TW201527884A - Active energy ray-curable resin composition, and spacer for display elements and/or color filter protective film using same - Google Patents

Abstract

Provided are: an active energy ray-curable resin composition that is capable of forming a spacer for display elements and a color filter protective film, which have excellent heat-resistant transparency, flatness, flexibility and toughness; a spacer for display elements; and a color filter protective film. A resin composition according to the present invention contains (A) a reactive polycarboxylic acid compound, (B) a reactive compound other than the compound (A), (C) a photopolymerization initiator and (D) an organic solvent. The compound (A) is obtained by at least additionally reacting a reaction product of (a) an epoxy resin represented by general formula (1) and (b) a compound having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in each molecule with (d) a polybasic acid anhydride. (In formula (1), each of R1-R8 represents a hydrogen atom or the like, and G represents a glycidyl group.).

Description

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

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

As the material for the display device, a resin composition composed of a binder polymer, a photopolymerizable monomer, a photopolymerization initiator, or the like is used. In recent years, materials for display devices have rapidly spread as "materials used in LCDs, ELs, PDPs, FEDs (SEDs), rear projection displays, electronic papers, and digital cameras, especially for display elements and display element peripheral materials. For example, a color liquid crystal display (LCD). In general, the color liquid crystal display device has a structure in which a color filter is placed opposite to an electrode substrate such as a TFT substrate, and a gap portion of about 1 to 10 μm is provided, and a liquid crystal compound is filled in the gap portion, and a sealing material is sealed around the color filter. .

The color filter has a structure in which a black matrix layer formed in a predetermined pattern for shielding a boundary portion between pixels is sequentially formed on a transparent substrate from the side of the near transparent substrate, and red is usually formed to form each pixel ( R), green (G), and blue (B) are colored layers, a protective film, and a transparent electrode film which are arranged in a predetermined order. Further, an alignment film is provided on the inner surface side of the color filter and the electrode substrate opposed thereto. Further, in the gap portion, in order to color the color filter and the electrode base The cell gap between the plates is maintained constant and uniform, and a ball having a certain particle diameter as a spacer or a columnar or strip-shaped spacer having a height corresponding to the cell gap is dispersed. Further, a color image is obtained by controlling the light transmittance of the liquid crystal layer located behind each of the pixels colored in the respective colors. The color filter as described above is used not only for a color liquid crystal display device but also for other display devices such as an EL, a rear projection display, and the like.

The coloring layer, the protective film, and the spacer described above can be formed using a resin. The colored layer needs to be formed into a predetermined pattern corresponding to the pixels of the respective colors. Regarding the protective film, in consideration of the adhesion or sealing property of the sealing portion, it is preferable to cover only the region in which the colored layer is formed on the transparent substrate. Further, the spacer needs to be accurately disposed in the black matrix layer forming region, that is, the non-display region. Therefore, the coloring layer, the protective film, and the columnar spacer are formed by using a curable resin which can easily define a region to be hardened by a photomask.

In addition, when the coated surface of the curable resin is exposed to form a colored layer, a protective film or a columnar spacer, and the organic solvent is used for development, the operation and waste liquid treatment are complicated, and the economy and stability are lacking. Therefore, a curable resin which can introduce an acidic group into a curable resin and can be developed by an aqueous alkaline solution after exposure has been developed. In such applications, when a conductive film is formed and a transparent electrode is formed, a relatively high temperature (200-260 ° C or more) is applied. Therefore, those having high heat resistance are sought, and in particular, color resists and spacers are excellent in heat-resistant coloring property.

In Patent Document 1, as a polymer component of a photosensitive resin composition for a photoresist spacer and a color filter, an acid-modified epoxy acrylate having a cresol novolac epoxy resin is used as a primary amine compound. A photosensitive resin obtained by neutralization. However, such a salt containing a primary amine compound or a composition of water is inferior in coatability and flatness, and is insufficient in suitability to a device such as a slit coater.

Further, in Patent Document 2, as the polymer component of the photosensitive resin composition for the photoresist spacer, an acid-modified epoxy acrylate of a cresol novolac epoxy resin or a phenol novolak epoxy resin is used. However, there is a problem that radiation sensitivity and developability are poor and it is not a level of satisfactory satisfaction.

In Patent Document 3, as a protective component of a color filter or a polymer component of a resist ink composition for a flexible printed wiring board, an active energy ray-curable resin obtained by: p-cresol novolac is used. The varnish epoxy resin is added with acrylic acid or dimethylolpropionic acid to obtain a reactant, and the reactant is modified with caprolactone to further modify tetrahydrophthalic anhydride. The polymer component which is a main component of the composition is excellent in developability and flexibility, but there is a problem that the elastic recovery ratio required as a photoresist spacer is poor.

Patent Document 4 discloses a case where a resin composition containing an epoxy carboxylic acid ester compound is used for an optical material. However, there is no description about a spacer for a display element or a color filter protective film.

Prior technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2004-109752

Patent Document 2: Japanese Laid-Open Patent Publication No. 2007-010885

Patent Document 3: Japanese Laid-Open Patent Publication No. 2004-300266

Patent Document 4: International Publication No. 2008/004630

An object of the present invention is to provide an active energy ray-curable resin composition which is excellent in developability, hardenability, and high-speed coating property, and which is excellent in heat-resistant transparency, flatness, flexibility, and toughness. A spacer for the display element and a color filter protective film.

The present inventors have made an effort to solve the above problems, and as a result, have found that a resin composition having a specific compound and composition can solve the above problems, and the present invention has been completed.

That is, the present invention relates to the following:

(1) An active energy ray-curable resin composition for a display element spacer or a color filter protective film, which comprises a reactive polycarboxylic acid compound (A) or a reactive polycarboxylic acid compound (A) The reactive compound (B), the photopolymerization initiator (C), and the organic solvent (D), and the reactive polycarboxylic acid compound (A) further reacts the polybasic acid anhydride (d) with the reactant (E). Further, the reactant (E) is a reactant of the epoxy resin (a), the compound (b), and the optional compound (c) represented by the formula (1), and the compound (b) is a compound When the molecule has one or more ethylenically unsaturated groups capable of being polymerized and one or more carboxyl groups, the compound (c) is one having at least two or more hydroxyl groups and one or more carboxyl groups in one molecule.

(wherein R ₁ to R ₈ each may be the same or different and represent a hydrogen atom, an alkyl group of C1 to C4, or a halogen atom; and G represents an epoxy group)

(2) The present invention relates to a spacer for a display element according to (1) or an active energy ray-curable resin composition for a color filter protective film, wherein the reactive polycarboxylic acid compound (A) further comprises a polybasic acid anhydride (d) A reaction product obtained by reacting the reactant (E), wherein the reactant (E) is a reactant of the epoxy resin (a), the compound (b), and the compound (c) represented by the formula (1) The compound (b) has one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule, and the compound (c) has at least two or more hydroxyl groups and one or more carboxyl groups in one molecule. By.

(3) The present invention relates to a spacer for a display element according to (1) or (2) or an active energy ray-curable resin composition for a color filter protective film, wherein R ₁ ~ of the general formula (1) R ₈ is a hydrogen atom.

(4) The present invention relates to a spacer for a display element, which is formed from the active energy ray-curable resin composition according to any one of the above (1) to (3).

(5) The present invention relates to a color filter protective film which is formed from the active energy ray-curable resin composition according to any one of the above (1) to (3).

The active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention is excellent in developability, has high radiation sensitivity, and is excellent in heat-resistant transparency, flatness, flexibility, and toughness. A spacer for the display element and a color filter protective film.

Hereinafter, the present invention will be described in detail.

The reactive polycarboxylic acid compound (A) of the present invention is obtained by further reacting a polybasic acid anhydride (d) with a reactant, and the above-mentioned reactant is an epoxy resin (a) or a compound represented by the formula (1). b) and, if necessary, the reactant of the compound (c), wherein the compound (b) has one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule, and the compound (c) is a compound A molecule having at least two or more hydroxyl groups and one or more carboxyl groups in one molecule.

That is, the reactive polycarboxylic acid compound (A) of the present invention can be obtained by reacting the polybasic acid anhydride (d) with the reactant (E) of the epoxy resin (a) and the compound (b), or for the ring. The reactant (E) of the oxygen resin (a), the compound (b) and the compound (c) is obtained by reacting the polybasic acid anhydride (d) with it.

In the present invention, an ethylenically unsaturated group and a hydroxyl group are introduced into a molecular chain by an epoxycarboxylic acid esterification reaction, whereby the characteristics of the present invention can be exhibited.

In the general formula (1) of the epoxy resin (a), R ₁ to R ₈ may be the same or different and are appropriately selected from a hydrogen atom, an alkyl group of C1 to C4, or a halogen atom. Examples of the alkyl group of C1 to C4 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tertiary butyl group; and, as the halogen atom, a chlorine atom is exemplified. , bromine atom, iodine atom, etc. In the present invention, R ₁ to R _{8 are} preferably a hydrogen atom.

The epoxy compound (a) for producing the reactive polycarboxylic acid compound (A) of the present invention can contain the general formula (2)

(wherein R ₁ to R ₈ each may be the same or different and each represents a hydrogen atom, an alkyl group of C1 to C4, or a halogen atom)

The phenol compound having 80 mol% or more of the compound represented by the above is obtained by epimerization. This manufacturing method is described in Japanese Laid-Open Patent Publication No. 2005-200527, and can be manufactured according to this method. That is, the phenol resin of the formula (2) is synthesized by condensation reaction of phenol, a C1-C4 alkyl-substituted phenol, or a halogen-substituted phenol with glyoxal, and the phenol resin is epoxidized. The epoxy resin (a) of the formula (1) is obtained.

Further, as a commercially available product, GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.) or JER1031S (manufactured by Japan Epoxy Resins) in which R ₁ to R ₈ of the general formula (1) are all hydrogen atoms can be obtained.

The epoxy compound (a) used in the present invention has a melting point or a softening point of 100 ° C or more. also, The epoxy equivalent is in the range of 120 to 200 g/eq., more preferably in the range of 155 to 180 g/eq.

In the present invention, the compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule is added to the reactant in order to impart reactivity to the active energy ray. There is no limitation as long as one or more ethylenically unsaturated groups and carboxyl groups are present in the molecule. As such, a monocarboxylic acid compound and a polycarboxylic acid compound are mentioned.

Examples of the monocarboxylic acid compound having one carboxyl group in one molecule include (meth)acrylic acid or crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a saturated or unsaturated dibasic acid and an unsaturated group. The reactant of the monoepoxypropyl compound. In the above, examples of the (meth)acrylic acid include (meth)acrylic acid, β-styrylacrylic acid, β-mercaptoacrylic acid, and (meth)acrylic acid dimer, as saturated or unsaturated. a half ester of a molar anhydride such as a mono(meth)acrylate derivative having one hydroxyl group in one molecule, as a saturated or unsaturated dibasic acid and monoepoxypropyl (meth)acrylate Semi-esters of the molar reactants such as derivatives.

Further, as a polycarboxylic acid compound having two or more carboxyl groups in one molecule, a half ester of a molar reactant such as a (meth) acrylate derivative having a plurality of hydroxyl groups in one molecule may be mentioned as a saturated salt. Or a half ester of a molar reaction of an unsaturated dibasic acid and a glycidyl (meth) acrylate derivative having a plurality of epoxy groups.

In the case of the sensitivity of the active energy ray-curable resin composition, the reaction product of (meth)acrylic acid, (meth)acrylic acid and ε-caprolactone or cinnamic acid is preferably used. . As the compound (b), those having no hydroxyl group in the compound are preferred.

In the present invention, the compound (c) having at least two or more hydroxyl groups and one or more carboxyl groups in one molecule is added to the reactant for introducing a hydroxyl group into the carboxylate compound.

In the present invention, specific examples of the compound (c) having at least two or more hydroxyl groups and one or more carboxyl groups in the molecule, which are used as needed, may, for example, be dimethylolpropionic acid or dimethylolbutanoic acid. (butane acid), a monocarboxylic acid containing a polyhydroxy group such as dimethylol acetic acid, butyric acid, dihydroxymethylvaleric acid or dihydroxymethylhexanoic acid. Particularly preferred examples thereof include dimethylolpropionic acid and the like.

Among these, in consideration of the stability of the reaction between the epoxy resin (a) and the compound (b) and the compound (c), the compound (b) and the compound (c) are preferably monocarboxylic acids, even if When the monocarboxylic acid and the polycarboxylic acid are used in combination, it is also preferred that the total amount of the monocarboxylic acid/the total amount of the polycarboxylic acid is 15 or more.

In this reaction, the total feed ratio of the carboxylic acid of the epoxy resin (a), the compound (b), and the compound (c) to be used as needed should be appropriately changed depending on the use. That is, in the case where all of the epoxy groups have been subjected to carboxylic acid esterification, since the unreacted epoxy group is not present, the storage stability of the reactive epoxy carboxylate compound form is high. In this case, only the reactivity brought about by the introduced double bond is utilized.

On the other hand, by intentionally reducing the amount of the carboxylic acid compound to be fed, the unreacted residual epoxy group remains, and the reactivity of the introduced unsaturated bond and the reaction with the remaining epoxy group can be used in combination, for example. Polymerization or thermal polymerization using a photocationic catalyst. However, in this case, attention should be paid to the study on the preservation and production conditions of the reactive epoxy carboxylate compound (E).

In the case of producing a reactive epoxy carboxylate compound (E) which does not retain an epoxy group, the total of the compound (b) and optionally the compound (c) is preferably relative to the above epoxy resin (a) ) 1 equivalent is 90 to 120 equivalent %. If it is the range, it can be in a relatively stable strip. Manufactured under the condition. When the total amount of the compound (b) and the compound (c) to be used as required is more than the above, the excess compound (b) and the compound (c) remain, which is not preferable.

Further, when the epoxy group is intentionally left, the total of the compound (b) and the compound (c) is preferably from 20 to 90% by weight based on 1 equivalent of the epoxy resin (a). In the case of deviating from this range, the further reaction of the epoxy group does not proceed sufficiently. In this case, great attention needs to be paid to the gelation of the reaction and the stability over time of the reactive epoxy carboxylate compound (E).

In the case of using the compound (b) and the compound (c), the ratio of the compound (b) to the molar ratio of the carboxylic acid is preferably from 95:5 to 5:95, more preferably from 95:5 to 5:95. It is in the range of 95:5~40:60. If it is this range, the sensitivity to the active energy ray is good, and a sufficient amount of hydroxyl groups can be introduced in order to react the polybasic acid anhydride (d) with the reactive epoxy carboxylic acid ester compound (E).

The carboxylic acid esterification reaction can be carried out without a solvent, or can be carried out by dilution with a solvent. The solvent which can be used herein is not particularly limited as long as it is a solvent which is inert to the carboxylic acid esterification reaction.

The amount of the solvent to be used is preferably adjusted in accordance with the viscosity or use of the obtained resin, and is preferably 90 to 30 parts by weight, more preferably 80 to 50 parts by weight, per 100 parts by weight of the solid content.

Specific examples thereof include an aromatic hydrocarbon solvent such as toluene, xylene, ethylbenzene or tetramethylbenzene, and an aliphatic hydrocarbon solvent such as hexane, octane or decane, and the like. Petroleum ether, white gasoline, solvent petroleum brain, etc., ester solvent, ether solvent, ketone solvent, and the like.

Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate; cyclic esters such as γ-butyrolactone; ethylene glycol monomethyl ether acetate; and diethyl 2 Alcohol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate And mono- or polyalkylene glycol monoalkyl ether monoacetate such as butanediol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate, etc. Polycarboxylic acid alkyl esters and the like.

Examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol. A glycol ether such as ethyl ether, triethylene glycol dimethyl ether or triethylene glycol diethyl ether; or a cyclic ether such as tetrahydrofuran.

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

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

In the reaction, it is preferred to use a catalyst for promoting the reaction, and the amount of the catalyst used is relative to the reactant, that is, the epoxy resin (a), the carboxylic acid compound (b), and the compound (c) to be used as needed. And 100 parts by weight of the total amount of the solvent and other reactants added depending on the case, usually 0.1 to 10 parts by weight. The reaction temperature at this time is usually 60 to 150 ° C, 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, and benzyltrimethylammonium iodide. , known general alkaline touches such as triphenylphosphine, triphenylphosphonium, methyltriphenylphosphonium, chromium octoate, zirconium octoate, etc. Media and so on.

Further, as the thermal polymerization inhibitor, it is preferred to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenyl bitter, diphenylamine, 3,5-di. - Tert-butyl-4-hydroxytoluene and the like.

This reaction system is appropriately sampled, and the time point at which the acid value of the sample is 5 mgKOH/g or less, preferably 3 mgKOH/g or less is taken as the end point.

As a preferable molecular weight range of the reactive epoxy carboxylate compound (E) obtained in the above manner, the polystyrene-equivalent weight average molecular weight obtained by GPC is in the range of 500 to 50,000, more preferably 1,000 to 30,000.

When it is less than the above molecular weight, the toughness of the cured product cannot be sufficiently exhibited, and when it is excessively larger than the above value, the viscosity is high and coating or the like is difficult.

Next, the acid addition step will be described in detail. The acid addition step is carried out for the purpose of obtaining a reactive polycarboxylic acid compound (A) by introducing a carboxyl group into the reactive epoxy carboxylate compound (E) obtained in the above step. In other words, the polyvalent acid anhydride (d) is subjected to an addition reaction with a hydroxyl group formed by a carboxylic acid esterification reaction, and a carboxyl group is introduced via an ester bond.

Specific examples of the polybasic acid anhydride (d) include, for example, a compound having an acid anhydride structure in the molecule, and particularly preferably an aqueous solution having excellent developability, heat resistance, hydrolysis resistance, and the like. Dicarboxylic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, Trimellitic anhydride or maleic anhydride.

The reaction for adding the polybasic acid anhydride (d) can be carried out by adding the polybasic acid anhydride (d) to the above-mentioned carboxylic acid esterification reaction liquid. The amount of addition should be changed as appropriate depending on the application.

With respect to the addition amount of the polybasic acid anhydride (d), for example, in the case where the reactive polycarboxylic acid compound (A) of the present invention is to be used as a resist for an alkali development type, it is preferred to obtain the reaction finally obtained. The acid value of the solid content component of the polycarboxylic acid compound (A) (according to JIS K 5601-2-1:1999) is calculated as a value of 40 to 120 mg ‧ KOH / g, more preferably 60 to 120 mg ‧ KOH / g Anhydride (d). When the acid value of the solid content component is in this range at this time, the alkaline aqueous solution developability of the photosensitive resin composition of the present invention shows good developability. That is, the patterning property is good and the management range for overdevelopment is also wide, and no excess acid anhydride remains.

In the reaction, in order to promote the reaction, it is preferred to use a catalyst, and the amount of the catalyst to be used is added with the epoxy compound (a), the carboxylic acid compound (b), and the compound used as needed (c). The total amount of the reactive epoxy carboxylate compound (E), the polybasic acid anhydride (d), the solvent to be used, and other reactants obtained is 100 parts by weight, usually 0.1 to 10 parts by weight. The reaction temperature at this time is usually 60 to 150 ° C, 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, and benzyltrimethylammonium iodide. , triphenylphosphine, triphenylsulfonium, methyltriphenylphosphonium, chromium octoate, zirconium octoate, and the like.

The acid addition reaction can be carried out without a solvent, or can be carried out by diluting with a solvent. The solvent which can be used herein is not particularly limited as long as it is inert to the acid addition reaction. Further, in the case where the solvent is used in the carboxylic acid esterification reaction in the previous step, the two reactions may be inert, and the solvent may be directly submitted to the next step, that is, the acid addition reaction. The solvent which can be used can be the same as that of the user in the esterification reaction with a carboxylic acid.

The preferred amount of solvent to be used should be based on the viscosity or use of the resulting resin. When it is adjusted, it is preferably used in an amount of 90 to 30 parts by weight, more preferably 80 to 50 parts by weight, based on 100 parts by weight of the solid content component.

Further, it may be carried out in a separate or mixed organic solvent such as the reactive compound (B) described later. In this case, it is preferably used as a composition when it is used as a curable composition.

Further, the thermal polymerization inhibitor or the like is preferably the same as those exemplified in the above-mentioned carboxylic acid esterification reaction.

This reaction is appropriately sampled and used as the end point when the acid value of the reactant is in the range of plus or minus 10% of the set acid value.

As a preferable molecular weight range of the reactive polycarboxylic acid compound (A), the polystyrene-equivalent weight average molecular weight obtained by GPC is in the range of 500 to 50,000, more preferably 1,000 to 30,000.

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

The reactive compound (B) which can be used in the present invention includes so-called reactivity such as a radical reaction type acrylate, a cationic reaction type other epoxy compound, and a vinyl compound which reacts both. Oligomers.

Examples of the radically reactive acrylates include monofunctional (meth) acrylates, bifunctional (meth) acrylates, trifunctional or higher (meth) acrylates, and polyester (meth) acrylates. , (meth) acrylate oligomer, polyester (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, and the like.

As the monofunctional (meth) acrylate, for example, an acrylonitrile group can be cited. a hydroxy group-containing (meth) acrylate such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate; Alkane-1,4-dimethanol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isodecyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (meth)acrylic acid An aliphatic (meth) acrylate such as dicyclopentenyl ester or dicyclopentenyloxyethyl (meth)acrylate; phenoxyethyl (meth)acrylate or phenyl (meth)acrylate Ethoxylate, p-cumylphenoxyethyl (meth)acrylate, tribromophenoxyethyl (meth)acrylate, phenylthioethyl (meth)acrylate, ( Aromatic (methyl) such as 2-hydroxy-3-phenoxypropyl methacrylate, phenylphenol (poly)ethoxy (meth) acrylate, phenylphenol epoxy (meth) acrylate )Acrylate.

Examples of the bifunctional (meth) acrylate include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol. Di(meth)acrylate, tricyclodecane dimethanol (meth) acrylate, bisphenol A (poly) ethoxy di(meth) acrylate, bisphenol A (poly) propoxy bis (a) Acrylate, bisphenol F (poly) ethoxy di(meth) acrylate, ethylene glycol di(meth) acrylate, (poly) ethylene glycol di(meth) acrylate, hydroxy trimethyl A bis(meth) acrylate of an ε-caprolactone adduct of neopentyl glycol acetate (for example, manufactured by Nippon Kayaku Co., Ltd., KAYARAD HX-220, HX-620, etc.).

Examples of the trifunctional or higher polyfunctional (meth) acrylate include di(trimethylolpropane)tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, and trimethylol. Octane tri(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acrylate, trimethylolpropane (poly)propoxy tri(meth)acrylate, trimethylol Propane (poly) hydroxymethyl group such as ethoxy (poly) propoxy tri(meth) acrylate; neopentyl alcohol tri(meth) acrylate, neopentyl alcohol polyethoxy tetra (methyl) Acrylate, neopentyl alcohol (poly) propoxy tetra (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dicotyl Alcohols such as alcohol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; tris [(methyl) propylene methoxyethyl] isocyanurate, caprolactone Modified three [(meth)acryloxyethyl]isocyanurate; succinic acid modified pentaerythritol triacrylate, succinic acid modified dipentaerythritol pentaacrylate.

Examples of the (poly)ester (meth) acrylate oligomer include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, and polyethylene glycol. , (poly)propylene glycol, isoglycols, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1, 8-octanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol Equivalent linear or branched alkyl diols, alicyclic alkyl diols such as cyclohexane-1,4-dimethanol, bisphenol A (poly) ethoxy diol or bisphenol A (poly) A reaction product of a diol compound such as a propoxy diol and a dibasic acid or an acid anhydride thereof, that is, a reaction product of (poly)esterdiol and (meth)acrylic acid.

Examples of the (meth)acrylic acid amide oligomer include a diol compound (for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and 1,4-butane). Alcohol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1 , 5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, Polyethylene glycol, polypropylene glycol, bisphenol A polyethoxy diol, bisphenol A polypropoxy diol, etc.) or the diol compound and a dibasic acid or an anhydride thereof (for example, succinic acid, hexamethylene) Acid, azelaic acid, diacid acid, isophthalic acid, a reaction of a terephthalic acid, a phthalic acid or an anhydride thereof, that is, a polyester diol, and an organic polyisocyanate (for example, tetramethylene diisocyanate, hexamethylene diisocyanate, 2, 2, 4) - chain saturated hydrocarbon isocyanate such as trimethylhexamethylene diisocyanate or 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane a cyclic saturated hydrocarbon isocyanate such as diisocyanate, methylene bis(4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate or hydrogenated toluene diisocyanate, 2,4-toluene diisocyanate, 1, 3-phenyldimethyl diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate, 1, Reaction of an aromatic polyisocyanate such as 5-naphthalene diisocyanate), followed by addition of a hydroxyl group-containing (meth) acrylate.

The epoxy (meth) acrylate oligomer is a carboxylic acid ester compound of a compound having an epoxy group and (meth)acrylic acid. For example, a phenol novolak type epoxy (meth)acrylate, a cresol novolak type epoxy (meth)acrylate, a trihydroxyphenylmethane type epoxy (meth)acrylate, and a dicyclopentane can be mentioned. Diene 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 (meth) acrylate, epoxy (meth) acrylate containing naphthalene skeleton, glyoxal type epoxy (meth) acrylate, heterocyclic epoxy (methyl ) Acrylate and the like.

Examples of the vinyl compound 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 styrenes include styrene, methylstyrene, and ethylstyrene. As another vinyl compound, a triallyl isocyanurate is mentioned. An acid ester, trimethylallyl isocyanurate or the like.

Further, the cationically reactive monomer is usually not particularly limited as long as it is a compound having an epoxy group. For example, (meth)acrylic acid propyl acrylate, methyl epoxidized propyl ether, ethyl epoxidized propyl ether, butyl epoxidized propyl ether, bisphenol A diglycidyl ether, 3, 4-ring Oxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Cyracure UVR-6110, manufactured by Union Carbide, etc.), 3,4-epoxycyclohexylethyl-3,4-epoxy ring Hexane carboxylate, vinyl cyclohexene oxide ("ELR-4206" manufactured by Union Carbide Co., Ltd.), limonene dioxide ("Celloxide 3000" manufactured by Daicel Chemical Industry Co., Ltd.), propylene oxide cyclohexene , 3,4-epoxy-4-methylcyclohexyl-2-epoxypropane, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane- Two Alkane, bis(3,4-epoxycyclohexyl) adipate ("Cyracure UVR-6128" manufactured by Union Carbide, etc.), bis(3,4-epoxycyclohexylmethyl) adipate, double (3,4-epoxycyclohexyl)ether, bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexyl)diethyloxane, and the like.

Among these, the reactive compound (B) is preferably a monofunctional, bifunctional or trifunctional or higher (meth) acrylate from the viewpoint of improving the polymerizability and improving the strength of the obtained spacer or the like. .

The reactive compound (B) of the present invention may be used singly or in combination of two or more. In the composition, the use ratio of the reactive compound (B) is preferably from 30 parts by weight to 250 parts by weight, more preferably from 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 heat resistance and elastic properties of the composition, the resulting spacer for a display element, and the like are more preferable.

The photopolymerization initiator (C) of the present invention produces a reactive compound other than the reactive polycarboxylic acid compound (A) and the reactive polycarboxylic acid compound (A) by reacting with an active energy ray. The component of the active species that begins to polymerize. The photopolymerization initiator (C) may, for example, be an O-indenyl hydrazine compound, an acetophenone compound or a biimidazole compound.

As the O-indenyl ruthenium compound, for example, ethyl ketone-1-[9-ethyl-6-(2-methylbenzomethyl)-9H-carbazol-3-yl]-1-(O) can be mentioned. -Ethyl hydrazide), 1-[9-ethyl-6-benzylidene-9H-carbazol-3-yl]-octane-1-one oxime-O-acetate, 1-[9 -ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-n-butyl -6-(2-ethylbenzylidenyl)-9H-indazol-3-yl]-ethane-1-one oxime-O-benzoate, ethyl ketone-1-[9-ethyl- 6-(2-Methyl-4-tetrahydrofuranylbenzylidene)-9H-indazol-3-yl]-1-(O-acetamidoxime), ethyl ketone-1-[9-ethyl- 6-(2-Methyl-4-tetrahydropyranylbenzylidene)-9H-indazol-3-yl]-1-(O-acetamidopurine), ethyl ketone-1-[9- Ethyl-6-(2-methyl-5-tetrahydrofuranylbenzylidene)-9H-indazol-3-yl]-1-(O-ethylindenyl), ethyl ketone-1-[9- Ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidenyl}-9H-indazol-3-yl] -1-(O-Ethyl hydrazine) and the like. Among these, preferred is: ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-acetamidine) Ketone), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-1-(O -Ethyl hydrazine) or ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxy Benzyl hydrazino}-9H-indazol-3-yl]-1-(O-ethenyl hydrazine). These O-mercaptopurine compounds may be used singly or in combination of two or more.

Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.

As the α-amino ketone compound, for example, 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- Polin-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthiophenyl)-2- Orolinylpropan-1-one and the like.

Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1-(4-isopropylphenyl)-2-hydroxy-2-methyl. Propane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, and the like.

Among the acetophenone compounds, an α-amino ketone compound is preferred, and 2-benzyl-2-dimethylamino-1-(4-) is more preferred. Polinylphenyl)-butan-1-one or 2-dimethylamino-2-(4-methylbenzyl)-1-(4- Polin-4-yl-phenyl)-butan-1-one.

As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'- can be mentioned. Biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4- Dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4 ',5,5'-tetraphenyl-1,2'-biimidazole. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-double is preferred. (2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis(2,4,6-trichlorophenyl) -4,4',5,5'-tetraphenyl-1,2'-biimidazole, more preferably 2,2'-bis(2,4-dichlorophenyl)-4,4',5 , 5'-tetraphenyl-1,2'-biimidazole.

As the photopolymerization initiator (C), a commercially available product can also be used, and, for example, 2-methyl-1-(4-methylthiophenyl)-2- Orolinylpropan-1-one (Irgacure 907), 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Phenylphenyl)-butan-1-one (Irgacure 379), Ethyl-1-(9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl] 1-(O-Acetylhydrazine) (Irgacure OXE02) (above, Ciba Specialty Chemicals, Inc.) and the like.

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

Further, the photopolymerization initiator (C) described above may be used in combination with the curing accelerator (F). Examples of the hardening accelerator which can be used together include triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethylbenzoate, dimethylaminoacetophenone, and p-dimethylene. Hydrogen donors such as isoamyl benzoate, amines such as EPA, and 2-mercaptobenzothiazole. When the amount of the solid content of the resin composition of the present invention is 100% by weight, the amount of the curing accelerator is usually 0% by weight or more and 5% by weight or less.

As the organic solvent (D), those obtained by uniformly dissolving or dispersing the respective constituent components and not reacting with the respective constituent components can be preferably used. The organic solvent (D) is an ether solvent, an ether solvent, or a ketone solvent, in addition to the aromatic hydrocarbon solvent, the aliphatic hydrocarbon solvent, and the like, that is, petroleum ether, white gasoline, solvent petroleum brain, and the like. Etc., for example, 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, guanamines, ketones, and the like. These can be used alone or 2 The above is used in combination.

Specific examples of the organic solvent (D) include alcohols such as benzyl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Alcohol monoalkyl ethers; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and other propylene glycol monoalkyl ethers; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc. Glycol monoalkyl ethers; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate Diethylene glycol monoalkyl ether acetate; dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether and other dipropylene glycol monoalkyl ethers; dipropylene glycol monomethyl ether Dipropylene glycol monoalkyl ether acetates such as acid esters, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate; methyl lactate, ethyl lactate, lactine positive Ester, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate, etc.; hydroxy Ethyl acetate, ethyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-3-methylbutanoate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-methyl Ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, methyl acetate, ethyl acetate, pyruvic acid An aliphatic carboxylic acid ester such as methyl ester or ethyl pyruvate; N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethyl B Amidoxime such as guanamine; ketones such as N-methylpyrrolidone and γ-butyrolactone. These may be used alone or in combination of two or more.

The concentration of the solid content component in the composition is usually 10% by weight or more and 40% by weight or less, preferably 15% by weight or more and 35% by weight or less. By making the composition solid When the concentration of the form component is in the above range, the coating property can be improved, the film thickness uniformity can be improved, and the occurrence of uneven coating can be effectively suppressed.

The viscosity of the composition at 25 ° C is usually 1.0 mPa ‧ s or more and 1,000 mPa ‧ s or less. It is preferably 2.0 mPa ‧ or more and 100 mPa ‧ or less. By setting the viscosity of the composition to the above range, it is possible to achieve a balance in which the film thickness uniformity is maintained and the degree of uniformity can be uniform even if uneven coating occurs.

In the photosensitive resin composition of the present invention, the alkali-soluble resin (G) used as needed may be, for example, a monomer having a hydroxyl group, an acid anhydride having an ethylenic double bond, or a monomer having a carboxyl group. A monomer having an epoxy group, a monomer having a phenolic hydroxyl group, a monomer having a sulfonic acid group, another monomer, and the above-mentioned monofunctional (meth) acrylate are copolymerized and produced.

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

Specific examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, 3-methylphthalic anhydride, and methyl-5- Decalene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-butene -1- butyl succinic anhydride and the like.

Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, or the like. salt.

Specific examples of the monomer having an epoxy group include (meth)acrylic acid propyl acrylate and 3,4-epoxycyclohexyl methacrylate.

Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene. Further, one or more hydrogen atoms of the benzene rings may be an alkyl group such as a methyl group, an ethyl group or a n-butyl group; an alkoxy group such as a methoxy group, an ethoxy group or a n-butoxy group; a halogen atom; a halogenated alkyl group in which one or more hydrogen atoms are substituted by a halogen atom; a nitro group; a cyano group; a decylamino group or the like substituted monomer.

Examples of the monomer having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, (meth)allylsulfonic acid, and 2-hydroxy-3-(methyl)allyloxypropanesulfonic acid. 2-sulfoethyl (meth)acrylate, 2-sulfopropyl (meth)acrylate, 2-hydroxy-3-(methyl)propenyloxypropanesulfonic acid, 2-(methyl)propene oxime Amine-2-methylpropanesulfonic acid and the like.

Examples of the other monomer include hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, and (meth) acrylates. Methyl) acrylamide, aromatic vinyl compound, chloroolefin, conjugated diene. These compounds may also contain a functional group, and examples of the functional group include a carbonyl group and an alkoxy group. In particular, since the partition walls formed of the composition are excellent in heat resistance, they are preferably (meth) acrylates or (meth) acrylamides.

When the alkali-soluble resin (G) is produced by copolymerization, it can be produced by radically polymerizing an unsaturated compound in the presence of a polymerization initiator in a solvent. Can use the above dissolve The agent may be used singly or in combination of two or more.

As the polymerization initiator used for the polymerization reaction for producing the alkali-soluble resin (G), those known as radical polymerization initiators can be generally used. Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-(2,4-dimethylvaleronitrile), and 2, An azo compound such as 2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile); benzamidine peroxide, laurel peroxide, tertiary butyl peroxypivalate, An organic peroxide such as 1,1'-bis-(tributylbutyl peroxide) cyclohexane and hydrogen peroxide. In the case where a peroxide is used as a radical polymerization initiator, a peroxide may be used together with a reducing agent as a redox type initiator.

In the polymerization reaction for producing the alkali-soluble resin (G), a molecular weight modifier can be used in order to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tertiary-dodecyl mercaptan, and sulfur. Mercaptans such as glycolic acid; xanthogenates such as dimethyl xanthate sulfide and diisopropyl xanthate disulfide; terpinolene and α-methylstyrene polymers.

The above-mentioned monomer having a hydroxyl group, an acid anhydride having an ethylenic double bond, a monomer having a carboxyl group, a monomer having an epoxy group, a monomer having a phenolic hydroxyl group, a monomer having a sulfonic acid group, and the like are reactive. The monomer (e) as the group (e) is, for example, a compound (f) having a functional group capable of bonding to the above reactive group and an ethylenic double bond.

(1) an acid anhydride having an ethylenic double bond (f) to a monomer (e) having a hydroxyl group, (2) a compound (f) having an isocyanate group and an ethylenic double bond, and a monomer (e) having a hydroxyl group, ( 3) a compound having a ruthenium chloride group and an ethylenic double bond (f) to a monomer having a hydroxyl group (e), (4) a compound having a hydroxyl group and an ethylenic double bond (f), and an acid anhydride having an ethylenic double bond (e), (5) a compound having an epoxy group and an ethylenic double bond (f) to a monomer having a carboxyl group (e), (6) a compound having a carboxyl group and an ethylenic double bond (f), and a monomer having an epoxy group (e).

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

Specific examples of the compound having an isocyanate group and an ethylenic double bond include 2-(meth)acryloxyethyl isocyanate and 1,1-(bis(methyl)acryloxymethyl)ethyl. Isocyanate, etc.

Specific examples of the compound having a ruthenium chloride group and an ethylenic double bond include (meth) acrylonitrile.

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 the copolymer is reacted with a compound (f) having a functional group capable of bonding with a reactive group and an ethylenic double bond, the solvent exemplified for the synthesis of the above copolymer can be used as a solvent for the reaction.

Further, it is preferred to blend a polymerization inhibitor. As the polymerization inhibitor, a publicly known polymerization inhibitor can be used, and specific examples thereof include 2,6-di-tri-butyl-p-cresol.

Further, a catalyst or a neutralizing agent may be added. For example, when a copolymer having a hydroxyl group is reacted 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 and dibutyltin di(pentene). Acid monoester), dioctyltin dilaurate, dioctyltin bis (maleic acid monoester), dibutyltin diacetate, and the like.

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

The Mw of the alkali-soluble resin (G) is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 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 (characteristics of forming a desired pattern shape correctly) can be improved.

Further, the photosensitive resin composition of the present invention may optionally contain a surfactant, a leveling agent, an antifoaming agent, a filler, an ultraviolet absorber, a photostabilizer, an antioxidant, a polymerization inhibitor, a crosslinking agent, and an adhesive. Additives, pigments, dyes, etc., give each target functionality. Examples of the leveling agent and the antifoaming agent include a fluorine compound, a polyoxymethylene compound, and an acrylic compound. Examples of the ultraviolet absorber include a benzotriazole compound, a benzophenone compound, and the like. Examples of the light stabilizer include a hindered amine compound and a benzoate compound; examples of the antioxidant include a phenol compound; and examples of the polymerization inhibitor include p-methoxyphenol. And methyl hydroquinone, hydroquinone, etc., and the poly-isocyanate, a melamine compound, etc. are mentioned as a crosslinking agent.

Further, as the resin (so-called inert polymer) which does not exhibit reactivity to the active energy ray, for example, other epoxy resins, phenol resins, amine ester resins, polyester resins, ketone-formaldehyde resins, cresol resins, and the like may be used. Xylene resin, diallyl phthalate resin, styrene resin, guanamine resin, natural and synthetic rubber, acrylic resin, polyolefin resin, and the like Modified material. These are preferably used in the resin composition in the range of up to 40 parts by weight.

The active energy ray-curable resin composition of the present invention usually contains the reactive polycarboxylic acid compound (A) in an amount of 5 to 69% by weight, preferably 8 to 59% by weight, and usually contains other reactive compound (B). 3 to 64% by weight, preferably 5 to 59% by weight, usually containing 1 to 10% by weight of the photopolymerization initiator (C), preferably 1 to 7% by weight, usually containing an organic solvent (D) 60 to 90% The weight % is preferably 65 to 85% by weight. It may also contain other components 0 to 80% by weight as needed.

<Method for Forming Display Spacer and Color Filter Protective Film>

A spacer for a display element formed of the composition is preferably included in the present invention. The method for forming a spacer for a display element includes (1) a step of applying the composition onto a substrate to form a coating film, (2) a step of irradiating at least a part of the coating film with radiation, and (3) a step of irradiating the radiation. a step of developing the applied coating film, and (4) a step of heating the developed coating film.

A method of forming a photoresist 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 the 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, and a gravure coater. Notch wheel coater, etc. Here, an example of forming on the transparent common electrode provided on the colored layer will be described.

Heat it as needed (pre-bake). The drying temperature is preferably 50 ° C or higher, more preferably 70 ° C or higher, and further preferably less than 150 ° C, and more preferably 120 ° C or lower. The drying time is preferably 30 seconds or longer, more preferably 1 minute or longer, further preferably 20 minutes or shorter, and further preferably 10 minutes or shorter.

Then, the mask of the photosensitive resin composition layer is exposed by the active energy ray in a predetermined mask. In the photosensitive resin composition of the present invention, even a mask opening having a diameter of about 5 to 10 μm (area of about 20 to 100 μm ² ) can be accurately, that is, a diameter of 6 to 12 μm (area of 30 to 120 μm ^{2 ).} The scope of the formation.

The active energy ray used for the exposure is not particularly limited as long as the photosensitive resin composition of the present invention can be cured. The active energy ray-curable resin composition of the present invention is easily hardened by an active energy ray. Here, specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, and laser rays, particle beams such as α rays, β rays, and electron beams. In view of the preferred use of the present invention, among these, ultraviolet light, laser light, visible light, or an electron beam is preferred. The amount of exposure is not particularly limited, but is preferably 20 to 1,000 mJ/cm ² .

Then, development is performed by removing the unexposed portion by the developer. Here, as the developer for development, an organic solvent can be used, and an alkaline aqueous solution is preferably used. Examples of the alkaline aqueous solution usable as the developing solution include aqueous solutions of inorganic salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydrogencarbonate; hydroxytetramethylammonium and hydroxytetraethylammonium; An aqueous solution of an organic salt. These may be used singly or in combination of two or more kinds thereof, or an activator such as an anionic surfactant, a cationic surfactant, an amphoteric surfactant or a nonionic surfactant, or a water-soluble solution such as methanol or ethanol may be added. Use as an organic solvent. Thick alkali in alkaline aqueous solution The degree is preferably from 0.1 to 5% by weight from the viewpoint of obtaining appropriate developability. As the developing method, there are an immersion method, a shower method, a liquid discharge method, and a vibration immersion method, and a shower method is preferred. The temperature of the developer is preferably from 25 to 40 °C. The development time is appropriately determined depending on the film thickness or the solubility of the photoresist.

In order to perform hardening more reliably, heating (baking) may be performed as needed. In the case of baking, the baking temperature is preferably from 120 to 250 °C. The baking time varies depending on the type of the heating machine. For example, when the heating step is performed on the hot plate, it can be set to 5 minutes to 30 minutes, and when the heating step is performed in the oven, it can be set to 30 minutes. ~90 minutes. A stage baking method in which two or more heating steps are performed may be used.

The film thickness of the spacer formed as described above is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, still more preferably 0.1 μm to 4 μm.

The spacer formed in the formation method has no coating unevenness and high flatness, and is soft and has small plastic deformation. It can be preferably used for a display element such as a liquid crystal display element or an organic EL display element.

The color filter protective film is preferably from 0.5 μm to 100 μm, more preferably from 1 μm to 10 μm.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited by the examples. In the examples, "parts" means parts by weight and "%" means weight% unless otherwise stated.

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

1) Epoxy equivalent: It was measured by the method according to JIS K7236:2001.

2) Softening point: Measurement was carried out by the method according to JIS K7234:1986.

3) Acid value: The measurement was carried out by the method according to JIS K0070:1992.

Example 1-1~1-3 [Preparation of Reactive Polycarboxylic Compound (A)]

GTR-1800 (manufactured by Nippon Chemical Co., Ltd.; epoxy equivalent: 170 g/eq) as an epoxy resin (a) was added in the amount shown in Table 1, and acrylic acid (abbreviated as AA, Mw = 72) as the compound (b) The amount described in Table 1 is the amount of dimethylolpropionic acid (abbreviated as DMPA, Mw = 134) as the compound (c). 3 g of triphenylphosphine as a catalyst was added, and propylene glycol monomethyl ether monoacetate as a solvent was added so that the solid content component became 80% by weight of the reaction liquid, and the reaction was carried out at 100 ° C for 24 hours to obtain a reactive epoxy resin. Carboxylate compound (E) solution. The solid content of the solid content (AV: mgKOH/g) 5 or less is set as the reaction end point, and the reaction proceeds to the next reaction. The acid value is determined by using a reaction solution and converted to an acid value in the form of a solid component.

Then, the reactive epoxy carboxylate compound (E) solution is added as a polybasic acid anhydride (d) tetrahydrophthalic anhydride (abbreviated as THPA) in the amount shown in Table 1, and is 100 parts by weight relative to the solid content component. The propylene glycol monomethyl ether monoacetate as a solvent was added in an amount of 65 parts by weight, and after heating to 100 ° C, an acid addition reaction was carried out to obtain a solution of the reactive polycarboxylic acid compound (A). The solid content acid value (AV: mgKOH/g) is shown in Table 1.

Comparative Example 1-1, 1-2 [Preparation of comparative polycarboxylic acid compound for comparison]

A cresol novolac type epoxy resin EOCN-103S (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 200 g/eq) was added, and the amount described in Table 1 as the compound (b) was described as the compound (c). Dimethylolpropionic acid (abbreviated as DMPA, Mw = 134) is described in Table 1. add 3 g of triphenylphosphine as a catalyst was added, and propylene glycol monomethyl ether monoacetate as a solvent was added so that the solid content component became 80% by weight of the reaction liquid, and the mixture was reacted at 100 ° C for 24 hours to obtain a carboxylate compound. Solution. The solid content of the solid content (AV: mgKOH/g) of 5 mgKOH/g or less was set as the reaction end point, and it progressed to the next reaction.

Then, the amount of the tetrahydrogen phthalic anhydride (abbreviated as THPA) as a polybasic acid anhydride is added to the reactive epoxy carboxylate compound solution in the amount shown in Table 1, and is 65 parts by weight based on 100 parts by weight of the solid content component. Propylene glycol monomethyl ether monoacetate as a solvent was added, and after heating to 100 ° C, an acid addition reaction was carried out to obtain a comparative reactive polycarboxylic acid compound solution. The solid content acid value (AV: mgKOH/g) is shown in Table 1.

Comparative Example 1-3 [Preparation of Reactive Caprolactone Modified Polycarboxylic Acid Compound for Comparison]

Adding cresol novolak type epoxy resin EOCN-103S (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 200 g/eq) 200 g, acrylic acid 58 g, dimethylolpropionic acid 40 g, and triphenylphosphine 3 g as a catalyst, The propylene glycol monomethyl ether monoacetate as a solvent was added as a solvent so that the solid content became 80% by weight of the reaction liquid, and the reaction was carried out at 100 ° C for 24 hours. Further, 68 g of ε-caprolactone was added and the reaction was carried out for 8 hours. Then, 91 g of tetrahydrophthalic anhydride (abbreviated as THPA) as a polybasic acid anhydride was added, and propylene glycol monomethyl ether monoacetate as a solvent was added so as to be 65 parts by weight based on 100 parts by weight of the solid content component. After heating to 100 ° C, an acid addition reaction was carried out to obtain a comparative polycaprolactone-modified polycarboxylic acid compound solution for comparison. The solid content acid value (AV: mgKOH/g) was 70 mgKOH/g.

Furthermore, the unit of the numerical value in Table 1 is g (gram).

Moreover, the details of each component used in the 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: Ethyl-1-(9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-ethylindenyl) (Irgacure) OXE02, manufactured by BASF)

<Organic solvent (D)>

PGMEA: propylene glycol monomethyl ether acetate

DEGDM: Diethylene glycol dimethyl ether

<Other optional ingredients> <Interacting Agent (H)>

H-1: Polyoxo-based surfactant (manufactured by Dow Corning Toray Silicones, SH8400FLUID)

<Preparation of the composition> Example 2-1

Addition of the solution (B) as a reactive compound (B) in an amount corresponding to 100 parts by weight (solid content) of the reactant obtained in Example 1-1 as the reactive polycarboxylic acid compound (A) -1) 100 parts by weight of (C-1) 10 parts by weight of the photopolymerization initiator (C), and PGMEA or DEGDM as an organic solvent is added as a desired concentration of the solid content component, and mixed as an interface The composition (S-1) was prepared by filtering 0.30 parts by weight of (H-1) of the active agent (H) using a membrane filter having a pore size of 0.2 μm. Furthermore, the value of the organic solvent in Table 2 is the mass ratio of PGMEA to DEGDM.

Example 2-2~2-3 and Comparative Example 2-1~2-3

The examples 2-2 to 2-3 and the comparative examples 2-1 to 2- were prepared in the same manner as in Example 2-1 except that the types and blending amounts of the respective components were as described in Table 2. The composition of 3. Furthermore, the value of the organic solvent in Table 2 is the mass ratio of PGMEA to DEGDM.

<evaluation>

The composition of Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3 and the spacer formed of the coating films were evaluated as follows. The evaluation results are shown together in Table 3.

(viscosity)

The viscosity (mPa ‧ s) of each composition at 25 ° C was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., TV-200).

(solid content concentration)

0.3 g of the composition was accurately weighed and placed in an alumina dish, about 1 g of diethylene glycol dimethyl ether was added, and then dried at 175 ° C for 60 minutes on a hot plate, and the solid content in the composition was determined according to the weight before and after drying. Constituent concentration (% by mass).

(appearance of the film)

This composition was applied onto a 100×100 mm chromium film-forming glass using a slit die coater (manufactured by Technomachine Co., Ltd., physicochemical mold), and dried under reduced pressure to 0.5 Torr, and thereafter dried at 100 rpm on a hot plate. The film was prebaked at ° C for 2 minutes to form a coating film, and further exposed to an exposure amount of 200 mJ/cm ² to form a film having a film thickness of 4 μm from the upper surface of the chromium film-forming glass. The appearance of the coating film was observed with a naked eye under a sodium lamp. At this time, the strips of the entire coating film are formed (one or a plurality of linear spots are formed in the coating direction or the direction intersecting the coating direction), the misty spots (cloud-like spots), and the tip spots (substrate) Support the appearance of spotted spots formed on the tip. The case where the spots are almost invisible is judged as "○ (good)", and a part of the case where it is slightly permitted is judged as "△ (slightly bad)", and the case where it is clearly visible is judged as "x (bad)".

(flatness)

It was measured using a needle contact type measuring machine (manufactured by Tokyo Precision Co., Ltd., Surfcom) The film thickness of the coating film on the chromium film-forming glass produced by the above method. The film thickness uniformity was measured by measuring the film thickness at nine measurement points and calculating according to the following formula. The nine measurement points are set to X in the short axis direction of the substrate and Y in the long axis direction, (X[mm], Y[mm]) are (50, 10), (50, 20), ( 50, 30), (50, 40), (50, 50), (50, 60), (50, 70), (50, 80), (50, 90). When the film thickness uniformity is 2% or less, the film thickness uniformity can be judged to be good.

Film thickness uniformity (%) = {FT (X, Y) max - FT (X, Y) min} × 100 / {2 × FT (X, Y) avg.}

In the above formula, FT(X, Y)max is the maximum of the film thicknesses at the nine measurement points, and FT(X, Y)min is the minimum of the film thickness at the nine measurement points, FT(X, Y) avg. is the average of the film thicknesses at the nine measurement points.

(High speed coating property)

It was applied onto a 100 mm × 100 mm alkali-free glass substrate by a slit coater, and as a coating condition, the coating liquid was ejected from the nozzle so that the distance between the substrate and the nozzle was 150 μm and the film thickness after the exposure was 2.5 μm. The moving speed of the nozzle was varied within a range of 120 mm/sec. to 200 mm/sec., and the maximum speed at which no streaks due to liquid breakage were generated was determined. At this time, when the stripe spot does not occur even at a speed of 180 mm/sec or more, it can be judged that the coating can be performed at a high speed.

(radiation sensitivity)

The composition was applied onto a 100 mm × 100 mm ITO-sputtered glass substrate by spin coating, and then prebaked on a hot plate at 90 ° C for 3 minutes to form a film having a film thickness of 3.5 μm. . Then, the obtained coating film was exposed to a mask having a circular pattern having a diameter of 12 μm as an opening portion by using an ultraviolet exposure apparatus (Oak Co., Ltd., model: HMW-680GW). Thereafter, it was developed with a 0.05 mass% potassium hydroxide aqueous solution at 25 ° C for 60 seconds, and then washed with pure water for 1 minute, and further post-baked in an oven at 230 ° C for 30 minutes, thereby forming an interval formed by the pattern film. Things. At this time, the residual film rate after the post-baking (the film thickness after the post-baking film × 100 / film thickness after the exposure (before post-baking)) was 90% or more, and the value was used as the sensitivity. . When the value is 55 mJ/cm ² or less, the sensitivity is good.

(developing residue)

Moreover, the upper surface of the substrate was observed by visual observation to confirm the presence or absence of residue. The evaluation criteria are as follows.

○... no residue.

△...Slight residue.

×...There are many residues.

(compression performance)

In the same manner as the evaluation of the radiation sensitivity, the spacer is formed on the substrate, and the spacer formed by the columnar pattern is formed on the substrate, except that the exposure amount is the exposure amount determined by the sensitivity determined in the evaluation of the radiation sensitivity. At this time, the diameter of the reticle that was separated at the time of exposure was changed so that the diameter of the bottom of the pattern after baking was 20 μm. The spacer was subjected to a compression test using a micro-compression tester (Fischerscope H100C, manufactured by Fischer Instruments Co., Ltd.) using a 50 μm square planar indenter at a load of 50 mN, and the change in the compressive displacement amount of the corresponding load was measured, and 50 mN was determined. The recovery rate (%) was calculated from the displacement at the load and the displacement at the load of 50 mN. In this case, when the recovery ratio is 70% or more and the displacement at a load of 50 mN is 0.15 μm or more, the spacer has a compression performance with both high recovery rate and flexibility.

(total light transmittance)

It was coated on a 50 mm × 50 mm alkali-free glass substrate using a spin coater, dried under reduced pressure to 0.5 Torr, and then prebaked on a hot plate at 100 ° C for 2 minutes to form a coating film, which was further 200 mJ/cm ^{2 .} The exposure amount was exposed, whereby a film having a film thickness of 4 μm was formed. The evaluation substrate having the above-mentioned cured coating film was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., TC-H3DPK).

(heat resistant transparency)

The evaluation substrate having the above-mentioned cured coating film was subjected to heat treatment at 250 ° C for 1 hr, and the transmittance of light at a wavelength of 400 nm and 540 nm was measured using a spectrophotometer (manufactured by Hitachi, Ltd., U-3310).

According to the above results, it is clear that the active energy ray-curable composition containing the reactive polycarboxylic acid compound (A) of the present invention and the compositions of Comparative Examples 2-1 to 2-3 of Examples 2-1 to 2-3 Compared with the developability and the curability, it is excellent in heat-resistant transparency, flatness, flexibility, and toughness. Further, in Example 2-1 in which the DMPA (c) was also used in the preparation of the reactive polycarboxylic acid (A), the second embodiment was found to have more excellent compression properties than in Example 2-3.

The present invention will be described in detail with reference to the specific embodiments thereof, and it is obvious to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

In addition, the present application is based on a Japanese patent application filed on Nov. 28, 2013 (Japanese Patent Application No. 2013-246535). Also, all references cited herein are incorporated in their entirety.

[Industrial availability]

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

Claims (5)

An active energy ray-curable resin composition for a display element spacer or a color filter protective film, comprising a reactive polycarboxylic acid compound (A) and a reactive compound other than the reactive polycarboxylic acid compound (A) (B) And a photopolymerization initiator (C) and an organic solvent (D), and the reactive polycarboxylic acid compound (A) is obtained by reacting a polybasic acid anhydride (d) with a reactant (E), and the reactant ( E) a reaction product of the epoxy resin (a), the compound (b), and the optional compound (c) represented by the formula (1), wherein the compound (b) has one or more molecules per molecule. In the case of a polymerized ethylenically unsaturated group and one or more carboxyl groups, the compound (c) is a compound having at least two or more hydroxyl groups and one or more carboxyl groups in one molecule. (wherein R ₁ to R ₈ each may be the same or different and each represents a hydrogen atom, an alkyl group of C1 to C4, or a halogen atom; and G represents a glycidyl group). The active element ray-curable resin composition for a display element or the color filter protective film according to the first aspect of the invention, wherein the reactive polycarboxylic acid compound (A) further comprises a polybasic acid anhydride (d) The reaction product (E) is obtained by a reaction, and the reaction (E) is a reaction of the epoxy resin (a), the compound (b), and the compound (c) represented by the formula (1). The compound (b) has one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule, and the compound (c) has at least two or more hydroxyl groups and one or more molecules per molecule. Carboxyl group. The active element ray-curable resin composition for a display element or the color filter protective film according to the first or second aspect of the invention, wherein R ₁ to R ₈ of the formula (1) are a hydrogen atom. A spacer for a display element, which is formed by the active energy ray-curable resin composition according to any one of claims 1 to 3. A color filter protective film formed by the active energy ray-curable resin composition according to any one of claims 1 to 3.