KR20160091339A - Active energy ray curable resin composition, and display element spacer and/or color filter protective film using same - Google Patents

Abstract

A spacer for a display element excellent in heat resistance transparency, flatness, flexibility and toughness, and an active energy ray curable resin composition capable of forming a color filter protective film, a display element spacer and a color filter protective film are provided. The resin composition of the present invention contains a reactive polycarboxylic acid compound (A), a reactive compound (B) other than the compound (A), a photopolymerization initiator (C) and an organic solvent (D) (D) obtained by reacting at least a reaction product of an epoxy resin (a) represented by the following general formula (1) and a compound (b) having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in one molecule with a polybasic acid anhydride will be. (Wherein n represents an integer of 0 to 2)

Description

TECHNICAL FIELD [0001] The present invention relates to an active energy ray-curable resin composition, a spacer for a display element using the same, and / or a protective film for a color filter,

The present invention relates to an active energy ray-curable resin composition, a display element spacer and / or a color filter protective film.

As a material for a display device, a resin composition comprising a binder polymer, a photopolymerizable monomer and a photopolymerization initiator has been used. In recent years, as a material used for display device materials "LCD, EL, PDP, FED (SED), rear projection display, electronic paper, A display device (LCD) is rapidly spreading. In general, a color liquid crystal display device has a structure in which a gap portion of about 1 to 10 mu m is provided by opposing an electrode substrate such as a color filter and a TFT substrate, a liquid crystal compound is filled in the gap portion and the periphery thereof is sealed with a sealing material I am taking.

The color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate so as to shield a boundary portion between pixels, and red (R), green (G), and blue A coloring layer, a protective film, and a transparent electrode film are stacked in this order from the side close to the transparent substrate. An alignment film is provided on the inner surface side of the color filter and the electrode substrate opposed thereto. In order to keep the cell gap constant and uniform between the color filter and the electric substrate, a pillar having a certain particle diameter is dispersed as a spacer, or a spacer having a columnar or stripe shape having a height corresponding to the cell gap Respectively. A color image is obtained by controlling the light transmittance of the liquid crystal layer behind each colored pixel in each color. Such a color filter is not limited to a color liquid crystal display device but is also used for other display devices such as EL and rear projection displays.

The colored layer, the protective film, and the spacer may be formed using a resin. The colored layer needs to be formed in a predetermined pattern for each pixel of each color. It is preferable that the protective film is capable of covering only the region where the colored layer on the transparent substrate is formed in consideration of the sealing property and tightness of the sealing portion. In addition, it is necessary to accurately set the spacer in the formation region of the black matrix layer, that is, in the non-display region. For this reason, the colored layer, the protective film and the columnar spacers are formed by using the curable resin which can easily limit the area to be cured by the photomask.

Further, when development is carried out using an organic solvent after exposure of the coated surface of the curable resin in order to form a colored layer, a protective film, or columnar spacers, it is troublesome in terms of handling and wastewater treatment and economic efficiency and stability are insufficient. To develop an alkali aqueous solution after exposure to light, thereby developing a curable resin. For these applications, a high temperature (200-260 占 폚 or higher) is applied at the time of formation of an orientation film and formation of a transparent electrode, so that it is required to have a very high heat resistance, particularly excellent in color resist and spacer have.

Patent Document 1 uses a photosensitive resin obtained by neutralizing an acid-modified epoxy acrylate of a cresol novolac epoxy resin with a primary amino compound as a polymer component of a photosensitive resin composition for a photo spacer and a color filter. However, in a composition containing such a salt of a primary amino compound or water, the coating property and the flatness are poor, and it can not be said that the applicability to a device such as a slit coater is sufficient.

In Patent Document 2, acid-modified epoxy acrylate of cresol novolak epoxy resin or phenol novolak epoxy resin is used as a polymer component of the photosensitive resin composition for a photo-spacer. However, there has been a problem that the radiation sensitivity and developability deteriorate and the level is not sufficiently satisfactory.

Patent Document 3 discloses that a reaction product obtained by adding acrylic acid and dimethylol propionic acid to a cresol novolac epoxy resin as a polymer component of a protective film for a color filter or a resist ink composition for a flexible printed wiring board is modified with caprolactone, Ray hardenable resin is used. The polymer component, which is the main component of the composition, is excellent in developability and flexibility, but has a problem that the elastic recovery rate required for the photo-spacer deteriorates.

Patent Document 4 discloses that a resin composition containing an unsaturated group-containing polycarboxylic acid is suitable for a solder resist. However, no description is given for a spacer for a display element or a protective film for a color filter.

Japanese Patent Application Laid-Open No. 2004-109752 Japanese Patent Application Laid-Open No. 2007-010885 Japanese Patent Application Laid-Open No. 2004-300266 Japanese Patent No. 2704661

The present invention provides an active energy ray-curable resin composition which is excellent in developability, curability, and high-speed coating property and which is excellent in heat resistance transparency, flatness, flexibility and toughness, and a color filter protective film .

DISCLOSURE OF THE INVENTION In order to solve the above problems, the present inventors have conducted intensive studies and found that a specific compound and a resin composition having a composition solve the above problems, and have reached the present invention.

That is,

(1) a spacer for a display element or a spacer for a display element containing a reactive polycarboxylic acid compound (A), a reactive compound (B) other than the reactive polycarboxylic acid compound (A), a photopolymerization initiator (C) Wherein the reactive polycarboxylic acid compound (A) is obtained by reacting an epoxy resin (a) represented by the general formula (1) with at least one polymerizable ethylenic unsaturated group in one molecule and one (D) is further reacted with the reaction product (E) of the compound (b) having a carboxyl group and the compound (c) having at least two hydroxyl groups and at least one carboxyl group in one molecule, Wherein the active energy ray-curable resin composition is a polycarboxylic acid compound (A).

(Wherein n represents an integer of 0 to 2)

(2) In the present invention, the reactive polycarboxylic acid compound (A) is obtained by reacting the epoxy resin (a) represented by the general formula (1) with at least one polymerizable ethylenic unsaturated group and at least one carboxyl group (D) is further reacted with the compound (b) having a hydroxyl group and the compound (c) having at least two hydroxyl groups and at least one carboxyl group in a molecule and the reaction product (E) A) according to the above (1), or an active energy ray-curable resin composition for a color filter protective film.

(3) The present invention also relates to a spacer for a display element formed from the active energy ray-curable resin composition according to (1) or (2).

(4) The present invention also relates to a color filter protective film formed from the active energy ray-curable resin composition described in (1) or (2) above.

The active energy ray-curable resin composition comprising the reactive polycarboxylic acid compound (A) of the present invention is excellent in the developing property, has a high radiation sensitivity, and is excellent in heat resistance, transparency, flatness, flexibility and toughness, A filter protective film can be provided.

Hereinafter, the present invention will be described in detail.

The reactive polycarboxylic acid compound (A) in the present invention is obtained by reacting the epoxy resin (a) represented by the general formula (1) with a compound having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in one molecule (d) is further reacted with the reaction product (E) of the compound (b) having a hydroxyl group and the compound (c) having at least two hydroxyl groups and at least one carboxyl group in one molecule.

That is, the reactive polycarboxylic acid compound (A) in the present invention can be obtained by reacting the reaction product (E) of the epoxy resin (a) and the compound (b) with the polybasic acid anhydride (d) Is obtained by reacting a reaction product (E) of the compound (b) and the compound (c) with a polybasic acid anhydride (d).

In the present invention, the characteristics of the present invention are exhibited by introducing an ethylenic unsaturated group and a hydroxyl group into the molecular chain by an epoxycarboxylation reaction.

The epoxy resin (a) represented by the general formula (1) in the present invention is a copolymer of (4 (4 (1,1-bis (p- hydroxyphenyl) ethyl), a, , Phenol compound (PA1)) with epihalohydrin. The present epoxy resin is represented by the following representative structure.

(Wherein n represents an integer of 0 to 2)

The present epoxy resin is generally available as TECMORE VG 3101L (product of Printec Co.), NC-6300C (product of Nippon Kayaku Co., Ltd.), NC-6300H (product of Nippon Kayaku Co., Ltd.) Can also be obtained by the following production method.

The epoxy resin (a) used in the present invention is more preferably a solid at room temperature. In the present invention, an epoxy resin (a) having a softening point of 50 to 100 캜 or a melting point of 50 to 190 캜 is usually used, but it is preferred that the softening point is 60 to 100 캜 or the melting point is 60 to 190 캜. The epoxy equivalent of 130 to 500 g / eq. Is usually used in the present invention, but is preferably 150 to 400 g / eq., More preferably 170 to 300 g / eq. When the epoxy equivalence is too small, the resin tends to be hard and fragile. When the epoxy equivalent is too large, hardness hardly occurs and the glass transition point may be lowered.

Examples of the epihalohydrin used in the reaction of the phenol compound (PA1) with epihalohydrin include epichlorohydrin,? -Methyl epichlorohydrin,? -Methyl epichlorohydrin, epibromohydrin, and the like In the present invention, epichlorohydrin which is industrially easily available is preferable. The epihalohydrin is used in an amount of usually 2 to 15 moles, preferably 4 to 10 moles, per 1 mole of the hydroxyl group of the phenol compound (PA1). If too much epihalohydrin is used, not only the productivity is bad but also the softening point of the epoxy resin to be produced is lowered, which may not have a good effect on the tackiness when the prepreg is used. When the amount of epihalohydrin is 2 mol or less, the value of n becomes large, and gelation tends to occur during production.

In the epoxidation reaction, it is preferable to use an alkali metal hydroxide. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Further, the alkali metal hydroxide may be used as a solid matter or an aqueous solution thereof. For example, in the case of using an alkali metal hydroxide as an aqueous solution, an aqueous solution of an alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or atmospheric pressure, The epoxidation reaction can be carried out by removing water and continuously returning epihalohydrin into the reaction system. Further, when a solid is used, it is preferable to use a flaky one because of its ease of handling and solubility. The amount of the alkali metal hydroxide to be used is usually from 0.90 to 1.5 mol, preferably from 1.01 to 1.25 mol, and more preferably from 1.01 to 1.15 mol, based on 1 mol of the hydroxyl group of the phenol compound (PA1).

In the epoxidation reaction, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride, tetramethylphosphonium chloride, tetramethylphosphonium bromide, trimethylbenzylphosphonium chloride, A quaternary phosphonium salt such as triphenylbenzylphosphonium chloride or triphenylethyl bromide may be added as a catalyst. The amount of these quaternary salts to be used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the phenol compound (PA1).

In the epoxidation reaction, alcohols such as methanol, ethanol and isopropyl alcohol, ethers such as tetrahydrofuran and dioxane, aprotic polar solvents such as dimethylsulfone, dimethylsulfoxide and dimethylimidazolidinone are added It is preferable to carry out the reaction, and in the present invention, it is particularly preferable to use alcohols and / or ethers from the optical properties.

When the alcohols or ethers are used, the amount of the alcohols or ethers to be used is usually 2 to 50% by weight, preferably 4 to 20% by weight based on the amount of epihalohydrin used. On the other hand, when the aprotic polar solvent is used, its amount to be used is usually 5 to 100% by weight, preferably 10 to 80% by weight based on the amount of epihalohydrin used.

In the epoxidation reaction, the reaction temperature is usually from 30 to 90 캜, preferably from 35 to 80 캜. On the other hand, the reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours. This reaction may be a depressurized state at normal pressure or may be carried out under an azeotropic dehydration condition of water-epihalohydrin under reduced pressure. The reactants of these epoxidation reactions can be purified by removing epihalohydrin, a solvent, etc., after water washing or without heating under reduced pressure. Further, in order to obtain an epoxy resin having less hydrolyzable halogen, the recovered reaction product is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added, To ensure the ring-opening of halohydrin as a by-product.

In this case, the amount of the alkali metal hydroxide to be used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 mol of the hydroxyl group of the phenol compound (PA1) used for the epoxidation. The reaction temperature is usually from 50 to 120 캜, and the reaction time is usually from 0.5 to 2 hours.

In the epoxidation reaction, after completion of the reaction, the resulting salt is removed by filtration, washing with water and the like, and the solvent is further distilled off under reduced pressure to obtain an epoxy resin usable in the present invention. The epoxy resin obtained in this manner includes epoxy resins added by some of the solvents and water, and those in which halogen is left without ring closure.

The epoxy resin (a), which is the reaction product of the phenolic compound (PA1) and the epihalohydrin thus obtained, is excellent in productivity and handleability and satisfies any one of the following conditions for imparting high mechanical strength to the cured product .

1. The epoxy equivalent is preferably 195 to 245 g / eq., More preferably 200 to 240 g / eq.

2. In Gel Permeation Chromatography, the phenol compounds (PA1) were connected in an amount of 30% by area or less by epihalohydrin, 20% by area or less in 3 connections, and more preferably 2 Area% or less, and three connected parts are 15 area% or less. And the other is a monomer of the epoxy resin (a).

The compound (b) having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group per molecule in the present invention is reacted to impart reactivity to the active energy ray. The ethylenic unsaturated group and the carboxyl group are not limited as long as they have one or more ethylenic unsaturated groups and carboxyl groups, respectively. These include monocarboxylic acid compounds and polycarboxylic acid compounds.

Examples of the monocarboxylic acid compound having one carboxyl group per molecule include (meth) acrylic acid, crotonic acid,? -Cyanosinic acid, cinnamic acid, or a monoglycidyl compound containing a saturated or unsaturated dibasic acid and an unsaturated group . ≪ / RTI > Examples of the (meth) acrylic acids in the above include (meth) acrylic acid,? -Styryl acrylic acid,? -Furfuryl acrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride, (Meth) acrylate derivatives and half-esters, which are inborn reactants, which are monohydric reactants of saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives, and the like.

As the polycarboxylic acid compound having two or more carboxyl groups in one molecule, a (meth) acrylate derivative having a plurality of hydroxyl groups in one molecule and a half ester, which is a bimolecular reactant, a compound having a saturated or unsaturated dibasic acid and a plurality of epoxy groups And half-esters, which are in-react products of glycidyl (meth) acrylate derivatives.

Among them, a reaction product of (meth) acrylic acid, (meth) acrylic acid and epsilon -caprolactone, or cinnamic acid is most preferable in terms of sensitivity when the resin composition is an active energy ray-curable resin. As the compound (b), it is preferable that the compound does not have a hydroxyl group.

The compound (c) having at least two hydroxyl groups and at least one carboxyl group in a molecule to be used in the present invention is reacted for the purpose of introducing a hydroxyl group into the carboxylate compound.

Specific examples of the compound (c) having at least two hydroxyl groups and at least one carboxyl group in a molecule in the present invention include dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylol And polyhydroxy-containing monocarboxylic acids such as valeric acid and dimethylolcaproic acid. Particularly preferred examples include dimethylolpropionic acid and the like.

Among them, in consideration of the stability of the reaction between the epoxy resin (a) and the compound (b) and the compound (c), the compounds (b) and (c) are preferably monocarboxylic acids, Even when carboxylic acid is used in combination, it is preferable that the value represented by the total molar amount of the monocarboxylic acid / the total molar amount of the polycarboxylic acid is 15 or more.

The charging ratio of the total amount of the carboxylic acid of the epoxy resin (a), the compound (b) and the compound (c) to be used in this reaction in the reaction should be appropriately changed depending on the application. That is, when all the epoxy groups are carboxylated, unreacted epoxy groups do not remain, so that the storage stability of the reactive epoxycarboxylate compound is high. In this case, only the reactivity due to the introduced double bond is used.

On the other hand, by deliberately reducing the amount of the carboxylic acid compound to leave the unreacted residual epoxy groups, the reactivity by the introduced unsaturated bonds and the reaction by the remaining epoxy groups, for example, the polymerization reaction by the light-ion catalyst or the thermal polymerization reaction It is also possible to use them in combination. However, in this case, attention must be paid to examination of the preservation and production conditions of the reactive epoxycarboxylate compound (E).

When the total amount of the compound (b) and the compound (c) to be used as needed is 90 to 120 equivalents based on 1 equivalent of the epoxy resin (a) when the reactive epoxy carboxylate compound (E) %. Within this range, production under relatively stable conditions is possible. If the total amount of the compound (b) and the compound (c) to be used is larger than the above, the excess compound (b) and the compound (c) remain undesirably.

When the epoxy group is left intentionally, it is preferable that the total amount of the compound (b) and the compound (c) to be used as needed is 20 to 90 equivalent% based on 1 equivalent of the epoxy resin (a). In the case of deviating from this range, the reaction by the epoxy group does not progress sufficiently. In this case, it is necessary to pay attention to the gelation during the reaction and the stability with time of the reactive epoxycarboxylate compound (E).

The ratio of the compound (b) to the compound (c) is 95: 5 to 5:95, 60 < / RTI > Within this range, the sensitivity to the active energy ray is good, and a sufficient hydroxyl group can be introduced to react the reactive epoxycarboxylate compound (E) with the polybasic acid anhydride (d).

The carboxylation reaction may be carried out by reacting in a solvent or by diluting with a solvent. The solvent usable here is not particularly limited as long as it is an inert solvent for the carboxylation reaction.

The amount of the solvent to be used should be appropriately adjusted depending on the viscosity and application of the resin to be obtained, but is preferably 90 to 30 parts by weight, more preferably 80 to 50 parts by weight, based on 100 parts by weight of the solid content.

Specific examples thereof include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane and decane; and mixtures thereof such as petroleum ether, white gasoline, solvent naphtha , Ester solvents, ether solvents, ketone solvents and the like.

Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate, cyclic esters such as? -Butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl Mono or polyalkylene glycol monoalkyl ether monoacetates such as ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate and butylene glycol monomethyl ether acetate , Polycarboxylic acid alkyl esters such as dialkyl glutaric acid, dialkyl succinate, dialkyl adipate and the like.

Examples of the ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, ketones such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol Glycol ethers such as diethyl ether, and cyclic ethers such as tetrahydrofuran.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone.

In addition, it can be carried out in a single or mixed organic solvent such as other reactive compound (B) described later. In this case, when the composition is used as a curable composition, the composition can be directly used as a composition, which is preferable.

In the reaction, it is preferable to use a catalyst in order to accelerate the reaction, and the amount of the catalyst to be used may vary depending on the reactants, that is, the epoxy resin (a), the carboxylic acid compound (b) Is generally 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of reactants to which a solvent or the like is added. The reaction temperature at that time is usually 60 to 150 占 폚, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, Boron, chromium octanoate, and zirconium octanoate, and the like.

Further, it is also possible to use, as a heat-hardening agent, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenyl picrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4-hydroxytoluene .

This reaction is referred to as the end point at which the acid value of the sample becomes 5 mgKOH / g or less, and preferably 3 mgKOH / g or less while appropriately sampling.

The weight average molecular weight of the reactive epoxycarboxylate compound (E) thus obtained is preferably in the range of 1,000 to 50,000, more preferably 2,000 to 30,000 in terms of polystyrene in GPC.

If the molecular weight is smaller than the molecular weight, the hardness of the cured product is not sufficiently exhibited. If the molecular weight is too large, the viscosity becomes high and the application becomes difficult.

Next, the process of the acid part will be described in detail. The acid part treatment is carried out for the purpose of introducing a carboxyl group into the reactive epoxycarboxylate compound (E) obtained in the previous step to obtain a reactive polycarboxylic acid compound (A). That is, the carboxyl group is introduced through the ester bond by addition reaction of the polybasic acid anhydride (d) to the hydroxyl group generated by the carboxylation reaction.

As specific examples of the polybasic acid anhydride (d), any compound having an acid anhydride structure in the molecule can be used, and examples thereof include anhydrous succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, Particularly preferred are hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride.

The reaction of adding the polybasic acid anhydride (d) can be carried out by adding the polybasic acid anhydride (d) to the carboxylation reaction solution. The amount of addition should be appropriately changed depending on the application.

When the reactive polycarboxylic acid compound (A) of the present invention is to be used as an alkali-developing type resist, the amount of the polybasic acid anhydride (d) to be added can be adjusted by adding the reactive polycarboxylic acid (d) It is preferable to add a calculated value such that the solid acid value (in accordance with JIS K5601-2-1: 1999) of the compound (A) is 40 to 120 mg · KOH / g, and more preferably 60 to 120 mg · KOH / g. When the solid acid value at this time is in this range, the developability of the aqueous alkali solution of the photosensitive resin composition of the present invention is satisfactory. That is, good patterning performance and management for the phenomenon are wide, and excessive acid anhydrides do not remain.

In the reaction, it is preferable to use a catalyst in order to accelerate the reaction. The amount of the catalyst to be used is not particularly limited as long as the amount of the catalyst to be reacted, that is, the reactivity obtained from the epoxy compound (a), the carboxylic acid compound (b) Is usually 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of reactants to which an epoxy carboxylate compound (E) and a polybasic acid anhydride (d), and optionally a solvent, and the like are added. The reaction temperature at that time is usually 60 to 150 占 폚, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, Boron, chromium octanoate, zirconium octanoate, and the like.

The acid part can be reacted in a solvent or diluted with a solvent. The solvent usable herein is not particularly limited as long as the acid moiety is an inert solvent for the reaction. Further, in the case where a solvent is used in the predominantly-in-situ carboxylation reaction, an acid moiety, which is the next step, may be directly provided to the reaction without removing the solvent, provided that the solvent is inert to both reactions. The solvent which can be used may be the same as that which can be used in the carboxylation reaction.

The amount of the solvent to be used should be appropriately adjusted depending on the viscosity and application of the resin to be obtained, but is preferably 90 to 30 parts by weight, more preferably 80 to 50 parts by weight, based on 100 parts by weight of the solid content.

In addition, it can be carried out in a single or mixed organic solvent such as a reactive compound (B) described later. In this case, when the composition is used as a curable composition, the composition can be directly used as a composition, which is preferable.

The thermal polymerization inhibitor and the like are preferably the same as those exemplified in the above carboxylation reaction.

This reaction is referred to as the end point, taking the point that the acid value of the reactant falls within the range of ± 10% of the set acid value while appropriately sampling.

The preferred molecular weight range of the reactive polycarboxylic acid compound (A) is in the range of 1,000 to 50,000, more preferably 2,000 to 30,000, in terms of polystyrene equivalent weight average molecular weight in GPC.

The use ratio of the reactive polycarboxylic acid compound (A) in the resin composition is usually about 5 to 69% by weight, preferably about 8 to 59% by weight.

Examples of the reactive compound (B) which can be used in the present invention include so-called reactive oligomers such as radical reaction type acrylates, cationic reaction type other epoxy compounds, and vinyl compounds which are responsive to both.

Examples of the radical reactive type acrylate include monofunctional (meth) acrylate, difunctional (meth) acrylate, trifunctional or more (meth) acrylate, urethane (meth) acrylate oligomer, polyester Acrylate oligomer, epoxy (meth) acrylate oligomer and the like.

As the monofunctional (meth) acrylate, for example, acryloylmorpholine; (Meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, (Meth) acrylate such as phenoxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and the like; Ethyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, phenylthioethyl (meth) acrylate, 2-hydroxy- (Meth) acrylate such as methoxy (meth) acrylate, phenylphenol ethoxy (meth) acrylate and the like.

Examples of the bifunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane di (Meth) acrylate, bisphenol A (poly) ethoxy (meth) acrylate, bisphenol A (poly) propoxy di (meth) acrylate, bisphenol F Di (meth) acrylate of ε-caprolactone adduct of neopentyl glycol diacrylate, glycol di (meth) acrylate, and (poly) ethylene glycol di (meth) acrylate hydroxypivalic acid (for example, Nippon Kayaku Co., Ltd.). Product, KAYARAD HX-220, HX-620, etc.).

Examples of the trifunctional or higher polyfunctional (meth) acrylate include dimethylol propane tetra (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol octane tri (meth) acrylate, trimethylol propane polyethoxy tri Methylol ethers such as trimethylolpropane (poly) propoxytri (meth) acrylate and trimethylolpropane (poly) ethoxy (poly) propoxytri (meth) acrylate; (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (metha) acrylate, pentaerythritol triethacrylate, pentaerythritol tri ) Erythritol such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; Tris [(meth) acryloyloxyethyl] isocyanurate, and caprolactone-modified tris [(meth) acryloyloxyethyl] isocyanurate; Succinic acid-modified pentaerythritol triacrylate, and succinic acid-modified dipentaerythritol pentaacrylate.

(Poly) ester (meth) acrylate oligomer include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, polyethylene glycol, Butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl- Straight-chain or branched alkyldiols such as pentane diol, 2,4-diethyl-1,5-pentane diol and 2-butyl-2-ethyl-1,3-propane diol, (Poly) ester diol, which is a reaction product of a diol compound such as bisphenol A (poly) ethoxy diol or bisphenol A (poly) propoxy diol with the above dibasic alkyl diol, bis Reactants and the like.

Examples of the urethane (meth) acrylate oligomer include diol compounds such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, Butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A polyethoxydiol, bisphenol A polypro Or a polyester diol which is a reaction product of these diol compounds with a dibasic acid or an anhydride thereof (for example, succinic acid, adipic acid, azelaic acid, dimeric acid, isophthalic acid, terephthalic acid, phthalic acid or an anhydride thereof) Organic polyisocyanates (e.g., tetramethylene diisocyanate, hexamer Chain saturated hydrocarbon isocyanates such as benzene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane di Cyclic saturated hydrocarbon isocyanates such as isocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate and hydrogenated toluene diisocyanate, 2,4-tolylene diisocyanate, Isocyanate, p-phenylenediisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-isopropyl-1,3-phenyldiisocyanate and 1,5-naphthalene diisocyanate) Reacted with a hydroxyl group-containing (meth) acrylate, Can.

As the epoxy (meth) acrylate oligomer, a compound having an epoxy group and a carboxylate compound of (meth) acrylic acid. Examples of the epoxy (meth) acrylate include phenol novolak type epoxy (meth) acrylate, cresol novolak type epoxy (meth) acrylate, trihydroxyphenyl methane type epoxy (meth) acrylate, dicyclopentadiene phenol type epoxy (Meth) acrylate, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, biphenol type epoxy (meth) acrylate, bisphenol A novolak type epoxy ) Acrylate, glyoxylated epoxy (meth) acrylate, heterocyclic epoxy (meth) acrylate, and the like.

Examples of vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds. Examples of the vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of the styrene include styrene, methylstyrene, and ethylstyrene. Examples of other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

The cationic reaction type monomer is not particularly limited as long as it is a compound having an epoxy group in general. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl- 4-epoxycyclohexanecarboxylate (manufactured by Union Carbide Corporation, such as Cyracure UVR-6110), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (Manufactured by Daicel Chemical Industries Ltd., " Celloxide 3000 ", etc.), allylcyclohexene dioxide, 3,4, -epoxy-4-methylcyclohexyl-2-propylene (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate Cyracure UVR-6128 "), bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl ), And the ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethyl siloxane and the like.

Of these, the reactive compound (B) is most preferably a monofunctional, bifunctional or trifunctional or more (meth) acrylate from the viewpoint of good polymerizability and improved strength of the resulting spacer or the like.

The reactive compound (B) of the present invention may be used alone or in combination of two or more. The proportion of the reactive compound (B) in the composition is preferably 30 parts by weight to 250 parts by weight, more preferably 50 parts by weight to 200 parts by weight, per 100 parts by weight of the reactive polycarboxylic acid compound (A). When the amount of the reactive compound (B) used is from 30 parts by weight to 250 parts by weight, the sensitivity of the composition and the heat resistance and elastic properties of the resulting spacer for a display element are improved.

Examples of the photopolymerization initiator (C) of the present invention include a photopolymerization initiator (C) which is capable of reacting with an active energy ray and capable of initiating polymerization of a reactive compound (B) other than the reactive polycarboxylic acid compound (A) and the reactive polycarboxylic acid compound It is a component that produces species. Examples of such photopolymerization initiators (C) include O-acyloxime compounds, acetophenone compounds, and imidazole compounds.

Examples of the O-acyloxime compound include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octan- Benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol- -9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol- Oxazol-3-yl) -1- (O-acetyloxime), ethanone -1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol- 3-yl] -1- (O-acetyloxime) -9H-carbazol-3- And the like. Among these, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- Yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- { Methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred. These O-acyloxime compounds may be used alone or in combination of two or more.

Examples of the acetophenone compound include an? -Amino ketone compound and? -Hydroxyketone compound.

Examples of the? -amino ketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- 1- (4-morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one .

Examples of the? -hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropane-1-one, 1- (4- 1-on, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and 1-hydroxycyclohexyl phenyl ketone.

Among these acetophenone compounds,? -Amino ketone compounds are preferable, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one are more preferred.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) 5'-tetraphenyl-1,2'-biimidazole, and the like. Of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis (2,4,6-trichlorophenyl) -4,4' (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2', 5'-tetraphenyl- - nonimidazole is more preferred.

The photopolymerization initiator (C) may be a commercially available product such as 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (Irgacure 907) (4-morpholinophenyl) -butan-1-one (Irgacure 379), ethanone-1- [9- ) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02) (above, Ciba Specialty Chemicals Corporation).

In the photosensitive resin composition of the present invention, the amount of the component (C) to be used is usually 1% by weight or more and 10% by weight or less, preferably 1% by weight or more when the solid content of the resin composition of the present invention is 100% 7% by weight or less.

The photopolymerization initiator (C) may also be used in combination with the curing accelerator (F). Examples of curing accelerators which can be used in combination include triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethylbenzoate, dimethylaminoacetophenone, p- dimethylaminobenzoic acid isoamino ester, EPA Amines, and 2-mercaptobenzothiazole. The amount of these curing accelerators to be used is generally 0% by weight or more and 5% by weight or less when the solid content of the resin composition of the present invention is 100% by weight.

As the organic solvent (D), it is suitably used that each constituent component is uniformly dissolved or dispersed and does not react with each constituent component. Examples of such organic solvents (D) include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and mixtures thereof such as petroleum ether, white gasoline, solvent naphtha, ester solvents, ether solvents, ketone solvents, For example, alcohols such as alcohols, ethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol monoalkyl ether acetates , Lactic acid esters, aliphatic carboxylic acid esters, amides, ketones and the like. These may be used alone or in combination of two or more.

Specifically, examples of the organic solvent (D) include alcohols such as benzyl alcohol; Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate and diethylene glycol monobutyl ether acetate; Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether; Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate and dipropylene glycol monobutyl ether acetate; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate and isoamyl lactate; Methyl ethyl ketone, ethyl 3-ethoxyacetate, ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxyacetate, Methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl acetate, Aliphatic carboxylic acid esters such as butylate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate and ethyl pyruvate; Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide and N, N-dimethylacetamide; And ketones such as N-methylpyrrolidone and? -Butyrolactone. These may be used alone or in combination of two or more.

The solid content in the composition is usually 10 wt% or more and 40 wt% or less, preferably 15 wt% or more and 35 wt% or less. By setting the solid content concentration of the above-mentioned composition within the above range, it is possible to effectively suppress the occurrence of the improvement in the coating property, the improvement in the uniformity of the film thickness and the uneven application.

The viscosity of the composition at 25 占 폚 is usually 1.0 mPa 占 퐏 or more and 1,000 mPa 占 퐏 or less. And preferably 2.0 mPa 占 퐏 or more and 100 mPa 占 퐏 or less. By setting the viscosity of the composition within the above range, it is possible to achieve a balance of a degree of spontaneous uniformity even if coating unevenness occurs, while maintaining film thickness uniformity.

Examples of the alkali-soluble resin (G) to be used in the photosensitive resin composition of the present invention include monomers having a hydroxyl group, acid anhydrides having an ethylenic double bond, monomers having a carboxyl group, monomers having an epoxy group, A monomer having a hydroxyl group, a monomer having a sulfonic acid group, other monomers, and the above-mentioned monofunctional (meth) acrylate.

Specific examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (Meth) acrylate, glycerin mono (meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N -Hydroxymethyl (meth) acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide and the like.

Specific examples of acid anhydrides having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, 3-methylphthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride , Anhydrous 3,4,5,6-tetrahydrophthalic acid, anhydrous cis-1,2,3,6-tetrahydrophthalic acid, and 2-buten-1-ylsuccinic anhydride.

Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof.

Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.

Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene and the like. Further, at least one hydrogen atom of these benzene rings may be substituted with an alkyl group such as a methyl group, an ethyl group or an n-butyl group; An alkoxy group such as a methoxy group, an ethoxy group or an n-butoxy group; A halogen atom; A haloalkyl group in which at least one hydrogen atom of the alkyl group is substituted with a halogen atom; A nitro group; Cyano; Amide groups and the like.

Examples of the monomer having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, (meth) allylsulfonic acid, 2-hydroxy-3- (meth) allyloxypropanesulfonic acid, (meth) Propyl, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid and the like.

Examples of other monomers include hydrocarbon-based olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylic esters, (meth) acrylamides, aromatic vinyl compounds, And conjugated dienes. These compounds may contain a functional group, and examples of the functional group include a carbonyl group and an alkoxy group. Particularly, since the barrier ribs formed from the composition are excellent in heat resistance, (meth) acrylic acid esters and (meth) acrylamides are preferable.

When the alkali-soluble resin (G) is copolymerized, it can be produced by radical polymerization of an unsaturated compound in the presence of a polymerization initiator in a solvent. The above-mentioned solvents may be used, and they may be used alone or in combination of two or more kinds.

As the polymerization initiator used in the polymerization reaction for producing the alkali-soluble resin (G), those generally known as radical polymerization initiators can be used. Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, and 1,1'-bis- (t-butylperoxy) cyclohexane, and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used as a redox type initiator together with a reducing agent.

In the polymerization reaction for producing the alkali-soluble resin (G), a molecular weight regulator can be used to adjust the molecular weight. Examples of the molecular weight regulator include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid; Xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide; Terpinolene, alpha -methylstyrene dimer, and the like.

(E) having a reactive group such as a monomer having a phenolic hydroxyl group or a monomer having a sulfonic acid group, such as the monomer having a hydroxyl group, the acid anhydride having an ethylenic double bond, the monomer having a carboxyl group, or the monomer having an epoxy group, As the compound (f) having a functional group capable of binding to the reactive group and an ethylenic double bond, for example, the following combinations can be mentioned.

(1) For the monomer (e) having a hydroxyl group, an acid anhydride (f) having an ethylenic double bond,

(2) Compounds (f) having an isocyanate group and an ethylenic double bond for the monomer (e) having a hydroxyl group,

(3) Compounds (f) and (f) having a hydroxyl group-containing monomer (e) and having an acyl chloride group and an ethylenic double bond,

(4) The compound (f) having a hydroxyl group and an ethylenic double bond for the acid anhydride (e) having an ethylenic double bond,

(5) Compounds (f) and (f) having an epoxy group and an ethylenic double bond for the monomer (e) having a carboxyl group,

(6) A compound (f) having a carboxyl group and an ethylenic double bond with respect to the monomer (e) having an epoxy group.

Specific examples of the acid anhydride having an ethylenic double bond include the above-mentioned examples.

Specific examples of the compound having an isocyanate group and an ethylenic double bond include 2- (meth) acryloyloxyethyl isocyanate and 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate.

Specific examples of the compound having an acyl chloride group and an ethylenic double bond include (meth) acryloyl chloride.

Specific examples of the compound having a hydroxyl group and an ethylenic double bond include the above-mentioned monomers having a hydroxyl group.

Specific examples of the compound having an epoxy group and an ethylenic double bond include the above-mentioned monomers having an epoxy group.

Specific examples of the compound having a carboxyl group and an ethylenic double bond include the above-mentioned monomers having a carboxyl group.

When a copolymer is reacted with a compound (f) having a functional group capable of binding to a reactive group and an ethylenic double bond, a solvent exemplified in the synthesis of the copolymer may be used as the solvent used in the reaction.

It is also preferable to blend a polymerization inhibitor. As the polymerization inhibitor, known publicly known polymerization inhibitors can be used, and specific examples thereof include 2,6-di-t-butyl-p-cresol.

A catalyst or a neutralizing agent may be added. For example, in the case of reacting a copolymer having a hydroxyl group with a compound having an isocyanate group and an ethylenic double bond, a tin compound or the like can be used. Examples of the tin compound include dibutyltin dilaurate, dibutyltin di (maleic acid monoester), dioctyltin dilaurate, dioctyltin di (maleic acid monoester), and dibutyltin diacetate.

For example, in the case of reacting a monomer having a hydroxyl group with a compound having an acyl chloride group and an ethylenic double bond, a basic catalyst may be used. Examples of the basic catalyst include triethylamine, pyridine, dimethylaniline, and tetramethylurea.

The Mw of the alkali-soluble resin (G) is preferably from 2 × 10 ^{3 to} 1 × 10 ⁵ , more preferably from 5 × 10 ^{3 to} 5 × 10 ⁴ . By setting the Mw of the alkali-soluble resin (G) to 2 × 10 ^{3 to} 1 × 10 ⁵ , the radiation sensitivity and developability of the composition (the property of accurately forming a desired pattern shape) can be increased.

The photosensitive resin composition of the present invention may further contain additives such as a surfactant, a leveling agent, a defoaming agent, a filler, an ultraviolet absorber, a photostabilizer, an antioxidant, a polymerization inhibitor, a crosslinking agent, It is also possible to give the functionality of Examples of the antistatic agent include a hindered amine compound, a benzoate compound, and the like. Examples of the antioxidant include a fluorine compound, a silicone compound, and an acrylic compound. Examples of the ultraviolet absorber include benzotriazole compounds, benzophenone compounds, Examples of the inhibitor include phenol compounds. Examples of the polymerization inhibitor include methoquinone, methylhydroquinone, hydroquinone and the like. Examples of the crosslinking agent include the above polyisocyanates and melamine compounds.

As a resin stream (so-called inert polymer) which does not show reactivity with other active energy rays, for example, other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins , Styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof. These are preferably used in the range of up to 40 parts by weight in the resin composition.

The active energy ray-curable resin composition of the present invention contains the reactive polycarboxylic acid compound (A) in an amount of usually 5 to 69% by weight, preferably 8 to 59% by weight, and the other reactive compound (B) (D) is usually 60 to 90% by weight, preferably 65 to 90% by weight, preferably 5 to 59% by weight, preferably 5 to 59% by weight, To 85% by weight. If necessary, other components may be contained in an amount of usually 0 to 80% by weight.

≪ Method of forming display spacer and color filter protective film >

The spacer for a display element formed of the composition is suitably included in the present invention. The method for forming a spacer for a display element is not particularly limited,

(1) a step of coating the composition on a substrate to form a coating film,

(2) a step of irradiating at least a part of the coating film with radiation,

(3) a step of developing the coating film irradiated with the radiation, and

(4) a step of heating the developed coating film

A method of forming a photo-spacer and / or a color filter protective film by photolithography using the active energy ray-curable resin composition of the present invention will be briefly described. The active energy ray-curable resin composition of the present invention is uniformly applied onto a substrate by a known method such as roll coating, spin coating, spray coating, or slit coating and dried to form a photosensitive resin composition layer. As a coating device, a known coating device can be used, and examples thereof include a spin coater, an air knife coater, a roll coater, a bar coater, a curtain coater, a gravure coater and a comma coater. Here, an example is described in which a transparent electrode is formed on a transparent common electrode provided on a colored layer.

If necessary, heat is applied and dried (prebaking). The drying temperature is preferably 50 占 폚 or higher, more preferably 70 占 폚 or higher, and preferably 150 占 폚 or lower, more preferably 120 占 폚 or lower. The drying time is preferably 30 seconds or more, more preferably 1 minute or more, and further preferably 20 minutes or less, and further preferably 10 minutes or less.

Subsequently, the photosensitive resin composition layer is exposed by an active energy ray through a predetermined photomask. The photosensitive resin composition of the present invention can be formed precisely even in the case of a mask opening having a diameter of about 5 to 10 m (an area of about 20 to 100 m ² ), that is, in a range of a diameter of 6 to 12 m (an area of 30 to 120 m ² ) have.

The active energy ray used for exposure is not particularly limited as long as it can cure the photosensitive resin composition of the present invention. The active energy ray-curable resin composition of the present invention is easily cured by an active energy ray. Specific examples of the active energy ray include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays and laser beams, particle beams such as alpha rays, beta rays and electron rays. Among these, ultraviolet rays, laser beams, visible rays, or electron beams are preferable in view of a suitable use of the present invention. The exposure dose is not particularly limited, but is preferably 20 to 1,000 mJ / cm 2.

Subsequently, the unexposed portion is removed by a developer to perform development. Here, an organic solvent may be used for the developing solution used in the development, but it is preferable to use an aqueous alkali solution. Examples of the aqueous alkali solution which can be used as a developer include aqueous solutions of inorganic salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and the like; And an aqueous solution of an organic salt such as hydroxytetramethylammonium, hydroxytetraethylammonium and the like. These may be used singly or in combination of two or more. In addition, a surfactant such as an anionic surfactant, a cationic surfactant, a positive surfactant or a nonionic surfactant, or a water-soluble organic solvent such as methanol or ethanol may be added. The concentration of the alkali in the aqueous alkali solution is preferably from 0.1 to 5% by weight from the viewpoint of achieving appropriate developability. The development method includes a dip method, a shower method, a puddle method, and a vibration immersion method, but a shower method is preferable. The temperature of the developing solution is preferably used at 25 to 40 占 폚. The development time is appropriately determined depending on the film thickness and the solubility of the resist.

Heating (baking) may be carried out as necessary in order to further ensure curing. When baking is performed, the baking temperature is preferably 120 to 250 占 폚. The baking time varies depending on the type of the heating apparatus. For example, the baking time can be set to 5 minutes to 30 minutes in the case of performing the heating process on the hot plate, and from 30 minutes to 90 minutes in the case of performing the heating process in the oven. A step baking method in which two or more heating steps are performed, or the like may be used.

The film thickness of the spacer thus formed is preferably 0.1 mu m to 8 mu m, more preferably 0.1 mu m to 6 mu m, and particularly preferably 0.1 mu m to 4 mu m.

The spacer formed in the above-described forming method is a spacer having high flatness, flexibility, and small plastic deformation without application unevenness. A liquid crystal display element, an organic EL display element, or the like.

The color filter protective film is preferably 0.5 mu m to 100 mu m, more preferably 1 mu m to 10 mu m.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless specifically stated otherwise in the examples, " part (s) " and "% "

The softening point, the epoxy equivalent, and the acid value were measured under the following conditions.

1) Epoxy equivalent: Measured by the method according to JIS K7236: 2001.

2) Softening point: Measured by the method according to JIS K7234: 1986.

3) Acid value: Measured according to the method according to JIS K0070: 1992

Examples 1-1 to 1-3

[Preparation of reactive polycarboxylic acid compound (A)

N = 0 (64%), n = 1 (23%), n = 2 or more (13%) in the general formula (1) as an epoxy resin (a) NC-6300H (product of Nippon Kayaku Co., Ltd.) (Abbreviated as AA, Mw = 72) as the compound amount in Table 1, and dimethylol propionic acid (abbreviated as DMPA, Mw = 134) as the compound (c) Were added in the amounts shown in Table 1. 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content was 80% by weight of the reaction solution and reacted at 100 DEG C for 24 hours to obtain a solution of the reactive epoxycarboxylate compound (E) . And the solid acid value (AV: mgKOH / g) of 5 or less was used as the reaction end point, and the reaction proceeded to the next reaction. The acid value measurement was carried out in the reaction solution and converted into the acid value as a solid content.

Subsequently, tetrahydrophthalic anhydride (abbreviated as THPA) as a polybasic acid anhydride (d) was added to the reactive epoxycarboxylate compound (E) solution in an amount of 65 parts by weight based on 100 parts by weight of the solid content as a solvent and propylene glycol mono Methyl ether monoacetate was added and heated to 100 占 폚, and then the acid moiety was reacted to obtain a solution of the reactive polycarboxylic acid compound (A). The solid acid value (AV: mgKOH / g) is shown in Table 1.

Comparative Examples 1-1 and 1-2

[Preparation of comparative reactive polycarboxylic acid compound]

Cresol novolak type epoxy resin EOCN-103S (epoxy equivalents: 200 g / eq, product of Nippon Kayaku Co., Ltd.) in the amount shown in Table 1, the amount of acrylic acid as the compound (b) Dimethylol propionic acid (abbreviated as DMPA, Mw = 134) was added in the amount shown in Table 1. 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content became 80% by weight of the reaction solution and reacted at 100 DEG C for 24 hours to obtain a carboxylate compound solution. And a solid acid value (AV: mgKOH / g) of 5 mgKOH / g or less as a reaction end point.

Subsequently, propylene glycol monomethyl ether monoacetate was added to the reactive epoxycarboxylate compound solution so that 65 parts by weight of the amount of the tetrahydric anhydride phthalic acid (abbreviated as THPA) as the polybasic acid anhydride was 100 parts by weight of the solid content as shown in Table 1 After heating to 100 ° C, the acid moiety was reacted to obtain a comparative reactive polycarboxylic acid compound solution. The solid acid value (AV: mgKOH / g) is shown in Table 1.

Comparative Example 1-3

[Preparation of reactive caprolactone-modified polycarboxylic acid compound for comparison]

200 g of cresol novolac epoxy resin EOCN-103S (epoxy equivalent 200 g / eq, product of Nippon Kayaku Co., Ltd.), 58 g of acrylic acid, 40 g of dimethylolpropionic acid, 3 g of triphenylphosphine as a catalyst, Monomethyl ether monoacetate was added so that the solid content was 80% by weight of the reaction solution, and the reaction was carried out at 100 占 폚 for 24 hours. Further, 68 g of? -Caprolactone was added and reacted for 8 hours. Subsequently, 91 g of tetrahydrophthalic anhydride (abbreviated as THPA) as a polybasic acid anhydride and propylene glycol monomethyl ether monoacetate were added so as to be 65 parts by weight based on 100 parts by weight of the solid content as a solvent. After heating to 100 ° C, To obtain a comparative reactive caprolactone-modified polycarboxylic acid compound solution. The solid acid value (AV: mgKOH / g) was 70 mgKOH / g.

The unit of the numerical values in Table 1 is g (grams).

Details of each component used in Examples and Comparative Examples are shown below.

≪ Reactive Compound (B) >

B-1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

≪ Photopolymerization initiator (C) >

C-1: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime) (Irgacure OXE02,

≪ Organic solvent (D) >

PGMEA: Propylene glycol monomethyl ether acetate

DEGDM: diethylene glycol dimethyl ether

<Other Optional Ingredients>

&Lt; Surfactant (H) >

H-1: Silicone surfactant (SH8400FLUID, product of Dow Corning Toray Co., Ltd.)

&Lt; Preparation of the composition &

Example 2-1

100 parts by weight of (B-1) as the reactive compound (B), 100 parts by weight of the reactive compound (B), and 100 parts by weight of the reactive polycarboxylic acid compound (A) were added to a solution containing 100 parts by weight (solid content) 10 parts by weight of (C-1) as an initiator (C-1) and PGMEA and DEGDM as organic solvents were added to a desired solid concentration and 0.3 part by weight of (H-1) as a surfactant (H) Mu] m membrane filter to prepare the above composition (S-1). The values of the organic solvents in Table 2 are the mass ratios of PGMEA and DEGDM.

Examples 2-2 to 2-3 and Comparative Examples 2-1 to 2-3

The compositions of Examples 2-2 to 2-3 and Comparative Examples 2-1 to 2-3 were prepared in the same manner as in Example 2-1 except that the kinds and blending amounts of the respective components were changed as shown in Table 2. The values of the organic solvents in Table 2 are the mass ratios of PGMEA and DEGDM.

<Evaluation>

The compositions of Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3 and the spacers formed of the coating films were evaluated as described below. The evaluation results are shown in Table 3 together.

(Viscosity)

The viscosity (mPa · s) of each composition at 25 ° C was measured using an E-type viscometer (product of TOKI SANGYO CO., LTD., TV-200)

(Solid concentration)

0.3 g of the composition was precisely weighed into an aluminum plate, about 1 g of diethylene glycol dimethyl ether was added, and the mixture was dried on a hot plate at 175 DEG C for 60 minutes. From the weight before and after drying, the solid content concentration (% by mass) I got it.

(Appearance of coating film)

The composition was coated on a 100 x 100 mm chromium-deposited glass using a slit die coater (Techno Machine Ltd., by Rika die), dried under reduced pressure to 0.5 Torr, and then prebaked on a hot plate at 100 캜 for 2 minutes And further exposed at an exposure amount of 200 mJ / cm &lt; 2 &gt; to form a film having a film thickness of 4 mu m from the upper surface of the chromium film formation glass. Under the sodium lamp, the appearance of the coating film was visually observed. At this time, line unevenness (unevenness of one or a plurality of straight lines which occur in a coating direction or in a direction crossing the coating direction), unevenness of fog (unevenness of cloud shape), unevenness of pin marks (point shape Of the unfavorable situation). (Good) ", a case where one of them is slightly visible is indicated as" DELTA (slightly bad) ", and a case where any of these unevenness is clearly seen is referred to as" x (bad) ".

(Flatness)

The film thickness of the coating film on the chromium film-coated glass fabricated as described above was measured using a needle contact measuring device (TOKYO SEIMITSU CO., LTD., SUBCOM). The film thickness uniformity was calculated from the following formula by measuring the film thickness at nine measurement points. The nine measurement points are (50,10), (50,20), (50,30), and (50) where (X [mm], Y , 40, 50, 50, 50, 60, 50, 70, 50, 80, 50, 90. When the film thickness uniformity is 2% or less, it can be judged that the film thickness uniformity is good.

Film thickness uniformity (%) = {FT (X, Y) max-FT (X, Y) min}

(X, Y) max is the maximum value among the film thicknesses at nine measurement points, FT (X, Y) min is the minimum value among the film thicknesses at nine measurement points, FT Is the average value of the film thickness at nine measurement points.

(High-speed coating property)

The coating liquid was ejected from the nozzle so that the distance between the substrate and the nozzle was 150 mu m and the film thickness after the exposure was 2.5 mu m as a coating condition for applying the coating liquid on a 100 mm x 100 mm inorganic glass substrate using a slit coater, Was varied in a range of 120 mm / sec to 200 mm / sec, and the maximum speed at which unevenness of line shape due to liquid removal did not occur was obtained. At this time, when line-shaped unevenness does not occur even at a speed of 180 mm / sec or more, it can be judged that high-speed application is possible.

(Radiation sensitivity)

The above composition was coated on a 100 mm x 100 mm ITO sputtered glass substrate by a spin coat method and then prebaked on a hot plate at 90 캜 for 3 minutes to form a coating film having a thickness of 3.5 탆. Subsequently, the resulting coating film was exposed to light through an ultraviolet exposure apparatus (ORC MANUFACTURING CO., LTD., Type HMW-680GW) through a photomask having a circular pattern with a diameter of 12 mu m formed as an opening. Thereafter, the resist film was developed with a 0.05 mass% aqueous solution of potassium hydroxide at 25 ° C for 60 seconds, washed with pure water for 1 minute, and further baked in an oven at 230 ° C for 30 minutes to form a spacer made from a patterned film. At this time, the minimum exposure amount at which the residual film ratio after post-baking (film thickness of post-baking film × 100 / film thickness after post-baking) was 90% or more was examined. When this value is 55 mJ / cm 2 or less, it is said that the sensitivity is good.

(Development residue)

In addition, the surface of the substrate was observed by naked eyes and the presence or absence of the residue was confirmed. The evaluation criteria are as follows.

○ ... No residue.

△ ... There is a little residue.

× ... There is a lot of residue.

(Compression performance)

A spacer having a circular columnar pattern was formed on the substrate in the same manner as in the evaluation of the radiation sensitivity, except that the exposure dose was set to an exposure dose corresponding to the sensitivity determined by the evaluation of the radiation sensitivity. At that time, the diameter of the photomask interposed at the time of exposure was changed so that the diameter of the pattern bottom portion after the post-baking became 20 占 퐉. This spacer was subjected to a compression test at a load of 50 mN using a micro compacting tester (Fisher Scope H100C, product of Fischer Instruments KK) using a planer indenter of 50 탆 x 50 탆 in shape, and a change in the amount of compressive displacement with respect to the load And the recovery rate (%) was calculated from the amount of displacement at the time of the load of 50 mN and the amount of displacement at the time of removing the load of 50 mN. At this time, when the recovery rate is not less than 70% and the displacement when load of 50 mN is not less than 0.15 탆, a spacer having both a high recovery rate and flexibility can be obtained.

(Total light transmittance)

Coated on a 50 mm x 50 mm alkali-free glass substrate using a spin coater, dried under reduced pressure to 0.5 Torr and then pre-baked on a hot plate at 100 캜 for 2 minutes to form a coating film and further exposed at an exposure amount of 200 mJ / To form a film having a thickness of 4 탆. The evaluation substrate having the cured coating film was measured using a haze meter (product of NIPPON DENSHOKU INDUSTRIES CO., LTD., TC-H3DPK).

(Heat resistance transparency)

The evaluation substrate having the cured coating film was heat-treated at 250 DEG C for 1 hour, and the transmittance of wavelength light of 400 nm and 540 nm was measured using a spectrophotometer (U-3310, Hitachi, Ltd.).

As apparent from the above results, the active energy ray-curable compositions containing the reactive polycarboxylic acid compound (A) in Examples 2-1 to 2-3 according to the present invention had the compositions of Comparative Examples 2-1 to 2-3 , It was clear that it was excellent in developability and curability, and excellent in heat-resistant transparency, flatness, flexibility and toughness. Further, it was found that Examples 2-1 and 2-2 in which DMPA (c) was also used for preparing the reactive polycarboxylic acid (A) had better compression performance than Example 2-3, which was not used .

Although the present invention has been described in detail with reference to specific embodiments thereof, it is apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

Further, the present application is based on Japanese Patent Application (Japanese Patent Application No. 2013-246535) filed on November 28, 2013, which is incorporated by reference in its entirety. Also, all references cited herein are incorporated by reference in their entirety.

(Industrial availability)

The active energy ray curable composition of the present invention can form a spacer for a display element and a protective film for a color filter which are excellent in developability, curability and high-speed coating ability and excellent in heat-resistant transparency, flatness, flexibility and toughness. Therefore, the composition is suitable as a material for forming a spacer for a display element such as a liquid crystal display element, an organic EL, or a color filter protective film.

Claims (4)

A spacer for a display element or a color filter protective film containing a reactive polycarboxylic acid compound (A), a reactive compound (B) other than the reactive polycarboxylic acid compound (A), a photopolymerization initiator (C) As an active energy ray curable resin composition,
The reactive polycarboxylic acid compound (A) is obtained by reacting the epoxy resin (a) represented by the general formula (1), the compound (b) having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in one molecule, (A) obtained by further reacting a reaction product (E) of a compound (c) having at least two hydroxyl groups and at least one carboxyl group in a molecule with a polybasic acid anhydride (d) Ray curable resin composition.

[Wherein n represents an integer of 0 to 2]
The method according to claim 1,
The reactive polycarboxylic acid compound (A) is obtained by reacting the epoxy resin (a) represented by the general formula (1), the compound (b) having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in one molecule, A spacer for a display element which is a reactive polycarboxylic acid compound (A) obtained by further reacting a reaction product (E) of a compound (c) having at least two hydroxyl groups and at least one carboxyl group in a molecule with a polybasic acid anhydride (d) Active energy ray curable resin composition for a color filter protective film. A spacer for a display element formed from the active energy ray-curable resin composition according to claim 1 or 2. A color filter protective film formed from the active energy ray-curable resin composition according to claim 1 or 2.