TW201323501A - Resin composition, photosensitive resin composition, spacer and display device - Google Patents

Abstract

This invention provides a resin composition capable of inhibiting the increase in the molecular weight of a copolymer (A1) formed by polymerization of an unsaturated carboxylic acid (a1) and an epoxide group-containing unsaturated compound (a2), a photosensitive resin composition containing the resin composition, a spacer formed by the photosensitive resin composition, and a display device having the spacer. In the present invention, a compound of formula (1) is formulated in a resin composition comprising an alkaline-soluble resin (A) of the copolymer (A1) formed by polymerization of the unsaturated carboxylic acid (a1) and the epoxide group-containing unsaturated compound (a2) and a solvent (S) comprising the propylene glycol monomethyl ether acetate.

Description

Resin composition, photosensitive resin composition, spacer, and display device

The present invention relates to a resin composition, a photosensitive resin composition containing the resin composition, a spacer formed using the photosensitive resin composition, and a display device including the spacer.

A photosensitive resin composition obtained by dissolving at least an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator in a solvent has been used in various applications. The photosensitive resin composition is widely used because it dissolves the alkali-soluble resin well, and it is easy to obtain a photosensitive resin composition which can form a coating film having a desired thickness, is excellent in evaporability, and is less toxic to human body. Methyl ether acetate (hereinafter also referred to as "PGMEA") is used as a solvent. Specific examples of the use of the photosensitive resin composition are, for example, applications for forming a spacer in a display device.

The display device utilizes a spacer that forms a space of a certain height between the two substrates for various purposes. For example, in the liquid crystal panel, since a liquid crystal material is sandwiched between transparent substrates such as two glass substrates, it is necessary to form a spacer between the two substrates to fill the liquid crystal material.

Conventionally, a spacer is used as a method of dispersing bead particles as spacers on the entire surface of a substrate. However, this method is difficult to form spacers with high positional accuracy, and since the pixel display portion also adheres to the beads, there is a problem that the contrast of the image or the display image quality is lowered.

On the other hand, a method of forming a spacer from a photosensitive resin composition is The photosensitive resin composition is applied onto a substrate, exposed to a specific mask, and developed to form a dot-like spacer. Therefore, according to this method, the spacer can be formed only in a specific portion other than the pixel display portion, and a display device capable of forming an image excellent in contrast or image quality can be manufactured.

In the photosensitive resin composition which can be preferably used in the method, it is proposed to use at least one selected from the group consisting of an ethylenically unsaturated carboxylic acid and an ethylenically unsaturated carboxylic anhydride, and an epoxy group containing an epoxy group. A copolymer obtained by copolymerizing at least an unsaturated compound is used as a photosensitive resin composition of an alkali-soluble resin (see Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2006-184841

However, in the photosensitive resin composition, at least one selected from the group consisting of an ethylenically unsaturated carboxylic acid and an ethylenically unsaturated carboxylic anhydride is used, and at least one of the epoxy group-containing ethylenically unsaturated compounds is copolymerized. When the copolymer is used as an alkali-soluble resin and a solvent containing PGMEA is used as a solvent, the molecular weight of the alkali-soluble resin is likely to increase due to self-reaction of the alkali-soluble resin, and the development of the photosensitive resin composition is lowered. The problem.

The present invention has been made in view of the conventional circumstances, and its object is to provide A resin composition capable of suppressing an increase in molecular weight of a copolymer (A1) obtained by polymerizing an unsaturated carboxylic acid (a1) and an epoxy group-containing unsaturated compound (a2), even when a solvent containing PGMEA is used, A photosensitive resin composition containing the resin composition, a spacer formed of the photosensitive resin composition, and a display device including the spacer.

The inventors of the present invention have repeatedly conducted active research to solve the above problems. As a result, it has been found to be an alkali-soluble resin (A) containing a copolymer (A1) obtained by polymerizing at least an ethylenically unsaturated carboxylic acid (a1) and an epoxy group-containing unsaturated compound (a2), and a PGMEA-containing product. In the resin composition of the solvent (S), a compound having a specific structure is blended, and a resin composition capable of suppressing an increase in the molecular weight of the alkali-soluble resin can be obtained, and the above problem can be solved by preparing the photosensitive resin composition using the resin composition. Thus, the present invention has been completed. Specifically, the present invention provides the following.

The first aspect of the present invention is a resin composition comprising an alkali-soluble resin (A), a compound represented by the following formula (1), and a solvent (S), wherein the alkali-soluble resin (A) contains at least an unsaturated a copolymer (A1) obtained by polymerizing a carboxylic acid (a1) and an epoxy group-containing unsaturated compound (a2), wherein the solvent (S) comprises propylene glycol monomethyl ether acetate, (wherein R ¹ and R ² each independently represent a hydrogen atom or an organic group, but at least one of R ¹ and R ² represents an organic group, and R ¹ and R ² may be bonded to each other to form a cyclic structure, or A bond containing a hetero atom, R ³ represents a single bond or an organic group, and R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a sulfhydryl group, a sulfide group, a decyl group, a decyl group, or a nitro group. , nitroso, sulfino, sulfo, sulfonato, phosphino, phosphinyl, phosphono, phospholipid Phosphonato), or an organic group, R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitroso group, and a nitro group. Sulfo, sulfo, sulfonate, phosphino, phosphinyl, phosphonium, phosphate, amine, ammonium, or organic, but R ⁶ and R ^{7 are} not hydroxyl, R ⁶ , R ⁷ , R ⁸ and R ⁹ may form a cyclic structure for the two or more bonds, or may contain a bond of a hetero atom, and R ¹⁰ represents a hydrogen atom or an organic group.

The second aspect of the present invention is a photosensitive resin composition containing a resin composition of the first form, a photopolymerizable monomer (B), and a photopolymerization initiator (C).

The third aspect of the present invention is a spacer formed of the photosensitive resin composition of the second aspect.

A fourth aspect of the present invention is a display device having a spacer of a third aspect.

According to the present invention, it is possible to provide an increase in the molecular weight of the copolymer (A1) obtained by polymerizing the unsaturated carboxylic acid (a1) and the epoxy group-containing unsaturated compound (a2) even when a solvent containing PGMEA is used. A resin composition, a photosensitive resin composition containing the resin composition, a spacer formed of the photosensitive resin composition, and a display device including the spacer.

Resin Composition

The resin composition of the present invention contains at least an alkali-soluble resin (A), a compound represented by the above formula (1), and a solvent (S), and the alkali-soluble resin (A) contains at least an unsaturated carboxylic acid (a1) and The copolymer (A1) containing the epoxy group-containing unsaturated compound (a2) is polymerized, and the solvent (S) contains propylene glycol monomethyl ether acetate (PGMEA). Since the resin composition of the present invention suppresses the increase in the molecular weight of the alkali-soluble resin (A) during storage, it can be preferably used for the preparation of the photosensitive resin composition described later. Hereinafter, each component contained in the resin composition of the present invention will be described.

<alkali soluble resin (A)>

The alkali-soluble resin means a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and a resin film having a film thickness of 1 μm is formed on the substrate, and is oxidized at 2.38 mass% at 23 ° C. When immersed in a tetramethylammonium (TMAH) aqueous solution for 1 minute, the film thickness is 0.01 μm or more.

The alkali-soluble resin (A) is a resin which has been conventionally used in a photosensitive resin composition, and is copolymerized by containing at least an unsaturated carboxylic acid (a1) and an epoxy group-containing unsaturated compound (a2). The substance (A1) is not particularly limited. When the copolymer (A1) contained in the alkali-soluble resin (A) is a PGMEA solution, the molecular weight is likely to increase due to self-reaction. However, since the resin composition of the present invention contains a compound represented by the formula (1) described later, the molecular weight of the copolymer (A1) can be suppressed from increasing. Further, by containing the copolymer A1, it is easy to obtain a spacer excellent in breaking strength and adhesion to a substrate.

The unsaturated carboxylic acid (a1) is exemplified by a monocarboxylic acid such as (meth)acrylic acid or crotonic acid; a dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, orthraic acid or itaconic acid; An acid anhydride or the like. Among these, (meth)acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the obtained resin, ease of availability, and the like. These unsaturated carboxylic acids (a1) may be used alone or in combination of two or more.

The proportion of the constituent unit derived from the unsaturated carboxylic acid (a1) in the copolymer (A1) is preferably 20% by mass or more, more preferably 20 to 30% by mass. When the copolymer (A1) contains a constituent unit derived from the unsaturated carboxylic acid (a1) in this range, the photosensitive composition can be easily used to prepare a photosensitive property excellent in developability. Resin composition.

The epoxy group-containing unsaturated compound (a2) is preferably an alicyclic epoxy group-containing unsaturated compound and an epoxy group-containing unsaturated compound having no alicyclic group, more preferably An unsaturated compound containing an alicyclic epoxy group.

Hereinafter, an alicyclic epoxy group-containing unsaturated compound containing a suitable epoxy group-containing unsaturated compound (a2) will be described. The unsaturated compound containing an alicyclic epoxy group is not particularly limited as long as it is an unsaturated compound containing an alicyclic epoxy group. The alicyclic group constituting the alicyclic epoxy group may be a single ring or a polycyclic ring. The monocyclic alicyclic group is exemplified by a cyclopentyl group, a cyclohexyl group and the like. Further, the polycyclic alicyclic group is exemplified by norbornyl group, isobornyl group, tricyclodecyl group, tricyclodecyl group, tetracyclododecyl group and the like. These alicyclic epoxy group-containing unsaturated compounds may be used singly or in combination of two or more.

Specifically, the unsaturated compound containing an alicyclic epoxy group is exemplified by a compound represented by the following formulas (a2-1) to (a2-16). In the above, in order to make the developability of the photosensitive resin composition prepared by using the resin composition moderate, it is preferably a compound represented by the following formulas (a2-1) to (a2-6), more preferably the following The compounds represented by the formulae (a2-1) to (a2-4).

In the above formula, R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ¹³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10. R ^{12 is} preferably a linear or branched alkylene group such as methylene, ethyl, propyl, tetramethylene, ethylethyl, pentamethylene or hexamethylene. R ^{13 is} preferably, for example, methylene, ethyl, propyl, tetramethylene, ethylethyl, pentamethylene, hexamethylene, phenyl, cyclohexyl, -CH ₂ - Ph-CH ₂ - (Ph represents a phenylene group).

Next, an epoxy group-containing unsaturated compound having no alicyclic group will be described. Oxidation-free desaturation without alicyclic groups The compounds are exemplified by glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-(meth)acrylate. Ethoxyalkyl (meth)acrylates such as epoxyheptyl ester; glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α- An α-alkyl acrylate epoxy alkoxylate such as 6,7-epoxyheptyl ethacrylate. Among these, from the viewpoints of copolymerization reactivity, resin strength after curing, and the like, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and (methyl) are preferred. ) 6,7-epoxyheptyl acrylate. These epoxy group-containing unsaturated compounds having no alicyclic group may be used singly or in combination of two or more.

Further, the proportion of the constituent unit derived from the epoxy group-containing unsaturated compound (a2) in the copolymer (A1) is preferably 30% by mass or more, more preferably 35% by mass or more, and most preferably 35%. 80% by mass. When the copolymer (A1) contains a constituent unit derived from the epoxy group-containing unsaturated compound (a2) in this range, the resin composition can be used to easily prepare an interval which is excellent in breaking strength and adhesion to the substrate. A photosensitive resin composition of the object. Further, in the epoxy group-containing unsaturated compound (a2), the ratio of the unsaturated compound containing an alicyclic epoxy group is preferably 50% by mass or more, more preferably 80% by mass or more, and most preferably 100% by mass. .

The copolymer (A1) may be one in which the unsaturated carboxylic acid (a1) and the above epoxy group-containing unsaturated compound (a2) together with an alicyclic group-containing unsaturated compound (a3) having no epoxy group. Aggregated.

An alicyclic group-containing unsaturated compound (a3) as long as it has a fat The cyclic unsaturated compound is not particularly limited. The alicyclic group may be a single ring or a polycyclic ring. The monocyclic alicyclic group is exemplified by a cyclopentyl group, a cyclohexyl group and the like. Further, the polycyclic alicyclic group is exemplified by adamantyl group, norbornyl group, isobornyl group, tricyclodecyl group, tricyclodecyl group, tetracyclododecyl group or the like. These alicyclic group-containing unsaturated compounds (a3) may be used singly or in combination of two or more.

Specifically, the alicyclic group-containing unsaturated compound (a3) is exemplified by the compounds represented by the following formulas (a3-1) to (a3-8). In the above, the photosensitive resin composition prepared by using the resin composition is preferably a compound represented by the following formulas (a3-3) to (a3-8), more preferably A compound represented by the formula (a3-3) or (a3-4).

In the above formula, R ²¹ represents a hydrogen atom or a methyl group, R ²² represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ²³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ^{22 is} preferably a single bond, a linear or branched alkyl group, such as methylene, ethyl, propyl, tetramethylene, ethyl ethyl, pentamethylene, hexamethylene base. R ^{23 is} preferably, for example, a methyl group or an ethyl group.

The proportion of the constituent unit derived from the unsaturated compound (a3) containing the above alicyclic group in the copolymer (A1) is preferably from 1 to 50% by mass, more preferably from 10 to 50% by mass, most preferably 15~45% by mass.

Further, the copolymer (A1) may be one which further polymerizes other compounds than the above. The other compounds are exemplified by (meth) acrylates, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes and the like. These compounds may be used alone or in combination of two or more. use.

The (meth) acrylates are exemplified by methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, and trioctyl (meth) acrylate. A linear or branched chain alkyl (meth)acrylate, chloroethyl (meth)acrylate, 2,2-dimethylhydroxypropyl (meth)acrylate, 2-(meth)acrylate Hydroxyethyl ester, trimethylolpropyl mono(meth)acrylate, benzyl (meth)acrylate, decyl (meth)acrylate, and the like.

The (meth) acrylamides are exemplified by (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl ( Methyl) acrylamide, N,N-aryl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (A Base) acrylamide and the like.

The allyl compound is exemplified by allyl acetate, allyl hexanoate, allyl octanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, ethenyl Allyl acetate, allyl lactate, etc.; allyloxyethanol and the like.

Vinyl ethers are exemplified by hexyl vinyl ether, octyl vinyl ether, mercapto vinyl ether, ethylhexyl vinyl ether, methoxy ethyl vinyl ether, ethoxyethyl vinyl ether, chlorine B Vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethyl An alkyl vinyl ether such as aminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether or tetrahydrofurfuryl vinyl ether; vinyl Phenyl ether, B A vinyl aryl ether such as an alkenyl tolyl ether, a vinyl chlorophenyl ether, a vinyl-2,4-dichlorophenyl ether, a vinyl naphthyl ether or a vinyl decyl ether.

The vinyl esters are exemplified by vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, vinyl dichloroacetate. , methoxyvinyl acetate, butoxy vinyl acetate, vinyl phenyl acetate, vinyl acetate, vinyl laurate, vinyl-β-phenylbutyrate, vinyl benzoate, water Vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

Styrenes are listed as styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene Alkylbenzene such as cyclohexylstyrene, mercaptostyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, ethoxymethylmethylstyrene Ethylene styrene such as ethylene; methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetra Chlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3- A halogenated styrene such as trifluoromethylstyrene.

The mass average molecular weight of the copolymer (A1) (Mw: the measured value in terms of styrene in terms of gel permeation chromatography (GPC), which is the same in the specification) is preferably from 2,000 to 200,000, more preferably from 5,000 to 30,000. When it is in the above range, the film formation ability of the photosensitive resin composition prepared by using the resin composition tends to be balanced, and the development performance after exposure tends to be balanced.

Further, the alkali-soluble resin (A) can also preferably be used in a composition containing at least a constituent unit derived from the unsaturated carboxylic acid (a1) and a portion polymerizable with a photopolymerizable monomer (B) to be described later. a unit copolymer (A2), or at least a constituent unit derived from the unsaturated carboxylic acid (a1) and a constituent unit derived from the epoxy group-containing unsaturated compound (a2), and having light which can be described later A resin of a copolymer (A3) which is a constituent unit of a polymerizable monomer (B). When the alkali-soluble resin (A) contains the copolymer (A2) or (A3), the adhesion of the photosensitive resin composition to the substrate and the breaking strength of the photosensitive resin composition after curing can be improved.

The copolymer (A2) and the copolymer (A3) may further be (meth)acrylates, (meth)acrylamides, allyl compounds described as other compounds in the copolymer (A1). And vinyl ethers, vinyl esters, styrenes, etc. are copolymerized.

The constituent unit having a portion polymerizable with the photopolymerizable monomer (B) is preferably a portion containing an ethylenically unsaturated group as a site polymerizable with the photopolymerizable monomer (B). The copolymer having the constituent unit may be contained in the copolymer (A2) by a part of a carboxyl group contained in the homopolymer of the unsaturated carboxylic acid (a1) and the above-mentioned epoxy group-containing unsaturated compound. The epoxy group is reacted to prepare. Further, the copolymer (A3) can be obtained by reacting an epoxy group having a constituent unit derived from the above unsaturated carboxylic acid (a1) and a constituent unit derived from the above-mentioned epoxy group-containing unsaturated compound (a2). One part of the base is prepared by reacting with an unsaturated carboxylic acid (a1).

The mass average molecular weight of the copolymer (A2) and the copolymer (A3) is preferably from 2,000 to 50,000, more preferably from 5,000 to 30,000. By becoming the above In addition, there is a tendency that the film formation ability of the photosensitive resin composition prepared by using the resin composition and the development performance after exposure are easily balanced.

Further, the alkali-soluble resin (A) contains, in addition to the resins selected from the copolymers (A1) and (A3), other conventionally alkali-soluble resins. However, the proportion of the resin selected from the copolymers (A1) and (A3) in the alkali-soluble resin (A) is preferably 80% by mass or more, more preferably 90% by mass or more, and most preferably 100% by mass.

Further, the content of the alkali-soluble resin (A) in the resin composition is not particularly limited. Typically, the content of the alkali-soluble resin (A) in the resin composition is preferably from 5 to 60% by mass, more preferably from 10 to 30% by mass. In this case, the resin composition having a low viscosity and easy work can be easily prepared.

<Compound represented by formula (1)>

The resin composition of the present invention contains a compound represented by the following formula (1). By including the compound in the resin composition containing the alkali-soluble resin (A) and the solvent (C) containing PGMEA, the amount of the alkali-soluble resin (A) can be suppressed.

In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom or an organic group, but at least one of R ¹ and R ² represents an organic group.

The organic group in R ¹ and R ² is exemplified by an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group or the like. The organic group may also have a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. Further, the organic group may be any of a linear chain, a branched chain, and a cyclic chain. The organic group is usually monovalent, but when it forms a cyclic structure, it can be a divalent or higher organic group.

R ¹ and R ² may be bonded to each other to form a cyclic structure, and may further contain a bond of a hetero atom. The cyclic structure is exemplified by a heterocycloalkyl group, a heteroaryl group or the like, and may be a condensed ring.

The bond other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as it does not impair the effects of the present invention, and is exemplified by a bond containing a hetero atom such as an oxygen atom, a nitrogen atom or a ruthenium atom. Specifically, it is an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, a guanamine bond, a urethane bond, or an imine bond (-N=C(-R)-, -C( =NR)-: R represents a hydrogen atom or an organic group, a carbonate bond, a sulfonyl bond, a sulfinium bond, an azo bond, or the like.

From the viewpoint of heat resistance, the bond other than the hydrocarbon group in the organic group of R ¹ and R ² is preferably an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, a guanamine bond, or an aminocarboxylic acid. Ester bond, imine bond (-N=C(-R)-, -C(=NR)-: R represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond .

The substituent other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as it does not impair the effects of the present invention, and is exemplified by a halogen atom, a hydroxyl group, a thiol group, a thioether group, a cyano group, an isocyano group, and a cyanic acid. Ester group, isocyanate group, thiocyanate group, isothiocyanate group, decyl group, decyl alcohol group, alkoxy group, alkoxycarbonyl group, amine carbaryl group, thioamine mercapto group, nitrate Base, nitroso, carboxyl, carboxylate, sulfhydryl, decyloxy, sulfinyl, sulfo, sulfonate, phosphino, phosphinyl, phosphonium, phosphate, hydroxyimine Base, alkyl ether group, alkenyl ether group, alkyl sulfide group, alkenyl sulfide group, aryl ether group, aryl sulfide group, amine group (-NH ₂ , -NHR, -NRR':R And R' each independently represents a hydrocarbon group). The hydrogen atom contained in the above substituent may also be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be any of a linear chain, a branched chain, and a cyclic group.

The substituent other than the hydrocarbon group in the organic group of R ¹ and R ² is preferably a halogen atom, a hydroxyl group, a thiol group, a thioether group, a cyano group, an isocyano group, a cyanate group, an isocyanate group or a thiocyanate group. , isothiocyanate, decyl, decyl, alkoxy, alkoxycarbonyl, amine, mercapto, thiocarbamyl, nitro, nitroso, carboxyl, carboxylate , fluorenyl, decyloxy, sulfinyl, sulfo, sulfonate, phosphino, phosphinyl, phosphonium, phosphate, hydroxyimino, alkyl ether, alkenyl ether, An alkyl sulfide group, an alkenyl sulfide group, an aryl ether group, an aryl sulfide group.

In the above, at least one of R ¹ and R ^{2 is} an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms, or preferably bonded to each other to form a heterocycloalkyl group or heteroaryl group having 2 to 20 carbon atoms. Base. The heterocycloalkyl group is exemplified by piperidinyl group, morpholinyl group and the like. The heteroaryl group is exemplified by an imidazolyl group, a pyrazolyl group or the like.

In the above formula (1), R ³ represents a single bond or an organic group.

The organic group in R ³ is exemplified by a group which removes one hydrogen atom from an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group or the like. The organic group may also have a substituent in the organic group. The substituents are exemplified as R ¹ and R ² . Further, the organic group may be either a linear chain or a branched chain.

In the above, R ^{3 is} preferably a single bond or a group in which one hydrogen atom is removed from an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms.

In the above formula (1), R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, Sulfonate, phosphino, phosphinyl, phosphonium, phosphate, or organic.

The substituents in R ⁴ and R ⁵ are exemplified as R ¹ and R ² . The organic group is the same as in the case of R ¹ and R ² , and the organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom. Further, the organic group may be any of a linear chain, a branched chain, and a cyclic chain.

In the above, each of R ⁴ and R ^{5 is} independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, and a carbon number of 7 to 16 An aryloxyalkyl group, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms and a alkoxy group having 1 to 10 carbon atoms Base, amidino group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and an ester group having 2 to 11 carbon atoms (-COOR, -OCOR: R represents a hydrocarbon group) An aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms substituted by an electron-donating group and/or an electron-donating group, a benzyl group or a cyano group substituted with an electron-donating group and/or an electron-donating group , methylthio. More preferably, both R ⁴ and R ⁵ are a hydrogen atom, or R ⁴ is a methyl group, and R ⁵ is a hydrogen atom.

In the above formula (1), R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitroso group, and a arylene group. Sulfo, sulfo, sulfonate, phosphino, phosphinyl, phosphonium, phosphate, amine, ammonium, or organic.

The organic groups in R ⁶ , R ⁷ , R ⁸ and R ⁹ are exemplified as R ¹ and R ² . The organic group is the same as in the case of R ¹ and R ² , and the organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom. Further, the organic group may be any of a linear chain, a branched chain, and a cyclic chain.

Further, in the above formula (1), R ⁶ and R ^{7 are} not a hydroxyl group.

R ⁶ , R ⁷ , R ⁸ and R ⁹ may be bonded to each other by two or more of them to form a cyclic structure, or may contain a bond of a hetero atom. The cyclic structure is exemplified by a heterocycloalkyl group, a heteroaryl group or the like, and may also be a condensed ring. For example, R ⁶ , R ⁷ , R ⁸ and R ⁹ may be bonded to two or more of them, and the atoms of the benzene ring bonded by R ⁶ , R ⁷ , R ⁸ and R ⁹ are combined to form naphthalene, anthracene and phenanthrene. Condensation ring of hydrazine, etc.

In the above, R ⁶ , R ⁷ , R ⁸ and R ^{9 are} each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, and a cycloalkenyl group having 4 to 13 carbon atoms. , an aryloxyalkyl group having 7 to 16 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, and a carbon number 1 to 10 alkoxy groups, 2 to 11 carbon atoms, 1 to 10 alkylthio groups, 1 to 10 carbon atoms, 2 to 11 carbon groups, carbon number 6~ An aryl group of 20, an electron-donating group and/or an electron-donating group having an aryl group having 6 to 20 carbon atoms, a substituted electron-donating group, and/or an electron-donating group, a cyano group, a cyano group, a methylthio group, Nitro.

Further, R ⁶ , R ⁷ , R ⁸ and R ⁹ may be bonded to two or more of them, and the atoms of the benzene ring bonded by R ⁶ , R ⁷ , R ⁸ and R ⁹ are shared to form naphthalene, anthracene, A condensed ring of phenanthrene, anthracene, etc

More preferably, R ⁶ , R ⁷ , R ⁸ and R ⁹ are each a hydrogen atom, or any one of R ⁶ , R ⁷ , R ⁸ and R ⁹ is a nitro group, and the other three are hydrogen atoms.

In the above formula (1), R ¹⁰ represents a hydrogen atom or an organic group.

The organic group in R ¹⁰ is exemplified as R ¹ and R ² . The organic group is the same as in the case of R ¹ and R ² , and the organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom. Further, the organic group may be any of a linear chain, a branched chain, and a cyclic chain.

Since the compound represented by the above formula (1) has a -OR ¹⁰ group at the para position of the benzene ring, the solubility in a solvent is good.

In the above, R ^{10 is} preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a methyl group.

Among the compounds represented by the above formula (1), the most preferable specific examples are compounds represented by the following formula.

The method for synthesizing the compound represented by the above formula (1) is not particularly limited, and it can be synthesized according to the method described in the examples below.

In the resin composition, the content of the compound represented by the above formula (1) is not particularly limited as long as it does not impair the object of the present invention. The content of the compound represented by the above formula (1) is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the alkali-soluble resin (A).

<Solvent (S)>

The resin composition contains a solvent containing propylene glycol monomethyl ether acetate (PGMEA) as a solvent (S).

The PGMEA content in the solvent (S) is not particularly limited as long as it does not impair the object of the present invention, but is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 100% by mass. When the PGMEA content in the solvent (S) is 50% by mass or more, the molecular weight of the alkali-soluble resin (A) tends to increase, and the effect of the present invention is remarkable.

When the solvent (S) contains an organic solvent other than PGMEA, the other organic solvent is not particularly limited insofar as it does not impair the object of the present invention. Other organic solvents other than PGMEA are specifically exemplified by ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol single (poly)alkylene glycol monoalkyl ethers such as n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether (poly)alkylene glycol monoalkyl ether acetates such as acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate a ketone such as methyl ethyl ketone, cyclohexanone, 2-heptanone or 3-heptanone; an alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate; Ethyl 2-methylpropionate, 3- Oxypropanoate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyric acid Methyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate , isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, butyl Other esters such as n-butyl acrylate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoxyacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; toluene, An aromatic hydrocarbon such as xylene; an amide such as N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide. Among these, an alkanediol monoalkyl ether, an alkylene glycol monoalkyl ether acetate, and an alkyl lactate are preferable, and an alkanediol monoalkyl ether acetate is more preferable. These solvents may be used singly or in combination of two or more.

The content of the solvent (S) in the resin composition is not particularly limited, and the composition of the photosensitive resin composition prepared by using the resin composition can be appropriately determined.

<Method for Producing Resin Composition>

The resin composition of the present invention can be mixed (dispersed and kneaded) with a mixer such as a three-roll mill, a ball mill, or a sand mill to prepare the above components, and if necessary, filtered by a filter such as a membrane filter of 5 μm.

"Photosensitive Resin Composition"

The photosensitive resin composition contains light in addition to the above resin composition A polymerizable monomer (B) and a photopolymerization initiator (C). Hereinafter, each component contained in the photosensitive resin composition will be described.

<alkali soluble resin (A)>

The resin which can be used as the alkali-soluble resin (A) is as described above for the resin composition.

The content of the alkali-soluble resin (A) in the photosensitive resin composition is preferably from 40 to 85% by mass, more preferably from 45 to 75% by mass, based on the solid content of the photosensitive resin composition. By setting it as the said range, it exists in the tendency for the imaging property to be easy to balance.

<Compound represented by formula (1)>

The compound represented by the above formula (1) is as described above for the resin composition. The content of the compound represented by the above formula (1) in the photosensitive resin composition is the same as the content in the resin composition. The content of the compound represented by the above formula (1) is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the alkali-soluble resin (A). The compound represented by the above formula (1) may be added when the photosensitive resin composition is prepared by using the above resin composition.

<Photopolymerizable monomer (B)>

The photopolymerizable monomer (B) (hereinafter also referred to as "(B) component") contained in the photosensitive resin composition of the present invention can preferably use a monomer having an ethylenically unsaturated group. The monomer having an ethylenically unsaturated group has a single Functional monomers and polyfunctional monomers.

Monofunctional monomers are exemplified by (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) propylene oxime Amine, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl ( Methyl) acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-propenylamine - 2-methylpropanesulfonic acid, tert-butylacrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl hexyl ester, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (methyl) 2-phenoxy-2-hydroxypropyl acrylate, 2-(methyl)propenyloxy-2-hydroxypropyl phthalate, glycerol mono(meth) acrylate, (methyl) Tetrahydrofurfuryl acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, (methyl) Acid 2,2,2-trifluoroethyl acrylate, (meth) acrylate, 2,2,3,3-tetrafluoro-propyl, semi-phthalic acid derivative of (meth) acrylate. These monofunctional monomers may be used singly or in combination of two or more.

On the other hand, polyfunctional monomers are exemplified by ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(methyl) Acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylic acid Ester, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol II (Meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2, 2-double (4-(Methyl)propenyloxydiethoxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxypolyethoxyphenyl)propane, 2-hydroxy-3 -(Meth)acryloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di(meth) acrylate, diethylene glycol diglycidyl ether di(meth) acrylate, benzene Diglycidyl dicarboxylate di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane (meth) acrylate (ie , toluene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc. with (meth)acrylic acid 2- The reaction of a ethyl ethyl ester, a condensate of methylene bis(meth) acrylamide, (meth) acrylamide, methylene ether, a polyol and N- hydroxymethyl (meth) acrylamide Such as a polyfunctional monomer, or tripropylene formaldehyde. These polyfunctional monomers may be used singly or in combination of two or more.

Among the monomers having an ethylenically unsaturated group, the adhesion of the photosensitive resin composition to the substrate and the improvement of the breaking strength of the photosensitive resin composition after curing are preferably three or more A functional monomer, more preferably a polyfunctional monomer having more than six functional groups.

The content of the component (B) is relative to the solid content of the photosensitive resin composition The fraction is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass. In the above range, sensitivity, development, and dissociation tend to be balanced.

<Photopolymerization initiator (C)>

The photopolymerization initiator (C) (hereinafter also referred to as "(C) component)) contained in the photosensitive resin composition of the present invention is not particularly limited, and a conventional photopolymerization initiator can be used.

Specific examples of the photopolymerization initiator are 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy) Phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis ( 4-dimethylaminophenyl)one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethyl Amino-1-(4-morpholinylphenyl)-butan-1-one, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole -3-yl], 1-(O-acetylindenyl), 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzhydrylhydrazine)] , 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 4-benzylidene-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, 4-di Methyl methylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamine 2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethylketal, 1-phenyl-1,2-propanol Ketone -2- (O- ethoxycarbonyl) oxime, o - benzoyl benzoate, 2,4-diethyl Thiophenone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxan, 2, 4-Diethyl thioxanthene, 2-methyl thioxanthene, 2-isopropyl thioxanthene, 2-ethyl hydrazine, octamethyl hydrazine, 1,2-benzopyrene, 2,3-di Phenylhydrazine, azobisisobutyronitrile, benzhydryl peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2 -(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazole dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethyl Aminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybiphenyl Ketone, benzoin, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoate Butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone , p-t-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyl three Chloroacetophenone, p-t-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone; thioxanthone, 2-methylthioxanthone, 2-isopropyl Thiophenone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenyl acridine, 1,7-bis-(9-acridinyl) heptane 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-paran (trichloro) Methyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl] -4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3, 4-dimethoxy Phenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s -triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6 - bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4- Bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy Styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, and the like. Among them, the use of a lanthanide photopolymerization initiator is particularly preferable from the viewpoint of sensitivity. These photopolymerization initiators may be used singly or in combination of two or more.

The content of the component (C) is preferably from 0.5 to 30% by mass, more preferably from 1 to 20% by mass, based on the solid content of the photosensitive resin composition. When it is in the above range, sufficient heat resistance and chemical resistance can be obtained, and coating film formation energy can be improved, and curing failure can be suppressed.

Further, a photoinitiator may be combined in the component (C). The photoinitiating aids are exemplified by triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzene. Isoamyl formate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4,4'-double (two Methylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9 , 10-diethoxyanthracene, and the like. These photoinitiating aids may be used singly or in combination of two or more.

<Colorant (D)>

The photosensitive resin composition of the present invention may contain a coloring agent (D) as needed. In particular, when the photosensitive resin composition contains a light-shielding agent as a coloring agent, it can be suitably used for formation of a black spacer. In the case of a black spacer, light leakage from the spacer portion of the display device can be suppressed, and a display device capable of displaying a better image with high contrast can be manufactured.

The coloring agent (D) contained in the photosensitive resin composition of the present invention is not particularly limited, but is preferably classified into a pigment (Pigment) by, for example, a color index (CI; issued by The Society of Dyers and Colourists). The compound, specifically the one using the color index (CI) number attached below.

Examples of yellow pigments that can be used are listed as CI Pigment Yellow-1 (hereinafter, also referred to as "CI Pigment Yellow", only the number is listed), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24 , 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113 , 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168 , 175, 180, and 185.

Examples of the orange pigment which can be preferably used are CI Pigment Orange 1 (hereinafter, also referred to as "CI Pigment Orange", only the number is listed), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, and 73.

An example of a purple pigment which can be preferably used is C.I. Pigment Violet 1 (hereinafter, also referred to as "C.I. Pigment Violet", only the number is listed), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50.

Examples of red pigments which can be preferably used are CI Pigment Red 1 (hereinafter, also referred to as "CI Pigment Red", only numbers are listed), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265.

Examples of blue pigments which can be preferably used are CI Pigment Blue-1 (hereinafter, also referred to as "CI Pigment Blue", only numbers are listed), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, and 66.

Examples of the pigments of the above other hue which can be preferably used are listed as green pigments such as CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Brown 26, CI Pigment Brown. 28 and other brown pigments, CI pigment black 1, CI pigment black 7 and other black pigments.

Further, when a coloring agent is used as the light shielding agent, a black pigment is preferably used as the light shielding agent. Examples of the black pigment include metal oxides such as carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver, and composite oxides and gold. It is a sulfide, a metal sulfate or a metal carbonate, etc., whether it is an organic or inorganic pigment. Among these, carbon black having high light blocking property is preferably used.

As the carbon black, a conventional black carbon such as chimney black, furnace black, thermal black carbon, or lamp black can be used, but chimney black having excellent light shielding properties is preferably used. Further, carbon black coated with a resin can also be used.

Further, in order to adjust the color tone of carbon black, the above organic pigment may be appropriately added as an auxiliary pigment.

In order to uniformly disperse the above coloring agent in the photosensitive resin composition, a dispersing agent may be further used. As the dispersant, a polyethylenimine-based, urethane-based resin or acrylic resin-based polymer dispersant is preferably used. In particular, when carbon black is used as the colorant, an acrylic resin-based dispersant is preferably used as the dispersant.

Further, the inorganic pigment and the organic pigment may be used alone or in combination of two or more. When used in combination, it is preferably used in an amount of from 10 to 80 parts by mass based on 100 parts by mass of the total of the inorganic pigment and the organic pigment. Use a range of 20 to 40 parts by mass.

The amount of the coloring agent to be used in the photosensitive resin composition can be appropriately selected within the range not impairing the object of the present invention, and is usually 100 parts by mass, preferably 5 to 70% by mass based on the total of the solid content of the photosensitive resin composition. It is preferably 25 to 60 parts by mass. By being within the above range, a spacer of a desired shape can be formed.

In particular, when a black spacer is formed using a photosensitive resin composition, it is preferred that the OD value per 1 μm of the film of the black spacer is 0.5 or more. The amount of the opacifier in the photosensitive resin composition is adjusted. When the OD value per 1 μm of the film in the black spacer is 0.5 or more, light leakage from the spacer portion of the display device can be easily suppressed, and sufficient display contrast can be obtained.

The colorant is preferably dispersed in a dispersion at a suitable concentration using a dispersant, and then added to the photosensitive resin composition.

<Solvent (S)>

As the solvent (S) contained in the photosensitive resin composition, an organic solvent of the same kind as the solvent (S) which can be used in the above resin composition can be used. When the photosensitive resin composition is prepared, the solvent (S) may be added so that the photosensitive resin composition has a desired solid content concentration, or the resin composition may be concentrated. When the resin composition is concentrated, it is preferred to distill off the solvent (S) at a very low temperature under reduced pressure. When the resin composition contains a sufficient amount of the solvent (S) as the photosensitive resin composition, it is not necessary to add a new solvent (S) to the resin composition.

The content of the component (S) in the photosensitive resin composition is not particularly limited, and can be appropriately set depending on the coating film thickness by the concentration which can be applied to a substrate or the like. The viscosity of the photosensitive resin composition is preferably from 5 to 500 cp, more preferably from 10 to 50 cp, even more preferably from 20 to 30 cp. Further, the solid content concentration is preferably from 5 to 100% by mass, more preferably from 20 to 50% by mass.

<Other ingredients>

The photosensitive resin composition may contain a light absorbing agent as needed, and the interface may be live. Additives such as agents, adhesion promoters, thermal polymerization inhibitors, and defoamers. Any of the additives can be used by conventional ones. Examples of the light absorbing agent include 1,5-dihydroxynaphthalene and α-naphthol, and examples of the surfactant include compounds such as anionic, cationic, and nonionic. The adhesion promoters are conventionally known as decane. The coupling agent is exemplified by hydroquinone or hydroquinone monoethyl ether, and examples of the defoaming agent are polyfluorene-based or fluorine-based compounds.

<Modulation Method of Photosensitive Resin Composition>

The photosensitive resin composition can be mixed (dispersed and kneaded) by a mixer such as a three-roll mill, a ball mill, or a sand mill to prepare the above components, and if necessary, filtered by a filter such as a 5 μm membrane filter.

In addition, the photosensitive resin composition preferably has a photopolymerizable monomer (B) and a photopolymerization initiator added to the resin composition from the viewpoint of maintaining the molecular weight of the alkali-soluble resin (A) in a low state. After (C) and other components as needed, the solvent (S) is adjusted to a desired amount to prepare.

On the other hand, the photosensitive resin composition may be obtained by mixing an alkali-soluble resin (A), a compound represented by the above formula (1), a photopolymerizable monomer (B), a photopolymerization initiator (C), and After the other components are required, the solid content concentration of the photosensitive resin composition is adjusted to a desired range by a solvent (S). In this case, the molecular weight of the alkali-soluble resin (A) may be slightly increased before the preparation of the photosensitive resin composition, but the compound represented by the above formula (1) may be blended to prepare a photosensitive resin composition. After that, it is preferred that the increase in the molecular weight of the alkali-soluble resin (A) is suppressed.

Spacer and Display Device

The spacer of the present invention is the same as the conventional spacer formed using the photosensitive resin composition except that the above-mentioned photosensitive resin composition is used. Further, the display device of the present invention is the same as the conventional display device except that the spacer formed of the above-described photosensitive resin composition is provided. Specific examples of the display device are exemplified by a liquid crystal display device, an organic EL display device, and the like. Hereinafter, only the method of forming the spacer will be described.

The method of forming the spacer by using the photosensitive resin composition described above is not particularly limited, and can be appropriately selected from the method for forming a spacer for a conventional display device. A preferred method for forming the spacer is to include a coating step of applying the above-described photosensitive resin composition onto a substrate to form a photosensitive resin layer, and exposing the photosensitive resin layer to a pattern corresponding to a specific spacer. And a method of developing a photosensitive resin layer to be exposed to form a pattern of a pattern of spacers.

First, in the coating step, a contact transfer type coating device or a spin coater (rotary coating device) or a curtain flow coater is used using a roll coater, a reverse roll coater, a bar coater or the like. In the non-contact type coating device, the photosensitive resin composition of the present invention is applied onto a substrate on which a spacer is to be formed, and if necessary, the solvent is removed by drying to form a photosensitive resin layer.

Next, the substrate on which the photosensitive resin layer is formed on the surface is supplied to the exposure step. In the exposure step, the photosensitive resin layer is irradiated with an active energy ray such as ultraviolet rays or excimer laser light through a mask of a negative type, and the photosensitive resin layer is partially exposed in accordance with a pattern of a specific spacer. The exposure may use a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, or the like that emits ultraviolet light. The exposure amount varies depending on the composition of the photosensitive resin composition, but is preferably, for example, about 50 to 600 mJ/cm ² .

In the developing step, the photosensitive resin layer after exposure is developed with a developing liquid to form a spacer. The development method is not particularly limited, and a dipping method, a spray method, or the like can be used. Specific examples of the developing liquid are organic compounds such as monoethanolamine, diethanolamine, and triethanolamine, or aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. Since the photosensitive resin composition of the present invention exhibits an appropriate developing property by suppressing an increase in the molecular weight of the alkali-soluble resin, it can be appropriately developed.

Next, the spacer after the development is subjected to post-baking as needed to be heat-hardened. The post-baking temperature is preferably from 150 to 250 °C.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto.

In the examples and comparative examples, the following compounds 1 to 7 were used as the compound represented by the above formula (1), and the following comparative compounds 1 to 6 were used as the comparative compound for the compound represented by the above formula (1). The synthesis method of the compounds 1 to 7 is shown below. Further, in the examples and comparative examples, the compound represented by the above formula (1) and the comparative compound are also referred to as "addition compound".

[Synthesis method of Compound 1]

5.90 g (30 mmol) of 3-(4-methoxyphenyl)propene fluorene chloride was dissolved in 50 ml of dry diethyl ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine and 2.41 ml of diethanolamine (equivalent ratio 1.1) were added. ), stirred at room temperature for 1 hour. After washing with 50 ml of water, 50 ml of a saturated NaHCO ₃ aqueous solution, and 1N hydrochloric acid, the mixture was dried over magnesium sulfate and evaporated. The title compound 1 (4.65 g, 20 mmol) was obtained by hexane-ethyl acetate as a solvent. The yield of propylene chloride standard was 67%.

[Synthesis method of Compound 2]

7.25 g (30 mmol) of 3-(2-nitro-4-methoxyphenyl)propene fluorene chloride was dissolved in 50 ml of dry diethyl ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine and 2.25 ml of imidazole were added. (Equivalent ratio 1.1), stirred at room temperature for 1 hour. After washing with 50 ml of water, 50 ml of a saturated NaHCO ₃ aqueous solution, and 1N hydrochloric acid, the mixture was dried over magnesium sulfate and evaporated. The title compound 2 (4.08 g, 15 mmol) was obtained by hexane-ethyl acetate as a solvent. The yield of the propylene ruthenium chloride standard was 50%.

[Synthesis method of Compound 3]

7.25 g (30 mmol) of 3-(3-nitro-4-methoxyphenyl)propene fluorene chloride was dissolved in 50 ml of dry diethyl ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine was added, and the imidazole was 2.25 ml. (Equivalent ratio 1.1), stirred at room temperature for 1 hour. After washing with 50 ml of water, 50 ml of a saturated NaHCO ₃ aqueous solution, and 1N hydrochloric acid, the mixture was dried over magnesium sulfate and evaporated. The title compound 3 (4.08 g, 15 mmol) was obtained by hexane-ethyl acetate as a solvent. The yield of the propylene ruthenium chloride standard was 50%.

[Synthesis method of Compound 4]

7.67 g (30 mmol) of 2-methyl-3-(2-nitro-4-methoxyphenyl)propene fluorene chloride was dissolved in 50 ml of dry diethyl ether, and 4.59 ml of triethylamine was added (equivalent ratio 1.1). ), 2.25 ml of imidazole (equivalent ratio of 1.1), and stirred at room temperature for 1 hour. After washing with 50 ml of water, 50 ml of a saturated NaHCO ₃ aqueous solution, and 1N hydrochloric acid, the mixture was dried over magnesium sulfate and evaporated. The title compound 4 (4.29 g, 15 mmol) was obtained by hexane-ethyl acetate as a solvent. The yield of the propylene ruthenium chloride standard was 50%.

[Synthesis method of Compound 5]

5.90 g (30 mmol) of 3-(4-methoxyphenyl)propene fluorene chloride was dissolved in 50 ml of dry diethyl ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine and 2.25 ml of imidazole (equivalent ratio of 1.1) were added. Stir at room temperature for 1 hour. After washing with 50 ml of water, 50 ml of a saturated NaHCO ₃ aqueous solution, and 1N hydrochloric acid, the mixture was dried over magnesium sulfate and evaporated. The title compound 5 (3.41 g, 15 mmol) was obtained by hexane-ethyl acetate as a solvent. The yield of the propylene ruthenium chloride standard was 50%.

[Synthesis method of Compound 6]

7.25 g (30 mmol) of 3-(2-nitro-4-methoxyphenyl)propene fluorene chloride was dissolved in 50 ml of dry diethyl ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine was added, diethylamine. 2.41 ml (equivalent ratio 1.1) and stirred at room temperature for 1 hour. After washing with 50 ml of water, 50 ml of a saturated NaHCO ₃ aqueous solution, and 1N hydrochloric acid, the mixture was dried over magnesium sulfate and evaporated. The title compound 6 (5.55 g, 20 mmol) was obtained by hexane-ethyl acetate as a solvent. The yield of propylene chloride standard was 67%.

[Synthesis method of Compound 7]

7.25 g (30 mmol) of 3-(3-nitro-4-methoxyphenyl)propene fluorene chloride was dissolved in 50 ml of dry diethyl ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine was added, diethylamine. 2.41 ml (equivalent ratio 1.1) and stirred at room temperature for 1 hour. After washing with 50 ml of water, 50 ml of a saturated NaHCO ₃ aqueous solution, and 1N hydrochloric acid, the mixture was dried over magnesium sulfate and evaporated. The title compound 7 (5.55 g, 20 mmol) was obtained by hexane-ethyl acetate as a solvent. The yield of propylene chloride standard was 67%.

[Examples 1 to 14 and Comparative Examples 1 to 6]

The alkali-soluble resin (A) of the type and amount described in Table 1 and the additive compound were dissolved in PGMEA to prepare a resin composition having a resin concentration of 30% by mass. Using the obtained resin composition, the evaluation of the molecular weight increase was carried out according to the following method.

In addition, in Table 1, each shorthand symbol shows the following, and the numerical value in parentheses is a compounding quantity (mass part).

(alkali soluble resin (A))

As the alkali-soluble resin, a resin containing a unit derived from the following monomers in a mass ratio described below is used.

A-1: methacrylic acid: tricyclomethacrylate [5.2.1.0 ^2,6 ]癸-8-yl ester: 3,4-epoxycyclohexane-1-ylmethyl methacrylate=30: 45:35

A-2: methacrylic acid: tricyclo[meth] methacrylate [5.2.1.0 ^2,6 ] 癸-8-yl ester: 3,4-epoxycyclohexane-1-ylmethyl methacrylate = 30: 25:55

A-3: Methacrylic acid: Tricyclomethacrylate [5.2.1.0 ^2,6 ]decane-8-yl ester: 3,4-epoxycyclohexane-1-ylmethyl methacrylate: acrylic acid Epoxidized dicyclopentenyl ester = 30:45:35:35

A-4: Methacrylic acid: Tricyclo[meth] methacrylate [5.2.1.0 ^2,6 ]癸-8-yl ester: 3,4-epoxycyclohexane-1-ylmethyl methacrylate: acrylic ring Dicyclopentenyloxylate = 30:25:55:55

A-5: Methacrylic acid: Tricyclomethacrylate [5.2.1.0 ^2,6 ]decane-8-yl ester: 3,4-epoxycyclohexane-1-ylmethyl methacrylate: 2 -(3,4-epoxycyclohexane-1-yl)-6-methylpropenyloxyheptanoic acid=30:45:35:35

A-6: Methacrylic acid: Tricyclo[meth] methacrylate [5.2.1.0 ^2,6 ]癸-8-yl ester: 3,4-epoxycyclohexane-1-ylmethyl methacrylate: 2- (3,4-epoxycyclohexane-1-yl)-6-methylpropenyloxyheptanoic acid=30:25:55:55

A-7: Methacrylic acid: Tricyclomethacrylate [5.2.1.0 ^2,6 ]decane-8-yl ester: 3,4-epoxycyclohexane-1-ylmethyl methacrylate: A Glycidyl acrylate = 30:45:35:35

A-8: Methacrylic acid: Tricyclo[meth] methacrylate [5.2.1.0 ^2,6 ]癸-8-yl ester: 3,4-epoxycyclohexane-1-ylmethyl methacrylate: methyl Glycidyl acrylate = 30:25:55:55

[Evaluation of molecular weight increase]

The mass average molecular weight (Mw ¹ ) of the alkali-soluble resin contained in each resin composition was measured by gel permeation chromatography on the resin compositions of Examples 1 to 14 and Comparative Examples 1 to 6 which were just prepared. Next, the resin compositions of Examples 1 to 14 and Comparative Examples 1 to 6 were allowed to stand in a thermostatic chamber at 25 ° C for 168 hours (one week), and then each resin composition was measured by a gel permeation chromatography. The mass average molecular weight (Mw ² ) of the alkali-soluble resin. Using Mw ¹ and Mw ² , the increase rate of the molecular weight was calculated from the following formula. The molecular weight increase rate of each resin composition is shown in Table 1.

<Molecular weight increase rate calculation formula>

Molecular weight increase rate (%) = Mw ² / Mw ¹ × 100

Based on the calculated molecular weight increase rate, the degree of increase in molecular weight was determined in accordance with the following criteria. The judgment results are shown in Table 1.

○: The molecular weight increase rate is 120% or less

×: The molecular weight increase rate exceeds 120%

According to Table 1, it is understood that the molecular weight increase rate of the resin compositions of Examples 1 to 14 containing the compound represented by the above formula (1) is suppressed to 120% or less. On the other hand, the resin compositions of Comparative Examples 1 to 6 containing a comparative compound having a structure similar to the compound represented by the above formula (1) had a molecular weight increase rate of 125% or more. From these results, it is understood that when the compound represented by the above formula (1) is not added to the resin composition, at least the unsaturated carboxylic acid and the epoxy group-containing unsaturated compound contained in the resin composition are easily carried out. The molecular weight of the alkali-soluble resin of the polymerized copolymer is increased.

[Examples 15 to 28, and Comparative Examples 7 to 12]

Using the resin compositions immediately after preparation in Examples 1 to 14 and Comparative Examples 1 to 6, and the resin compositions stored at 25 ° C for 168 hours, Examples 15 to 28 and Comparative Examples 7 to 12 were prepared. A photosensitive resin composition. Specifically, the alkali-soluble resin (A) and the additive compound in the amounts shown in Table 2 were added, and the type and amount of the photopolymerizable monomer described in Table 2 were added to the resin composition of the type described in Table 2 (B). After the photopolymerization initiator (C), the solid content concentration was adjusted with PGMEA to prepare a photosensitive resin composition having a solid concentration of 15% by mass. Using the obtained photosensitive resin composition, the development of the photosensitive resin composition was evaluated by the following method.

In addition, in Table 2, each abbreviation symbol shows the following, and the numerical value in parentheses is a compounding quantity (mass part).

(Photopolymerizable monomer (B))

DPHA: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

(Photopolymerization initiator (C))

OXE01:1, 2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylidenefluorene)] ("IRGACURE OXE01" manufactured by BASF)

[Density evaluation]

The photosensitive resin composition prepared in each of the above Examples and Comparative Examples was applied onto a glass substrate (Eagle-XG, manufactured by Corning Incorporated) by a spin coater, and then dried at 80 ° C for 5 minutes to obtain 3.0 to 5.0 μm. A photosensitive resin layer having a film thickness. Next, the photosensitive resin layer was irradiated with ultraviolet rays through a mask having a dot pattern of 5 to 10 μm. Subsequently, it was developed by a spray in a potassium hydroxide aqueous solution having a concentration of 0.04% by mass which was heated to 23 ° C to form a dot pattern. Next, the developing property was evaluated by measuring the time until the unexposed portion was completely dissolved (BP: Breakpoint). The evaluation of the developing property was a photosensitive resin composition obtained by using the resin composition immediately after the preparation. This was carried out with a photosensitive resin composition obtained by using a resin composition which was stored at 25 ° C for 168 hours. The results are shown in Table 2.

According to Table 2, Examples 15 to 28 in which a photopolymerizable monomer (B) and a photopolymerization initiator (C) were added to the resin compositions of Examples 1 to 14 containing the compound represented by the above formula (1) The photosensitive resin composition is a photosensitive resin composition obtained by using the resin composition immediately after preparation, and a photosensitive resin composition obtained by using the resin composition after storage for 168 hours, the difference of BP is 0 to 5 seconds. It can be seen that there is almost no difference in the imaging time between the two.

On the other hand, a photopolymerizable monomer (B) and a photopolymerization initiation (C) are added to the resin composition of Comparative Examples 1 to 6 in which a comparative compound similar to the structure of the compound represented by the above formula (1) is added. The photosensitive resin composition of Comparative Examples 7 to 12, the photosensitive resin composition obtained using the resin composition immediately after preparation, and the photosensitive resin composition obtained by using the resin composition after storage for 168 hours, BP difference When the photosensitive resin composition was prepared without using the resin composition immediately after preparation, the development time was largely delayed.

Claims (6)

A resin composition comprising an alkali-soluble resin (A), a compound represented by the following formula (1), and a solvent (S), wherein the alkali-soluble resin (A) contains at least an unsaturated carboxylic acid (a1) and a ring-containing ring a copolymer (A1) obtained by polymerizing an oxy unsaturated compound (a2), wherein the solvent (S) comprises propylene glycol monomethyl ether acetate, (wherein R ¹ and R ² each independently represent a hydrogen atom or an organic group, but at least one of R ¹ and R ² represents an organic group, and R ¹ and R ² may be bonded to each other to form a cyclic structure, or may be A bond containing a hetero atom, R ³ represents a single bond or an organic group, and R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a sulfhydryl group, a sulfide group, a decyl group, a decyl group, or a nitro group. , nitroso, sulfino, sulfo, sulfonato, phosphino, phosphinyl, phosphono, phospholipid Phosphonato), or an organic group, R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitroso group, and a nitro group. Sulfo, sulfo, sulfonate, phosphino, phosphinyl, phosphonium, phosphate, amine, ammonium, or organic, but R ⁶ and R ^{7 are} not hydroxyl, R ⁶ , R ⁷ , R ⁸ and R ⁹ may form a cyclic structure for the two or more bonds, or may contain a bond of a hetero atom, and R ¹⁰ represents a hydrogen atom or an organic group. The resin composition of the first aspect of the invention, wherein the ratio of the unit derived from the epoxy group-containing unsaturated compound (a2) in the alkali-soluble resin (A) is 30% by mass. The resin composition of the first or second aspect of the invention, wherein the ratio of the unit derived from the unsaturated carboxylic acid (a1) in the alkali-soluble resin (A) is 20% by mass or more. A photosensitive resin composition containing the resin composition of the first aspect of the patent application, a photopolymerizable monomer (B), and a photopolymerization initiator (C). A spacer formed of a photosensitive resin composition as disclosed in claim 4 of the patent application. A display device comprising a spacer as in item 5 of the patent application.