TWI632429B - Photosensitive resin composition - Google Patents

Abstract

A photosensitive resin composition containing (A), (B), (C), and (D).

(A) A polymer having a structural unit having a phenolic hydroxyl group and not having a structural unit having a perfluoroalkyl group having 4 to 6 carbon atoms

(B) a polymer containing a structural unit having a perfluoroalkyl group having 4 to 6 carbon atoms

(C) Polymerizable compound

(D) a polymerization initiator.

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition.

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

In terms of such a photosensitive resin composition, for example, a photosensitive resin composition containing a copolymer of methacrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate is known as a resin (patent Reference 1).

Prior art literature Patent literature

Patent Document 1: Japanese Unexamined Patent Publication No. 2012-73603

The inkjet printing device is used to apply an ink containing an organic functional material to a recess defined by the partition wall formed on the substrate and the substrate. In this case, it is preferable that the wettability is so high that the surface of the recessed substrate is completely covered with ink, and to prevent the ink from leaking out of the intended area, and the wettability on the partition wall of the substrate surface is low (high liquid repellency). However, the wettability between the partition wall formed by the conventionally proposed photosensitive resin composition and the surface of the recessed substrate defined by the substrate may not be satisfied.

The present invention provides the following [1] to [7].

[1] A photosensitive resin composition containing (A), (B), (C), and (D).

(A) A polymer having a structural unit having a phenolic hydroxyl group and not having a structural unit having a perfluoroalkyl group having 4 to 6 carbon atoms

(B) a polymer containing a structural unit having a perfluoroalkyl group having 4 to 6 carbon atoms

(C) Polymerizable compound

(D) a polymerization initiator.

[2] (B) The photosensitive resin composition according to [1], which is a polymer further having a structural unit of at least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride.

[3] (D) is the one described in [1] or [2] containing at least one polymerization initiator selected from the group consisting of a biimidazole compound, an alkyl phenone compound, and an O-fluorenyl oxime compound Photosensitive resin composition.

[4] A pattern formed from the photosensitive resin composition according to any one of [1] to [3].

[5] A partition wall for inkjet printing formed from the photosensitive resin composition according to any one of [1] to [3].

[6] A display device including the pattern described in [4].

[7] A display device including the partition wall for inkjet printing according to [5].

According to the photosensitive resin composition of the present invention, a pattern having excellent wettability, that is, a pattern having high wettability on the surface of a recessed base plate defined by a partition wall and a substrate, and a pattern with high liquid repellency on the partition wall can be obtained.

1‧‧‧ display device

2‧‧‧ support substrate

3‧‧‧ next door

4‧‧‧Organic EL element

5‧‧‧ recess

6‧‧‧The first electrode

7‧‧‧The first organic EL layer (hole injection layer)

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

10‧‧‧ 2nd electrode

FIG. 1 is a schematic cross-sectional view in which a part of the display device 1 is enlarged.

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

The photosensitive resin composition of the present invention is a photosensitive resin composition containing (A), (B), (C), and (D).

(A) A polymer having a structural unit having a phenolic hydroxyl group and not having a structural unit having a perfluoroalkyl group having 4 to 6 carbon atoms (hereinafter referred to as "resin (A)") (B) Polymer with 4 to 6 carbon perfluoroalkyl structural units (hereinafter referred to as "resin (B)")

(C) Polymerizable compound

(D) Polymerization initiator

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

In this specification, the compounds exemplified as each component are not specifically described. Without limitation, they can be used alone or in combination.

The resin (A) is a resin containing a structural unit having a phenolic hydroxyl group, and the structural unit is derived from a monomer (a) having a phenolic hydroxyl group (hereinafter referred to as "(a)").

The resin (A) may further contain a structural unit derived from a monomer (x) other than (a) (however, it does not have a perfluoroalkyl group having 4 to 6 carbon atoms) (hereinafter referred to as "(x)").

(a) A monomer having a phenolic hydroxyl group and an ethylenically unsaturated double bond is preferred.

Monomers having phenolic hydroxyl and ethylenically unsaturated double bonds. Specific examples include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, hydroxyphenyl (meth) acrylate, and hydroxybenzene. (Meth) acrylamide, hydroxyphenylmaleimide, and the like.

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

(x) is a monomer other than (a) and is not particularly limited as long as it does not have a perfluoroalkyl group having 4 to 6 carbon atoms, for example, a monomer (b) having a cyclic ether structure with 2 to 4 carbon atoms (Hereinafter referred to as "(b)"), at least one monomer (e) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter referred to as "(e)"), Other monomers (c) (hereinafter referred to as "(c)"). It is preferably (b) and / or (c).

(b) A cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from the group consisting of an ethylene oxide, an oxetane ring, and a tetrahydrofuran ring. 1 type) monomer is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated double bond, and more preferably a cyclic ether structure having 2 to 4 carbon atoms and (methyl ) Acrylic fluorenyloxy monomer.

(b) Examples of the monomer (b1) having an ethylene oxide group (hereinafter referred to as "(b1)"), and the monomer (b2) having an oxetanyl group (hereinafter referred to as "(b2) ) "), A monomer (b3) having a tetrahydrofuranyl group (hereinafter referred to as" (b3) "), and the like.

(b1) Examples of the monomer include a monomer (b1-1) having a structure in which an unsaturated aliphatic hydrocarbon is epoxidized (hereinafter referred to as "(b1-1)"), and an unsaturated alicyclic hydrocarbon ring Oxidized structured monomer (b1-2) (hereinafter referred to as "(b1-2)").

(b1) A monomer having an epoxyethyl group and a (meth) acrylfluorenyloxy group is preferred, a structure having an unsaturated alicyclic hydrocarbon is epoxidized, and a monomer having a (meth) acrylfluorenyloxy group Better body. When these preferable monomers are used, the storage stability of the photosensitive resin composition is excellent.

(b1-1), specifically, for example, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl Glyceryl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl Glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) ) Styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) Phenyl) phenylethyl Ene, 2,3,4-ginseng (glycidyloxymethyl) styrene, 2,3,5-ginseng (glycidyloxymethyl) styrene, 2,3,6-ginseng (glycidyl Methoxymethyl) styrene, 3,4,5-gins (glycidyloxymethyl) styrene, 2,4,6-gins (glycidyloxymethyl) styrene, JP-A-7 Compounds described in Japanese Patent Publication No. -248625.

(b1-2), for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000; Daicel Chemical Industry Co., Ltd.) 3,4-epoxycyclohexyl methacrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxy cyclohexyl methacrylate (for example, Cyclomer (Registered trademark) M100; Daicel Chemical Industry Co., Ltd.), a compound represented by formula (I), a compound represented by formula (II), and the like.

[In the formula (I) and the formula (II), R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a 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 -, *} - R 3 -O -, * - R 3 -S-, or * -R ³ -NH-.

R ³ is an alkanediyl group having 1 to 6 carbon atoms.

＊ Bonding to O. ]

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ and R ² include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl. .

Examples of the hydroxy-substituted alkyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, and 1-hydroxy-1- Methylethyl, 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, and more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group having 1 to 6 carbon atoms represented by R ³ include methyl, ethyl, propane-1,2-diyl, propane-1,3-diyl, and butane-1,4. -Diyl, pentane-1,5-diyl, hexane-1,6-diyl, etc.

X ¹ and X ^{2 are} preferably a single bond, methyl group, ethyl group, * -CH ₂ -O- (* is a bond with O) group, * -CH ₂ CH ₂ -O- group, More preferred examples include a single bond and a * -CH ₂ CH ₂ -O- group.

Examples of the compound represented by formula (I) include compounds represented by formula (I-1) to formula (I-15). Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15) The compound represented is preferably, and the compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) is more preferable.

Examples of the compound represented by formula (II) include compounds represented by formula (II-1) to formula (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15) The compound represented is preferably, and the compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferable.

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more kinds. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, these content ratios [compound represented by the formula (I): compound represented by the formula (II)] are on a Mohr basis , Preferably 5:95 to 95: 5, and more preferably 20:80 to 80:20.

(b2) A monomer having an oxetanyl group and a (meth) acrylfluorenyloxy group is preferred. (b2), for example, 3-methyl-3- (meth) propenyloxymethyloxetane, 3-ethyl-3- (meth) propenyloxymethyloxy Heterocyclobutane, 3-methyl-3- (meth) propenyloxyethyloxetane, 3-ethyl-3- (meth) propenyloxyethyloxane Butane and so on.

(b3) A monomer having a tetrahydrofuranyl group and a (meth) acrylfluorenyloxy group is preferred.

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

(e) Examples include unsaturated carboxylic acids and unsaturated carboxylic anhydrides.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, vinyl benzoic acid, maleic acid, fumaric acid, citraconic acid, methyl fumaric acid, itaconic acid, vinyl phthalic acid, 3, 4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic 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] hept-2-ene, succinic acid mono [2- (meth) acrylfluorenyloxyethyl], phthalic acid mono [ 2- (meth) acrylfluorenyloxyethyl], α- (hydroxymethyl) acrylic acid, and the like.

Examples of unsaturated carboxylic acid anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrobenzene Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, etc. Unsaturated dicarboxylic acids and the like.

(c), for example, (meth) acrylates, N-substituted malay 醯 Imine unsaturated dicarboxylic acid diesters, alicyclic unsaturated compounds, styrenes, and other vinyl compounds. Among them, (meth) acrylates and styrenes are preferred.

Examples of (meth) acrylates include methyl methacrylate, meth (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and sec-butyl (Meth) acrylates, tert-butyl (meth) acrylates and other alkyl esters; cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclic [ 5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (commonly known in this technical field as dicyclopentyl (meth) acrylate.), Dicyclopentyloxyethyl (Meth) acrylate, tricyclic [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate (in this technical field, the common name is "dicyclopentene (meth) acrylate ".), Cycloalkyl esters such as isobornyl (meth) acrylate; hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Types; aryl (aryl) esters such as phenyl (meth) acrylate, benzyl (meth) acrylate, and the like.

Among the (meth) acrylates, alkyl esters are preferred.

Examples of the unsaturated dicarboxylic acid diesters include diethyl maleate, diethyl fumarate, and diethyl iconate.

Examples of the N-substituted maleimidines include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimine- 3-maleimide benzoate, N-succinimide-4-maleimide Butylamine, N-succinimide-6-maleimide hexanoate, N-succinimide-3-maleimide propionate, N- (9-acridyl) horse Laimide and so on.

Examples of the alicyclic unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1] heptane. 2-ene, 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-bis (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-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5 -Phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyl) (Oxycarbonyl) bicyclic unsaturated compounds such as bicyclo [2.2.1] hept-2-ene and the like.

Examples of the styrenes include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene. Among them, styrene and vinyl toluene are preferred.

Other vinyl compounds include, for example, (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2, 3-dimethyl-1,3-butadiene and the like.

Resin (A) may be composed only of structural units derived from (a) The resin is preferably a resin composed of a structural unit derived from (a) and a structural unit derived from (x).

When the resin (A) is a resin composed of the structural unit derived from (a) and the structural unit derived from (x), the ratio of the structural unit derived from each monomer to the total mole number of the structural unit constituting the resin (A) It is preferably within the following range.

Structural unit from (a); 5 ~ 70 mole% (more preferably 10 ~ 60 mole%)

Structural unit from (x); 30 ~ 95 mole% (more preferably 40 ~ 90 mole%)

The ratio of the structural unit of the resin (A) is within the above range, the storage stability of the photosensitive resin composition, the developability when a pattern is formed from the photosensitive resin composition, and the resistance of the obtained coating film and pattern Solvent properties, heat resistance, and mechanical strength tend to be good.

For the resin (A), refer to, for example, the method described in the document "Experimental Method of Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd., the first edition of the Chemical Co., Ltd., 1st issue, March 1, 1972) and the references cited in the document. Literature to make.

Specifically, for example, a specific amount of (a) and (x), a polymerization initiator, and a solvent to be used in a reaction vessel are placed in a reaction container, and for example, nitrogen is used to replace oxygen in the atmosphere to create a deoxidizing environment, and stirring Heating and holding method. In addition, the polymerization initiator, solvent, and the like used here are not particularly limited, and can be generally used by users in this field. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4- Dimethylvaleronitrile), etc.) or organic peroxides (benzylidene peroxide, etc.), and the solvent may be one that dissolves each monomer. As the solvent (E) of the photosensitive resin composition, a solvent described later can be used. . In order to adjust the molecular weight of the obtained resin, a chain transfer agent may be added during the polymerization reaction. Examples of the chain transfer agent include n-butanethiol, tert-butanethiol, n-dodecanethiol, 2-mercaptoethanol, ethanethiol acid, ethyl thiolate, ethylthiol 2-ethylhexyl acid ester, methoxybutyl ethionate, 3-mercaptopropionic acid, mercapto-containing silicone (KF-2001: manufactured by Shin-Etsu Chemical), and other thiols; chloroform, carbon tetrachloride Halogenated alkyl esters such as carbon tetrabromide and the like.

During the polymerization, a monomer in which the phenolic hydroxyl group (a) has been previously protected with a protective group can be used. Examples of the protecting group include tertiary alkyl groups such as tert-butyl, and fluorenyl groups such as ethylfluorenyl. After polymerizing using such a monomer previously protected with a protective group, the protective group is deprotected to obtain a resin (A).

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

The polystyrene equivalent weight average molecular weight of the resin (A) is preferably 3,000 to 100,000, and more preferably 5,000 to 50,000. When the weight average molecular weight of the resin (A) is within the aforementioned range, there is a tendency that the coating property is excellent and the film of the exposed portion is less likely to be generated during development, and the non-exposed portion is easily removed by development.

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

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

The content of the resin (A) is preferably 5 to 95% by mass, and more preferably 20 to 80% by mass relative to the total amount of the resin (A), the resin (B), the resin (A1), and the polymerizable compound (C). The best quality is 40-60% by mass. When the content of the resin (A) is within the aforementioned range, the developability of the photosensitive resin composition, the adhesion of the obtained pattern, the solvent resistance, and the mechanical properties tend to be good.

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

(d) Examples include compounds represented by formula (d-0).

[In the formula (d-0), R ^f is a perfluoroalkyl group having 4 to 6 carbon atoms.

R ^d is 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, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom or a hydroxyl group.

X ^d is a single bond, a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a bivalent alicyclic hydrocarbon group having 3 to 10 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and the aliphatic hydrocarbon group and the aliphatic -CH ₂ -contained in the cyclic hydrocarbon group may be substituted by -O-, -CO-, -NR ^e- , -S-, or -SO _2- . ]

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

Examples of the alkyl group having 1 to 21 carbon atoms in R ^d include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. , N-nonyl, n-decyl and other straight-chain alkyl groups; isopropyl, isobutyl, sec-butyl, isopentyl, 1-methylpentyl, 2-methylpentyl, 3 -Methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl , 5-methylhexyl, 1-ethylpentyl, 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-butylbutyl, 1-butyl-2-methylbutyl, 1-butyl-3-methylbutyl, tert-butyl, 1,1-dimethyl Propylpropyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethyl-2 -Methylpropyl, 1,1-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 2,2- Dimethylpentyl, 2,3-dimethyl Pentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3,4-dimethylpentyl, 1-ethyl-1-methylbutyl, 2-ethyl Branched alkyl groups such as 3-methylbutyl and the like.

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

Examples of the divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms in X ^d include methyl, ethyl, propane-1,3-diyl, propane-1,2-diyl, butane-1, 4-diyl, butane-1,3-diyl, butane-1,2-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1, 7-diyl, octane-1,8-diyl and the like.

Examples of the divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms in X ^d include cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, cycloheptanediyl, and cyclo Decanediyl and the like.

Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms in X ^d include phenylene and naphthyldiyl.

-CH ₂ -contained in a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms and a bivalent alicyclic hydrocarbon group having 3 to 10 carbon atoms is -O-, -CO-, -NR ^e- , -S- or- SO ₂ - substituted X ^d, and the like can be exemplified as formula (xd-1) ~ formula (xd-10) represented by the group.

X ^d is preferably an alkanediyl group having 1 to 6 carbon atoms, and ethylene is more preferred.

(d) A compound represented by the formula (d-0 ') is preferred.

[In the formula (d-0 '), R ^h is a perfluoroalkyl group having 4 to 6 carbon atoms.

R ^g is a hydrogen atom, a halogen atom, or a methyl group. ]

Examples of the compound represented by the formula (d-0) include compound (d-1) to compound (d-94). In the table, the formula numbers shown in column X ^{d are} the formula numbers of the above-mentioned examples. The compound (d-1) is, for example, a compound represented by the following formula (d-1).

The resin (B) contains at least one monomer selected from the group consisting of a structural unit derived from a perfluoroalkyl group having a carbon number of 4 to 6 and a group derived from an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. The polymer of the structural unit of the body (e) is preferable, and the resin containing the structural unit from (d) and the structural unit from (e) and the structural unit from (b) is more preferable. Since the resin (B) contains a structural unit derived from (e), it has excellent developability and can suppress the formation of residues or development. Uneven tendency.

Since the resin (B) contains the structural unit derived from (b), it tends to be excellent in solvent resistance, so it is preferable. The resin (B) may contain a structural unit derived from (c). (e), (b), and (c) may be the same as those described above, for example.

When the resin (B) is a polymer of (e) and (d), the ratio of the structural unit derived from each monomer to the total mole number of the structural unit constituting the resin (B) is preferably within the following range.

Structural unit from (e); 5-50% by mass (more preferably 10-40% by mass)

Structural unit from (d); 50 ~ 95 mass% (more preferably 70 ~ 90 mass%)

When the resin (B) is a polymer of (e), (b), and (d), the ratio of the structural unit derived from each monomer to the total mole number of the structural unit constituting the resin (B) is as follows The range is better.

Structural unit from (e); 5 ~ 40 mass% (more preferably 10 ~ 30 mass%)

Structural unit from (b); 5 ~ 80% by mass (more preferably 10 ~ 70% by mass)

Structural unit from (d); 10 ~ 80 mass% (more preferably 20 ~ 70 mass%)

When the resin (B) is a polymer of (e), (b), (c), and (d), the ratio of the structural unit derived from each monomer to the total mole number of the structural unit constituting the resin (B), The following range is preferable.

Structural unit from (e); 5 ~ 40 mass% (more preferably 10 ~ 30 mass) the amount%)

Structural unit from (b); 5 ~ 70 mass% (more preferably 10 ~ 60 mass%)

Structural unit from (c); 10-50% by mass (more preferably 20-40% by mass)

Structural unit from (d); 10 ~ 80 mass% (more preferably 20 ~ 70 mass%)

When the ratio of each structural unit is in the above-mentioned range, there is a tendency that the liquid repellency and developability are excellent.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 20,000, and more preferably 5,000 to 15,000. When the weight average molecular weight of the resin (B) is within the aforementioned preferred range, there is a tendency that the coating property is excellent, the film of the exposed portion is less likely to be generated during development, and the non-exposed portion is easily removed by development.

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

The content of the resin (B) is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass based on 100 parts by mass of the total amount of the resin (A), the resin (A1), and the polymerizable compound (C). When the content of the resin (B) is within the aforementioned preferred range, the developability is excellent when the pattern is formed, and the obtained pattern tends to have excellent liquid repellency.

The photosensitive resin composition of the present invention is a resin other than the resin (A) and the resin (B), that is, a resin having no phenolic hydroxyl group and a perfluoroalkyl group having 4 to 6 carbon atoms is not particularly limited. Resin (A1), for example Resin (A1-1): polymer polymerized by (e) and (b), resin (A1-2): polymer resin (A1) polymerized by (e) and (b) and (c) -3): (e) and (c) polymerized polymer and resin (A1-4): (e) and (c) polymerized polymer and (b) reacted resin, Resin (A1-5): A resin obtained by reacting a copolymer obtained by polymerizing (b) and (c) with (e).

Among them, resin (A1-1) and resin (A1-2) are preferred.

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

Structural unit from (e); 5 ~ 60 mole% (more preferably 10 ~ 50 mole%)

Structural unit from (b); 40 ~ 95 mole% (more preferably 50 ~ 90 mole%)

When the ratio of the structural unit of the resin (A1-1) is within the above range, there are storage stability of the photosensitive resin composition, developability when a pattern is formed from the photosensitive resin composition, and the obtained coating film and pattern. The solvent resistance tends to be good.

The ratio of the structural units derived from each monomer in the resin (A1-2) is preferably in the following range relative to the total number of moles of all the structural units constituting the resin (A1-2).

Structural unit from (e); 2 ~ 45 mole% (more preferably 5 ~ 40 mole%)

Structural unit from (b); 2 ~ 95 mole% (more preferably 5 ~ 80 mole%)

Structural unit from (c); 1 ~ 65 mole% (more preferably 5 ~ 60 mole%)

When the ratio of the structural unit of the resin (A1-2) is within the above range, there are storage stability of the photosensitive resin composition, developability when a pattern is formed from the photosensitive resin composition, and the obtained coating film and pattern. The solvent resistance tends to be good.

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

Structural unit from (e); 2 ~ 40 mole% (more preferably 5 ~ 35 mole%)

Structural unit from (c); 60 ~ 98 mole% (more preferably 65 ~ 95 mole%)

When the ratio of the structural unit of the resin (A1-3) is within the above range, there are storage stability of the photosensitive resin composition, developability when a pattern is formed from the photosensitive resin composition, and the obtained coating film and pattern. The solvent resistance tends to be good.

The resins (A1-1) to (A1-3) can be produced in the same manner as the resin (A).

Resin (A1-4) is a resin obtained by reacting a copolymer of (e) and (c) with (b).

The resin (A1-4) can be produced through, for example, a two-step process. In this case, you can also refer to the above-mentioned document "Experimental Methods for Polymer Synthesis" (by Otsu Takayuki Publishing House) (Shares) Chemical Doubt, 1st edition, 1st brush, issued on March 1, 1972), and the method described in JP 2001-89533.

First, as the first stage, the polymers of (e) and (c) were obtained in the same manner as in the method for producing the resin (A).

At this time, as in the above, the obtained copolymer can be used as it is after the reaction, as a concentrated or diluted solution, or as a solid (powder) by a method such as reprecipitation. Moreover, 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 units derived from (e) and (c) is preferably within the following range relative to the total number of moles of all the structural units constituting the polymer.

Tectonic units from (e); 5-50 mol% (more preferably 10-45 mol%)

Structural unit from (c); 50 ~ 95 mole% (more preferably 55 ~ 90 mole%)

Next, as a second stage, a part of the carboxylic acid or carboxylic anhydride derived from the polymer (e) obtained is reacted with the cyclic ether of the aforementioned (b). Since the cyclic ether is highly reactive and unreacted (b) is difficult to remain, the (b) used for the resin (A1-2) is preferably (b1) or (b2), and more preferably (b1-1).

Specifically, following the above description, the environment in the flask was replaced by nitrogen to air, and 580 mol% (b) relative to the number of moles of (e) was compared to the total amount of (e), (b), and (c). 0.001 to 5% by mass of a carboxyl group and a cyclic ether reaction catalyst (e.g., (dimethylaminomethyl) phenol, etc.), and the relative amounts of (e), (b), and (c) 0.001 to 5% by mass of a polymerization inhibitor (for example, hydroquinone, etc.) was placed in a flask, and a reaction was performed at 60 to 130 ° C for 1 to 10 hours to obtain a resin (A1-4). In addition, similar to the polymerization conditions, the addition method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the manufacturing equipment or polymerization.

At this time, the molar number of (b) is preferably 10 to 75 molar%, and more preferably 15 to 70 molar% relative to the molar number of (e). Within the aforementioned preferred range, the storage stability of the photosensitive resin composition, the developability when the pattern is formed from the photosensitive resin composition, and the solvent resistance, heat resistance, and mechanical strength of the obtained coating film and pattern And the balance of sensitivity tends to be good.

The resin (A1-5), as the first stage, can obtain polymers of (b) and (c) in the same manner as in the method for producing the resin (A).

At this time, as in the above, the obtained copolymer can be used as it is after the reaction, as a concentrated or diluted solution, or as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c) is preferably within the following range relative to the total number of moles of all the structural units constituting the polymer.

Structural unit from (b); 5 ~ 95 mole% (more preferably 10 ~ 90 mole%)

Structural unit from (c); 5 ~ 95 mole% (more preferably 10 ~ 90 mole%)

Further, in the same manner as the method for producing the resin (A1-4), the cyclic ether derived from (b) and the carboxylic acid or carboxylic acid anhydride contained in (e) in the polymers of (b) and (c) can be used. Obtained by reaction. The hydroxy group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride can be further reacted with a carboxylic acid anhydride.

The amount of (e) used in reaction with the aforementioned polymer is preferably 5 to 80 mole% relative to the mole number of (b). Since the cyclic ether is highly reactive and unreacted (b) is unlikely to remain, (b) is preferably (b1), and more preferably (b1-1).

The polystyrene equivalent weight average molecular weight of the resin (A1) is preferably 3,000 to 100,000, and more preferably 5,000 to 50,000. When the weight average molecular weight of the resin (A1) is within the aforementioned preferred range, it tends to be excellent in coatability, and it is difficult to reduce the film of the exposed portion during development, and the non-exposed portion is easily removed by development.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A1) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is within the aforementioned preferred range, it tends to be excellent in developability.

The resin (A1) has an acid value of 20 to 150 mgKOH / g, preferably 40 to 135 mgKOH / g, and more preferably 50 to 135 mgKOH / g.

When the resin (A1) is contained, its content is preferably 1 to 80% by mass, and more preferably 1 to 50% by mass relative to the total amount of the resin (A) and the resin (A1). When the content of the resin (A1) is within the aforementioned preferred range, the pattern can be formed with high sensitivity and excellent developability.

The photosensitive resin composition of this invention contains a polymerizable compound (C).

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

Polymerizable compound with one ethylenically unsaturated bond (C) For example, the same thing as the compound listed in said (a), (b), and (c) is mentioned, Among them, (meth) acrylate is preferable.

Examples of the polymerizable compound (C) having two ethylenically unsaturated bonds include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, and 1, 6-Hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, three Ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, bis (acryloxyethyl) ether of bisphenol A, ethoxylation Bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, 3-methylpentyl Alkanediol di (meth) acrylate and the like.

Examples of the polymerizable compound (C) having three ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and ginseng (2-hydroxyethyl) isocyanate. Cyanurate tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (methyl) Base) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol pentaerythritol hexa (methyl) Base) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, reactant of pentaerythritol tri (meth) acrylate and anhydride, dipentaerythritol penta (meth) acrylate and anhydride Reactant of tripentaerythritol hepta (meth) acrylate and anhydride, caprolactone-modified trimethylolpropane Alkane tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified ginseng (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone Lactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol Tetrakis (meth) acrylate, caprolactone-modified pentaerythritol penta (meth) acrylate, caprolactone-modified pentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol hepta (meth) Acrylate, caprolactone-modified pentaerythritol octa (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate and anhydride reactant, caprolactone-modified dipentaerythritol penta (meth) acrylic acid Reactants of esters and anhydrides, reactants of caprolactone-modified tripentaerythritol hepta (meth) acrylate and anhydrides, etc.

Among them, a polymerizable compound (C) having three ethylenically unsaturated bonds is preferred, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylic acid. Ester is better.

The content of the polymerizable compound (C) is preferably 5 to 95% by mass, and more preferably 20 to 80% by mass based on the total amount of the resin (A), the resin (A1), and the polymerizable compound (C).

When the content of the polymerizable compound (C) is within the aforementioned range, the sensitivity, the strength, 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 that can start polymerization by the action of light or heat, and a conventional polymerization initiator can be used.

Examples of the polymerization initiator (D) include O-fluorenyl oxime compounds and alkylbenzenes. Ketone compounds, biimidazole compounds, triazine compounds and fluorenylphosphine oxide compounds. In addition, a photo and / or thermal cationic polymerization initiator described in Japanese Patent Application Laid-Open No. 2008-181087 (for example, an onium cation and a Lewis acid-derived anion) may be used. Among them, at least one selected from the group consisting of a biimidazole compound, an alkyl phenone compound, and an O-fluorenyl oxime compound is preferable. Polymerization initiators containing these compounds are particularly preferred because they have a high sensitivity.

The O-fluorenyl oxime compound is a compound having a partial structure represented by formula (d1). In the following, * is a bond.

Examples of the O-fluorenyl oxime compound include N-benzyloxy-1- (4-phenylmercaptophenyl) butane-1-one-2-imine, and N-benzyloxy 1- (4-phenylmercaptophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylmercaptophenyl) -3-cyclopentyl Propane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] ethyl Alkane-1-imine, N-ethoxyl-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxolane Alkylmethyloxy) benzamidine} -9H-carbazol-3-yl] ethane-1-imine, N-ethoxyl-1- [9-ethyl-6- (2- Methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzyloxy-1- [9-ethyl-6- ( 2-methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one -2-imine and so on. Commercially available products such as IRGACURE (registered trademark) OXE01, OXE02 (above, manufactured by BASF), and N-1919 (made by ADEKA) can also be used.

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

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylmercaptophenyl) propane-1-one and 2-dimethylamine. 1- (4-morpholinophenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- 1- [4- (4-morpholinyl) phenyl] butane-1-one and the like. Commercial products such as IRGACURE (registered trademark) 369, 907, 379 (above, manufactured by BASF) can also be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1- [4- ( 2-hydroxyethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one Oligomers, α, α-diethoxyacetophenone, benzyldimethylketal, etc.

In terms of sensitivity, the alkyl phenone compound is preferably a compound having a partial structure represented by formula (d2).

Examples of the biimidazole compound include 2,2'-bis (2-chlorobenzene Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiphenyl Imidazole (refer to, for example, Japanese Patent Application Laid-Open No. 6-75372 and Japanese Patent Application Laid-Open No. 6-75373), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl Biimidazole, 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 (see, for example, Japanese Patent Application Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.), and 4,4 ', 5,5'-phenyl groups are carbonyl alkoxy (For example, refer to Japanese Patent Application Laid-Open No. 7-10913). Preferably, for example, 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 .

Examples of the triazine compound include 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-piperidyl-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 Group] -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. .

Examples of the fluorenylphosphine oxide compound include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide and the like.

Further polymerization initiator (D) can be exemplified by benzoin, Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, o-benzylidene benzoic acid methyl ester, 4-phenyldiphenyl Ketone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10-butyl-2-chloroacridone, Benzyl ester, phenylglyoxylic acid methyl ester, titanocene compound and the like. These are preferably used in combination with a polymerization initiator (D1) described later.

As the polymerization initiator having a group capable of causing chain transfer, a polymerization initiator described in Japanese Patent Application Publication No. 2002-544205 can be used.

The aforementioned polymerization initiator having a group capable of causing chain transfer can also be used as the component (c) constituting the resin (A).

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

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

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, and 4-dimethylamino group. Methyl benzoate, 4-dimethylamino benzoate ethyl ester, 4-dimethylamino benzoate isoamyl ester, 4-dimethylamino benzoate 2-ethylhexyl ester, benzoin Acid 2-dimethylaminoethyl ester, N, N-dimethyl-p-toluidine, 4,4'-bis (dimethylamino) benzophenone (general name; Michler's ketone), 4 , 4'-bis (diethylamino) benzophenone-like aromatic amine compound.

Examples of the carboxylic acid compound include phenylmercaptoacetic acid, methylphenylmercaptoacetic acid, ethylphenylmercaptoacetic acid, methylethylphenylmercaptoacetic acid, dimethylphenylmercaptoacetic acid, and methoxyphenylmercaptoacetic acid. , Dimethoxyphenyl mercaptoacetic acid, chlorophenyl mercaptoacetic acid, dichlorophenyl mercaptoacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycolic acid, naphthalene Aromatic heteroacetic acids such as oxyacetic acid.

The combination of the polymerization initiator (D) and the polymerization initiator (D1) includes, for example, an alkyl phenone compound and a thioxanthone compound, an alkyl phenone compound and an aromatic amine compound, and specifically, for example 2-morpholino-1- (4-methylmercaptophenyl) -2-methylpropane-1-one with 2,4-diethylthioxanthone, 2-dimethylamino-2-benzyl 1- (4-morpholinophenyl) butane-1-one with 2,4-diethylthioxanthone, 2-dimethylamino-2- (4-methylbenzyl)- 1- (4-morpholinophenyl) butane-1-one with 2,4-diethylthioxanthone, 2-morpholino-1- (4-methylmercaptophenyl) -2-methyl Propane-1-one and 2-isopropylthioxanthone and 4-isopropylthioxanthone, 2-morpholino-1- (4-methylmercaptophenyl) -2-methylpropane-1 -Ketone with 4,4'-bis (diethylamino) benzophenone, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1- Ketones with 4,4'-bis (diethylamino) benzophenone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) Butane-1-one and 4,4'-bis (diethylamino) benzophenone and the like.

Among them, a combination of an alkyl phenone compound and a thioxanthone compound is preferable, and 2-methyl-2-morpholino-1- (4-methylmercaptophenyl) propane-1-one and 2,4-bis Ethylthioxanthone, 2-methyl-2-morpholino-1- (4-methylmercaptophenyl) propane-1-one and 2-isopropylthioxanthone and 4-isopropylthioxanthone Ketones are better. For these combinations, a pattern with high sensitivity and high visible light transmittance can be obtained.

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

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

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

Solvents usable in the present invention include, for example, ester solvents (solvents containing -COO- and -O-free), ether solvents (solvents containing -O- and -COO-free), and ether esters. Solvent (solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- and -COO-free), alcohol solvent, aromatic hydrocarbon solvent, ammonium solvent, dimethyl Choose to use among Aya.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, N-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate Esters, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, cyclohexanol acetate, butyrolactone, and the like.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Alcohol monoethyl 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, phenyl ether, methyl anisole and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methyl acetate. Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate Esters, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy Methyl-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutane Methyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether Ethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.

Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2-pentan Ketones, cyclopentanone, cyclohexanone, isophorone, etc.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

Examples of the amidine solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

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

Among the solvents, an organic solvent having a boiling point of 1 atm of 120 ° C. or higher and 180 ° C. or lower is preferred from the viewpoints of coating properties and drying properties. Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 3 -Methoxy-1-butanol and the like are preferred. The solvent (E) is a preferable solvent such as this, and it is possible to suppress unevenness at the time of coating and improve the flatness of the coating film.

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

In other words, the solid content of the photosensitive resin composition is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass. When the content of the solvent (E) is within the aforementioned preferred range, the flatness of the film coated with the photosensitive resin composition is high. tendency. Here, the solid content refers to the amount of the solvent (E) removed from the photosensitive resin composition.

The photosensitive resin composition of the present invention may further contain a polyfunctional thiol compound (T). The polyfunctional thiol compound (T) refers to a compound having two or more thiol groups (-SH) in the molecule. 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.

Examples of the polyfunctional thiol compound (T) include hexanedithiol, decanedithiol, 1,4-bis (methylmercapto) benzene, butanediol bis (3-mercaptopropionate). , Butanediol bis (3-mercaptoacetate), ethylene glycol bis (3-mercaptoacetate), trimethylolpropane ginseng (3-mercaptoacetate), butanediol bis (3-mercaptoacetate) Propionate), trimethylolpropane (3-mercaptopropionate), trimethylolpropane (3-mercaptoacetate), pentaerythritol (3-mercaptopropionate), pentaerythritol (3 -Mercaptoacetate), hydroxyethyl ginseng (3-mercaptopropionate), pentaerythritol (3-mercaptobutyl), 1,4-bis (3-mercaptobutyloxy) butane, and the like.

The content of the polyfunctional thiol compound (T) is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 7 parts by mass relative to 100 parts by mass of the polymerization initiator (D). If the content of the polyfunctional thiol compound (T) is within the aforementioned preferred range, the sensitivity of the photosensitive resin composition tends to be high and the developability tends to be good.

The photosensitive resin composition of the present invention may contain a surfactant (F) (however, it is different from the resin (B)). Surfactants, for example Silicone-based surfactants, fluorine-based surfactants, silicone-based surfactants with fluorine atoms, and the like.

Examples of the silicone-based surfactant include a surfactant having a siloxane bond.

Specifically, Toray Silicone DC3PA, the same as SH7PA, the same as DC11PA, the same as SH21PA, the same as SH28PA, the same as SH29PA, the same as SH30PA, polyether modified silicone oil SH8400 (trade name: Dow Corning Toray Co., Ltd.), KP321, KP322 , KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (made by Momentive Performance Materials Japan), etc.

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

Specifically, for example, Fluorinert (registered trademark) FC430, same as FC431 (Sumitomo 3M (stock) system), MEGAFAC (registered trademark) F142D, same F171, same F172, same F173, same F177, same F183, same R30 (DIC (Stock system), EFTOP (registered trademark) EF301, same EF303, same EF351, same EF352 (Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, same S382, same SC101, same SC105 (Asahi Glass (Stock) system), E5844 ((share) Daikin Fine Chemical Research Institute) and so on.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specifically, for example, MEGAFAC (registered trademark) R08, same as BL20, same as F475, same as F477, Same as F443 (DIC (shares) system) and so on. Preferable examples include MEGAFAC (registered trademark) F475.

The content of the surfactant (F) relative to the total amount of the photosensitive resin composition 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, and more preferably 0.01% by mass or more and 0.05% by mass or less. %the following. By containing a 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 made good.

The photosensitive resin composition of the present invention may contain various additives such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, and chain transfer agents as necessary.

Adhesion promoters include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl ginseng (2-methoxyethoxy) silane, 3-glycidyloxypropyltrimethoxy Silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxy Silyl, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methyl Acrylic methoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, N-2- (aminoethylethyl) Group) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl Group) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- Phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, and the like.

The photosensitive resin composition of the present invention does not substantially contain a coloring agent such as a pigment or a dye. That is, the content of the toner in the photosensitive resin composition of the present invention is preferably less than 1% by mass, and more preferably less than 0.5% by mass.

The photosensitive resin composition of the present invention is filled in a quartz colorimetric tank with an optical path length of 1 cm, and the average transmittance in the case of measuring the transmittance under a condition of a measurement wavelength of 400 to 700 nm using a spectrophotometer is preferably 70% or more And more preferably 80% or more.

When the photosensitive resin composition of the present invention is used to form a coating film, the average transmittance of the coating film is preferably 90% or more, and more preferably 95% or more. This average transmittance is a coating film with a thickness of 3 μm after heat curing (for example, 100 to 250 ° C., 5 minutes to 3 hours of condition curing). The measurement is performed using a spectrophotometer at a measurement wavelength of 400 to 700 nm. average value. Thereby, a coating film excellent in transparency in the visible light region can be provided.

The photosensitive resin composition of the present invention can be patterned on, for example, a substrate made of glass, metal, plastic, or the like, or a substrate formed with a color filter, various insulating or conductive films, and a driving circuit. Form the desired shape. Furthermore, the pattern may be used as a part of a component of a display device or the like.

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

Coating can be performed using various coating apparatuses, such as a spin coater, a slit & spin coater, a slit coater, inkjet printing, a roll coater, a dip coater, etc. as mentioned above.

Then, drying or pre-baking is performed, and volatile components such as a solvent are removed and then dried. Thereby, a smooth unhardened coating film can be obtained.

The film thickness of the coating film at this time is not particularly limited, and can be appropriately adjusted depending on the material to be used, the application, and the like, and is, for example, about 1 to 6 μm.

Furthermore, the obtained uncured coating film is irradiated with light, such as ultraviolet rays generated by a mercury lamp or a light emitting diode, through a mask for forming a desired pattern. The shape of the photomask at this time is not particularly limited, and the shape or size may be selected according to the use of the pattern.

In recent years, exposure machines can cut off light up to 350 nm with a filter that cuts the wavelength range, or use light from the wavelength range around 436 nm, 408 nm, and 365 nm. After selective removal of the pass filter, the entire exposure surface is uniformly irradiated with slightly parallel light. If a mask is used to align the exposure machine, stepper, etc., the mask and the substrate can be aligned correctly at this time.

The exposed coating film is brought into contact with a developing solution, and a specific portion, for example, a non-exposed portion (ie, a non-pixel portion) is dissolved, and the target pattern shape can be obtained by development.

The developing method may be any of a liquid bath method, a dipping method, and a spray method. During further development, the substrate can be tilted at any angle.

The developer used for development is an aqueous solution of an alkaline compound as good.

The basic compound may be any of inorganic and organic basic compounds.

Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, and silicon. Potassium acid, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia, etc.

Examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, and diethylamine. Methylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine and the like.

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

The developing solution may contain a surfactant.

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

Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivatives, and ethylene oxide / propylene oxide block copolymerization. Products, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, etc. .

Anionic surfactants include, for example, sodium lauryl sulfate or higher alcohol sulfates such as sodium oleyl sulfate, sodium lauryl sulfate or alkyl sulfates such as ammonium lauryl sulfate, and dodecylbenzene. Sodium sulfonate or Alkyl aryl sulfonates such as sodium dodecylnaphthalene sulfonate.

Examples of the cationic surfactant include stearylamine hydrochloride, lauryltrimethylammonium chloride-like amine salt, or a fourth-order 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, and even more preferably 0.1 to 5% by mass.

After development, the pattern can be obtained by washing with water. Further, if necessary, post-exposure baking may be performed. Post-exposure baking is preferably performed in a temperature range of 150 to 240 ° C. for 10 to 180 minutes.

When the uncured coating film is exposed, a patterned photomask is not used, and light irradiation and / or development is omitted in its entirety to obtain a coating film having no pattern.

As an example of the display device of the present invention, an organic EL (electroluminescence) display device will be described below.

FIG. 1 is a cross-sectional view of a mode display in which a part of the display device 1 as an example of the display device of the present invention is enlarged. FIG. 2 is a plan view showing a mode display in which a part of the display device 1 as an example of the display device of the present invention is enlarged. The display device 1 is mainly composed of a support wall 2, a partition wall 3 that defines a predetermined region on the support substrate 2, and a plurality of organic EL elements 4 that are provided in the area defined by the partition wall 3. The partition wall 3 corresponds to the partition wall for inkjet printing of the present invention.

The partition wall 3 is formed on the support substrate 2, and is formed in a lattice shape or a stripe shape, for example. FIG. 2 shows a display device 1 provided with a grid-like partition wall 3 as an embodiment. In the same figure, the collar provided with the partition wall 3 is provided. Domain, cast a shadow.

A plurality of concave portions 5 defined by the partition wall 3 and the support substrate 2 are set on the support substrate 2. The recessed portion 5 corresponds to a region defined by the partition wall 3.

The partition walls 3 in the display device 1 are provided in a grid shape. Therefore, when viewed from one of the thickness directions Z of the support substrate 2 (hereinafter referred to as "planar view"), the plurality of concave portions 5 are arranged in a matrix. That is, the recesses 5 are arranged at a specific interval in the row direction X, and at the same time, the entire column is arranged at a specific interval in the column direction Y. The shape of each concave portion 5 in a plan view is not particularly limited. For example, the concave portion 5 is formed into a shape such as a substantially rectangular shape, a substantially elliptical shape, and an elliptical shape in plan view. In this embodiment, a substantially rectangular recessed portion 5 is provided in plan view. In this specification, the row direction X and the column direction Y are directions perpendicular to the thickness direction Z of the support substrate and mutually perpendicular directions.

As another embodiment, when a stripe-shaped partition wall is provided, for example, a plurality of partition wall members extending in the row direction X are arranged at specific intervals in the column direction Y. In this form, a stripe-shaped recessed portion is defined by the stripe-shaped partition wall and the support substrate region.

The partition wall is formed so that the width becomes narrower as it moves away from the support substrate. For example, the cross-sectional shape when the partition wall extending in the column direction Y is cut at a plane perpendicular to the extending direction (the column direction Y) is formed so that the width becomes narrower as it moves away from the support substrate. In FIG. 1, an isosceles trapezoid-shaped partition wall is compared with the upper bottom and the lower bottom on the supporting substrate side, and the lower bottom is wider than the upper bottom. In addition, the cross section of the partition wall actually formed does not have to be trapezoidal, and the straight portions and corners of the trapezoidal shape may have rounded corners.

The partition wall 3 preferably has a liquid-repellent property on the top surface. Moreover, the top surface refers to a plane existing on the surface of the partition wall 3 at a position farthest from the support substrate 2. Since the top surface of the partition wall 3 is liquid-repellent, it is possible to prevent the ink supplied to the area (the recess 5) surrounded by the partition wall 3 from being transmitted to the top surface of the partition wall 3 and overflowing into the adjacent area.

The organic EL element 4 is provided in a region (ie, the recessed portion 5) defined by the partition wall 3. When a grid-like partition wall 3 is provided in the display device 1, each organic EL element 4 is provided in each recessed portion 5. That is, the organic EL elements 4 are arranged in a matrix like the respective recesses 5, and are arranged on the support substrate 2 with a specific interval in the row direction X and a specific interval in the column direction Y.

The shape and arrangement of the partition wall 3 are appropriately set in accordance with the appearance of the display device such as the number of pixels, resolution, and the like, and the ease of manufacture. For example, the width of the row direction X or the column direction Y of the partition wall 3 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 the recess 5 The width in the row direction X or the column direction Y is about 10 μm to 200 μm. The width of the first electrode 6 in the row direction X or the column direction Y is approximately 10 μm to 200 μm.

The partition wall 3 can be formed by the photosensitive resin composition of the present invention in the aforementioned pattern forming method.

As another embodiment, when a stripe-shaped partition wall is provided, the organic EL element 4 is arranged in each of the recesses extending in the row direction X with a predetermined interval in the row direction X.

The display device 1 is provided with three types of organic EL elements 4. which is There are provided (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 configured by sequentially laminating a first electrode, an organic EL layer, and a second electrode on a support substrate side. In this specification, each of one or a plurality of layers provided between the first electrode 6 and the second electrode 10 is referred to as an organic EL layer. The organic EL element 4 includes at least one light emitting layer as an organic EL layer. In addition, the organic EL element may include an organic EL layer different from the light emitting layer in addition to one light emitting layer as necessary. For example, between the first electrode 6 and the second electrode 10, a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, and an electron injection layer are provided as an organic EL layer. In addition, 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 a first electrode 6 and a second electrode 10 as a pair of electrodes composed of an anode and a cathode. One of the first electrode 6 and the second electrode 10 is provided as an anode, and the other electrode is provided as a cathode. In the display device 1, a first electrode 6 having an anode function as a sequential layer, a first organic EL layer 7 having a hole injection layer function, a second organic EL layer 9 having a light emitting layer function, and a first electrode having a cathode function are used. The two electrodes 10 are formed on a support substrate 2.

The first electrodes 6 are each provided with an organic EL element 4. That is, the organic EL element 4 and the first electrode 6 having the same number are provided on the support substrate 2. The first electrode 6 is provided corresponding to the arrangement of the organic EL element 4, and is arranged in a matrix like the organic EL element 4. Next to the wall 3, except the first electrode 6 The area is formed in a grid shape, but is further formed so as to cover the peripheral edge portion of the first electrode 6 (see FIG. 1 for reference).

The first organic EL layer 7 corresponding to the hole injection layer is provided on the first electrode 6 in each of the recesses 5. The first organic EL layer 7 is provided with a different material or film thickness depending on the type of the organic EL element as necessary. From the viewpoint of the ease of forming the first organic EL layer 7, the entire first organic EL layer 7 can be formed of the same material and the same film thickness.

The first organic EL layer 7 is supplied with ink containing the material that becomes the first organic EL layer 7 to the area (recess 5) surrounded by the partition wall 3 by the inkjet method, followed by drying, heating, and / or light irradiation. , 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 in the recess 5. The light emitting layer as described above is provided depending on the type of the organic EL element. Therefore, the red light emitting layer 9R is provided in the recessed portion 5 where the red organic EL element 4R is provided, the green light emitting layer 9G is provided in the recessed portion 5 where the green organic EL element 4G is provided, and the blue light emitting layer 9B is provided in the recessed portion 5 where the blue organic EL element 4B is provided. .

The second electrode 10 is entirely formed in a display area in which the organic EL element 4 is provided. That is, 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 over the plurality of organic EL elements.

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

The pattern obtained from the photosensitive resin composition of the present invention is a substrate having a high wettability on the surface of the recessed substrate divided by the partition wall and the substrate, and a liquid-repellent property on the partition wall, so it can be used in particular as an inkjet method. Partition walls used for color filters, ITO electrodes of liquid crystal display elements, organic EL display elements, and circuit wiring boards. Furthermore, it can be used as, for example, a photo spacer, which constitutes a part of a color filter substrate and / or an array plate, a patternable protective film, an interlayer insulating film, a protrusion for controlling liquid crystal alignment, and a microscope. Components for touch panels such as lenses and coating layers for film thickness adjustment. The coating film without a pattern obtained as described above can be used as a protective film forming part of a color filter substrate and / or an array plate. . The aforementioned color filter substrate and array plate are preferably used for a liquid crystal display device, an organic EL display device, an electronic paper, and the like.

Examples

Hereinafter, the present invention will be described in more detail with examples. In the examples, "%" and "part" are mass% and mass parts without special notes.

(Synthesis example 1)

In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, a suitable amount of nitrogen was flowed in and replaced with a nitrogen environment. 166 parts of propylene glycol monomethyl ether acetate and 52 parts of methoxypropanol were added, and heated to 85 ° C while stirring. . Next, 233 parts of a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 or 9-based acrylate, 77 parts of p-vinyl benzoic acid, and propylene glycol monomethyl ether The mixed solution of 125 parts of acetate and 115 parts of methoxypropanol was dripped over 4 hours. On the other hand, a mixed solution in which 32 parts of 2,2-azobis (2,4-dimethylvaleronitrile) was dissolved in 210 parts of propylene glycol monomethyl ether acetate was dropped over 5 hours. After maintaining the same temperature for 3 hours after the dropping, the mixture was cooled to room temperature to obtain a copolymer (resin A1a) 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 A1a had a weight-average molecular weight Mw of 7.7 × 10 ³ and a molecular weight distribution of 1.90. The resin A1a has the following structural units.

(Synthesis example 2)

In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, nitrogen was allowed to flow at 0.02 L / min to create a nitrogen environment, and 200 parts of 3-methoxy-1-butanol and 3-methoxybutylacetic acid were added. 105 parts of ester were heated to 70 ° C while stirring. Next, 60 parts by mass of methacrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by Formula (I-1) and the compound represented by Formula (II-1) The compounds were mixed at a molar ratio of 50:50.) 240 parts and 140 parts of 3-methoxybutyl acetate were dissolved, and a solution was prepared. The solution was dissolved in a dropping funnel, and the solution was allowed to drip for 4 hours. Inside a 70 ° C flask.

On the other hand, a solution of 30 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts of 3-methoxybutyl acetate was used, and It took 4 hours for the dropping funnel to drip into the flask. After the dripping of the solution of the polymerization initiator, it was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin A1b) having a solid content of 32.6% and an acid value of 110 mgKOH / g (in terms of solid content) . The obtained resin A1b had a weight-average molecular weight Mw of 1.3 × 10 ⁴ and a molecular weight distribution of 2.50. The resin A1b has the following structural units.

(Synthesis example 3)

In a four-necked flask equipped with a reflux cooling tube, a nitrogen introduction tube, a thermometer and a stirring device, 78 parts of α-chloroacrylic acid 3,3,4,4,5,5,6,6,6-nonafluorohexyl ester, 19.5 parts of methacrylic acid, 19.5 parts of isobornyl methacrylate, 13 parts of glycidyl methacrylate, 12.7 parts of dodecanethiol, 266 parts of propylene glycol monomethyl ether acetate, and heated to 70 ° C , Stirring under nitrogen flow for 30 minutes. One part of azobisisobutyronitrile was added thereto, and polymerization was performed for 18 hours to obtain a solution of a copolymer (resin Ba) having a solid content of 33% and an acid value of 68 mg-KOH / g (in terms of solid content). The weight average molecular weight of the obtained resin Ba was 7.5 × 10 ³ . Resin Ba has the following structural units.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resins obtained in Synthesis Examples 1 to 3 were measured using the GPC method under the following conditions.

Installation; K2479 ((share) Shimadzu Corporation)

Column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0mL / min

Detector; RI

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

(Examples 1 to 4 and Comparative Example 1) <Adjustment of photosensitive resin composition>

Each of the components in Table 3 was mixed to obtain a photosensitive resin composition.

Each component in Table 3 is as follows. The parts listed in the column of resin are parts by mass in terms of solid content.

Resin (A); Aa: copolymer of p-hydroxystyrene and methyl methacrylate [copolymerization ratio of 50:50, weight average molecular weight; 8,000 to 12,000] (Maruka Lyncur (registered trademark) CMM; Maruzan Petroleum (Chemistry)

Resin (A1); A1a: Resin A1a obtained in Synthesis Example 1

Resin (A1); A1b: Resin A1b 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-morpholino-1- (4-methylmercaptophenyl) propane-1-one (IRGACURE (registered trademark) 907; manufactured by BASF)

Polymerization initiator (D); Db: ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (0- Ethyl oxime) (IRGACURE (registered trademark) OXE02; manufactured by BASF)

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

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

Solvent (E); Eb; Diethylene glycol ethyl methyl ether

Solvent (E); Ec; 3-methoxyl-butanol

Solvent (E); Ed; 3-methoxybutyl acetate

The solvent (E) is the solid content of the photosensitive resin composition. The solid content (%) in Table 3 is mixed. The values of the solvent components (Ea) to (Ed) in the solvent (E) are in the solvent (E). Quality ratio.

<Average transmittance of composition>

The obtained photosensitive resin compositions were each measured using an ultraviolet-visible near-infrared spectrophotometer (V-650; manufactured by JASCO Corporation) (quartz colorimetric tank, optical path length; 1 cm), and the average was measured from 400 to 700 nm. Transmission (%). The results are shown in Table 3.

<Production of Coating Film>

A 2-inch square glass substrate (EAGLE XG; manufactured by Corning Corporation) was sequentially washed with a neutral detergent, water, and alcohol, and then dried. On this glass substrate, each of the photosensitive resin compositions obtained above was spin-coated so that the film thickness after baking after exposure became 3.0 μm, and reduced using a reduced-pressure dryer (manufactured by MICROTEK). After drying under reduced pressure until the pressure became 66 kPa, preheating was performed on a hot plate at 80 ° C for 2 minutes to dry. After cooling, an exposure machine (TME-150RSK; Topcon, Co., Ltd., light source; ultra-high pressure mercury lamp) was used to irradiate light with an exposure amount of 50 mJ / cm ² (365 nm standard) in an atmospheric environment. In this case, the photosensitive resin composition was irradiated with an ultra-high pressure mercury lamp. After light irradiation, the coating film was immersed in a water-based developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide for 60 seconds at 23 ° C. After shaking, contact was made, and after that, heating at 230 ° C. for 20 minutes in an oven (post-exposure baking), a coating film was obtained.

<Average transmittance of coating film>

About the obtained coating film, the average transmittance | permeability (%) in 400-700 nm was measured using the micro-spectrometer (OSP-SP200; manufactured by OLYMPUS). A higher transmittance means a smaller absorption. The results are shown in Table 3.

<Contact angle>

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

The higher the contact angle, the higher the liquid repellency. The higher the contact angle in the coating film, the higher the contact angle in a pattern formed using the same photosensitive resin composition. The barrier ribs are formed of a photosensitive resin composition having a high contact angle, and the barrier ribs are liable to repel ink when the ink is transferred by an inkjet printing device in the barrier ribs. Therefore, for example, if a color filter is produced by the inkjet method, it is difficult to generate ink color mixing between adjacent pixel regions. The results are shown in Table 5.

<Pattern formation>

A 2-inch square glass substrate (EAGLE XG; manufactured by Corning Corporation) was sequentially washed with a neutral detergent, water, and alcohol, and then dried. On the glass substrate, each of the photosensitive resin compositions was spin-coated so that the film thickness after baking after exposure became 3.5 μm, and the degree of reduced pressure was reduced with a reduced-pressure dryer (manufactured by MICROTEK). After drying under reduced pressure up to 66 kPa, pre-baking was performed on a hot plate at 80 ° C for 2 minutes to dry. After cooling, the distance between the substrate coated with the photosensitive resin composition and the mask made of quartz glass was 10 μm, and an exposure machine (TME-150RSK; Topcon, stock, light source; ultra-high pressure mercury lamp) was used in an atmospheric environment. And irradiate light with an exposure amount of 50 mJ / cm ² (based on 365 nm). In this case, the photosensitive resin composition is irradiated with an optical filter (UV-33; manufactured by Asahi Kogyo Co., Ltd.) through the light emitted from the ultra-high pressure mercury lamp. As the photomask, a photomask having a pattern (having a square light-transmitting portion with a side of 13 μm on one side and a space between the squares of 100 μm) (that is, a light-transmitting portion) formed on the same plane was used.

After light irradiation, the coating film was immersed at 25 ° C for 100 seconds in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide. It was developed after shaking, washed with water, and baked in an oven for 15 minutes at 235 ° C to obtain a pattern.

<Wettability> [Preparation of solution for wettability evaluation]

N, N-dimethylacetamidamine (manufactured by Wako Pure Chemical Industries, Ltd., 99.5% or more), and 1,3-dimethyl-2-imidazolinone (Tokyo Chemical Industry Co., Ltd., 99.0% or more). The selected solvent 2 has a low viscosity, so cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd., 98.0% or more) is added as a viscosity adjusting material so that the liquid can be filled in the inkjet printing device as a mixed solvent .

In addition, because the solvent monomer is difficult to observe the coating range after drying, rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd., purity 95% or higher) is used as a solute.

The solutions were prepared in three types of Table 4 below.

[Evaluation of wettability]

An inkjet printing device (Litlex 120L, manufactured by ULVAC) was used in the partition wall, and the solution described above was filled in the partition wall at 1000 points per 200 pL, and dried using a microscope (MX61L manufactured by OLIMPUS, lens LCPFLN20xLCD) for 30 minutes. Observe whether the solute diffuses to the end of the partition. When all the solutions shown in Table 4 were spread in all 30 places, the wettability was good, and the rest were ×. The results are shown in Table 5.

From the results of the examples, it can be seen that from the photosensitive resin composition of the present invention, it is possible to obtain a coating film and a pattern that are excellent in wettability while maintaining no contact angle of color mixing of the ink.

Industrial availability

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

Claims (7)

A photosensitive resin composition characterized by containing (A), (B), (C), and (D), (A) having a structural unit having a phenolic hydroxyl group and a unit derived from an alkyl (meth) acrylate A polymer (C) having a structural unit and not having a structural unit of a perfluoroalkyl group having 4 to 6 carbons (C) A polymerizable compound containing a structural unit of a perfluoroalkyl group having 4 to 6 carbons (D) Polymerization initiator Here, the content of the resin (A) is 5 to 95% by mass based on the total amount of the resin (A), the resin (B), and the polymerizable compound (C). The content is 0.001 to 10 parts by mass based on 100 parts by mass of the total amount of the resin (A) and the polymerizable compound (C), and the content of the polymerizable compound (C) is relative to that of the resin (A) and the polymerizable compound (C). The total amount is 5 to 95% by mass, and the content of the polymerization initiator (D) is 0.5 to 30 parts by mass based on 100 parts by mass of the total amount of the resin (A) and the polymerizable compound (C). The photosensitive resin composition according to claim 1, wherein (B) is a polymer having a structural unit of at least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. The photosensitive resin composition according to claim 1 or 2, wherein (D) is a polymerization containing at least one selected from the group consisting of a biimidazole compound, an alkyl phenone compound, and an O-fluorenyl oxime compound. Initiator. A pattern is formed by the photosensitive resin composition according to any one of claims 1 to 3. A partition wall for inkjet printing, which is formed from the photosensitive resin composition according to any one of claims 1 to 3. A display device including a pattern described in claim 4. A display device including the partition wall for inkjet printing according to claim 5.