an ultraviolet-visible near-infrared spectrophotometer (V-650; manufactured by JASCO Corporation) (quartz unit, optical path length; 1 cm) was used to measure the average transmission at 400 to 700 nm. rate(%). The results are shown in Table 3.

<Production of Coating Film>

2 The glass substrate (EAGLE XG; manufactured by CONNING Co., Ltd.) was washed with a neutral detergent, water and alcohol in order, and then dried. Each of the photosensitive resin compositions obtained above was spin-coated on the glass substrate so that the film thickness after post-baking was 3.0 μm, and dried under reduced pressure in a vacuum dryer (manufactured by Microtech Co., Ltd.). After the pressure was 66 kPa, it was dried by prebaking at 80 ° C for 2 minutes on a hot plate. After cooling, an exposure machine (TME-150RSK; TOPCON, light source; ultrahigh pressure mercury lamp) was used, and light having an exposure amount of 50 mJ/cm ² (365 nm reference) was irradiated in an atmosphere. Further, at this time, an ultrahigh pressure mercury lamp was used for the irradiation of the photosensitive resin composition. After illuminating, the coating film was immersed and shaken at 23 ° C for 60 seconds in a water-based developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, followed by heating at 230 ° C in an oven. A coating film was obtained for 20 minutes (post-baking).

<Average transmittance of coating film>

With respect to the obtained coating film, an average transmittance (%) at 400 to 700 nm was measured using a microscopic spectrophotometer (OSP-SP200; manufactured by OLYMPUS). A high transmission rate means that absorption is small. The results are shown in Table 3.

<Contact angle>

With respect to the obtained coating film, the contact angle of anisole was measured using a contact angle meter (DGD Fast/60; manufactured by GBX Corporation).

The higher the contact angle, the higher the liquid repellency. When the contact angle of the coating film is high, the pattern contact angle formed even by using the same photosensitive resin composition is high. The partition wall is formed of a photosensitive resin composition having a high contact angle, and the ink is easily repelled when the ink is transferred by the ink jet device while being surrounded by the partition wall. Therefore, for example, when a color filter is produced by an inkjet method, ink color mixing is less likely to occur between adjacent pixel regions. The results are shown in Table 5.

<Form Formation>

The glass substrate (EAGLE XG; manufactured by CONNING Co., Ltd.) on which ITO was deposited on the surface was washed with a neutral detergent, water and 2-propanol, and then dried. Each of the photosensitive resin compositions obtained above was spin-coated on the glass substrate so that the film thickness after post-baking was 1.0 μm, and dried under reduced pressure in a vacuum dryer (manufactured by Microtech Co., Ltd.). After the pressure was 66 kPa, it was dried by prebaking at 90 ° C for 2 minutes on a hot plate.

After cooling, the distance between the substrate on which the photosensitive resin composition was applied and the mask made of quartz glass was set to 100 μm, and an exposure machine (TME-150RSK; TOPCON, light source; ultrahigh pressure mercury lamp) was used in the atmosphere. In the atmosphere, light having an exposure amount of 200 mJ/cm ² (365 nm reference) was irradiated. In addition, as the mask, the pattern is formed on the same plane (the shape of the light-shielding portion is a shape (ellipse) in which the four corners are rounded in a rectangular shape of 300 μm in the longitudinal direction and 100 μm in the short-axis direction).

After illuminating, the aqueous solution of tetramethylammonium hydroxide (TOKUYAMA, TOKUSO SD25) was diluted with pure water to a developing solution prepared to have a concentration of 2.38%, and the coating film was shaken at 23 ° C. After 60 seconds of side development, after washing with water, post-baking was carried out in an oven at 230 ° C for 20 minutes to obtain a pattern.

<Wettability>

[Production of solution for wettability evaluation]

The solvent for evaluating the wettability of the partition wall was selected from N,N-dimethylacetamide (manufactured by Wako Pure Chemical Co., Ltd., 99.5% or more) and 1,3-dimethyl-2-imidazolidinone ( Tokyo Chemical Industry Co., Ltd., 99.0% Upper) two. Since the selected two solvents have low viscosity, cyclohexanone (manufactured by Wako Pure Chemical Co., Ltd., 98.0% or more) is added as a viscosity adjusting material, and as a mixed solvent, the liquid can be applied to the partition wall by the ink jet device. Filling.

Further, since the solvent monomer was difficult to be observed by drying under a microscope, Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd., purity: 95% or more) was used as the solute.

The solution was prepared in three of the following Tables 4.

[Wettability evaluation]

The above-described solution was filled in a partition wall with a partition wall of 1000 parts per 200 pL in each partition wall using an inkjet apparatus (Litlex 120L manufactured by ULVAC Co., Ltd.), and dried using a microscope (MX61L manufactured by OLIMPUS). , lens LCPFLN20 × LCD), the solute is extended to the end of the partition wall for 30 parts of observation. In all of the solutions shown in Table 4, when 30 parts were coated, the wettability was good and the evaluation was ○, and the evaluation was ×. The results are shown in Table 5.

As a result of the examples, it is understood that the photosensitive resin composition of the present invention does not cause ink color mixing and maintains a contact angle, thereby obtaining a coating film and a pattern excellent in wettability.

[Industrial availability]

According to the photosensitive resin composition of the present invention, a pattern excellent in wettability can be obtained, that is, the wettability of the surface of the concave substrate divided by the partition wall and the substrate is high, and the liquid repellency on the partition wall is high. type.

Claims (6)

A photosensitive resin composition containing (A), (B), (C), and (D), and the content of (A) is 45 mass% or more and 80 mass based on the total content of (A) and (C) (A) a structural unit containing an structural unit derived from an aromatic carboxylic acid having an ethylenically unsaturated bond, an unsaturated compound derived from a cyclic ether structure having a carbon number of 2 to 4, and having no carbon a polymer of a structural unit of 4 to 6 perfluoroalkyl groups, (B) a polymer having a structural unit having a perfluoroalkyl group having 4 to 6 carbon atoms, (C) a polymerizable compound, and (D) polymerization Starting agent. The photosensitive resin composition of claim 1, wherein (D) contains at least one polymerization initiator selected from the group consisting of a biimidazole compound, a benzophenone compound, and an O-mercaptopurine compound. A pattern formed by the photosensitive resin composition of claim 1 or 2. A partition wall for inkjet which is formed of the photosensitive resin composition of claim 1 or 2. A display device comprising a pattern as claimed in claim 3. A display device comprising the separation wall for inkjet as claimed in claim 4.