KR20160090282A - Active energy ray-curable resin composition, and spacer for display elements and/or color filter protective film using same - Google Patents

Abstract

[식 중 R₁∼R₈은 수소원자 등을, G는 글리시딜기를 나타낸다.]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) is further reacted with 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 a molecule, .

Wherein R ₁ to R ₈ represent a hydrogen atom or the like, and G represents a glycidyl group.

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 color filter protective film using the same. BACKGROUND ART [0002]

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

A resin composition comprising a binder polymer, a photopolymerizable monomer and a photopolymerization initiator has been used as a material for a display device. In recent years, as a material used for a display device material "LCD, EL, PDP, FED (SED), rear projection display, electronic paper, digital camera, A liquid crystal display (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 formed 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 have.

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 formed on the inner surface side of the color filter and the electrode substrate facing the color filter. In order to uniformly maintain the cell gap between the color filter and the electrode substrate in the gap portion, a pillar having a certain particle diameter is dispersed as a spacer, or a columnar or striped spacer having a height corresponding to the cell gap is formed . A color image is obtained by controlling the light transmittance of the liquid crystal layer behind each of the pixels colored with 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 an EL and a rear projection display.

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. Further, the spacer needs to be accurately formed in the formation region of the black matrix layer, that is, in the non-display region. Therefore, the colored layer, the protective film, and the columnar spacer are formed by using the curable resin which can easily confine the area to be cured by the photomask.

Further, if development is carried out using an organic solvent after exposure of the coated surface of the curable resin in order to form the colored layer, the protective film or the columnar spacer, it is complicated in terms of handling and waste solution treatment, A curing resin which is capable of developing with an aqueous alkaline solution after exposure has been developed. For these applications, a high temperature (200 to 260 DEG C or more) 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, and particularly excellent in color resist and spacer have.

Patent Document 1 uses a photosensitive resin capable of 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 the case of such a composition containing a salt of a primary amino compound or water, the coating property and the flatness are inferior, and therefore it is not necessarily sufficient to suit the apparatus such as a slit coater.

In Patent Document 2, acid-modified epoxy acrylate of cresol novolac epoxy resin or phenol novolak epoxy resin is used as a polymer component of the photosensitive resin composition for a photo-spacer. However, there is a problem that the radiation sensitivity and developability are not so low as to be 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 elasticity recovery rate required for the photo-spacer is inferior.

Patent Document 4 discloses the use of a resin composition containing an epoxy carboxylate compound as an optical material, but there is no description for a spacer for a display element or a protective film for a color filter at all.

Japanese Patent Application Laid-Open No. 2004-109752 Japanese Patent Application Laid-Open No. 2007-010885 Japanese Patent Application Laid-Open No. 2004-300266 International Publication No. 2008/004630

Disclosed is a spacer for a display element and a protective film for a color filter which are excellent in heat resistance, flatness, flexibility and toughness, and which are excellent in developability, curability and high-speed coating property, .

In order to solve the above problems, the inventors of the present invention have conducted intensive studies, and as a result, found that a specific compound and a resin composition having a composition solve the above problems, and have arrived at the present invention.

That is,

(1) 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), and an organic solvent (D) An active energy ray-curable resin composition for a color filter protective film,

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 polybasic acid anhydride (d) with a reaction product (E) of a compound (c) having at least two hydroxyl groups and at least one carboxyl group in a molecule, To a curable resin composition.

(Wherein R ₁ to R _{8, which} may be the same or different, each represent a hydrogen atom, an alkyl group having ₁ to ₄ carbon atoms, or a halogen atom, and G denotes a glycidyl group.

(2) The present invention also relates to a process for producing a reactive polycarboxylic acid compound (A), wherein the reactive polycarboxylic acid compound (A) is obtained by reacting the epoxy resin (a) represented by the general formula (1) with one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups A reactive polycarboxylic acid compound (A) obtained by further reacting a polybasic acid anhydride (d) with a compound (b) and a reactant (E) of a compound (c) having at least two hydroxyl groups and at least one carboxyl group in a molecule, ) Or the active energy ray-curable resin composition for a color filter protective film according to (1).

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

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

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

(Effects of the Invention)

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 an epoxy resin (a) represented by the general formula (1) with a compound (b) having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in a molecule ) And a compound (c) having at least two hydroxyl groups and at least one carboxyl group in a molecule, if necessary, and further reacting the polybasic acid anhydride (d).

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) Can be 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.

R ₁ to R ₈ in the general formula (1) as the epoxy resin (a) may be the same or different and are each suitably selected from a hydrogen atom, an alkyl group having from ₁ to ₄ carbon atoms, or a halogen atom. Examples of the C1-C4 alkyl group include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- Iodine atom and the like. In the present invention, it is preferable that R ₁ to R ₈ are hydrogen atoms.

The epoxy compound (a) for producing the reactive polycarboxylic acid compound (A) of the present invention is a compound represented by the general formula (2)

(Wherein R ₁ to R _{8, which} may be the same or different, each represent a hydrogen atom, an alkyl group having ₁ to ₄ carbon atoms, or a halogen atom)

Can be obtained by glycidylating a phenol compound containing at least 80 mol% of a compound represented by the following formula (1). For example, Japanese Patent Application Laid-Open No. 2005-200527 discloses a production method thereof, and it can be produced in accordance with this method. That is, the phenolic resin of the general formula (2) is synthesized by a condensation reaction of phenol, a C1 to C4 alkyl group-substituted phenol, a halogeno-substituted phenol or the like with glyoxazine, Can be obtained.

It is also possible to obtain GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.) or JER1031S (manufactured by Japan Epoxy Resin Co., Ltd.) in which R ₁ to R _{8 in} the general formula (1) are all hydrogen atoms as a commercial product.

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

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,? -Cyano cinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and a monoglycidyl compound containing an unsaturated group . Examples of the (meth) acrylic acid include a (meth) acrylic acid, a? -Styryl acrylic acid,? -Furfuryl acrylic acid, a (meth) acrylic acid dimer, a saturated or unsaturated dibasic acid anhydride and a hydroxyl group (Meth) acrylate derivatives and half-esters, which are in-voiced reactants, and half-esters, which are monoglycidyl (meth) acrylate derivatives with a saturated or unsaturated dibasic acid and monoglycidyl (meth) acrylate derivatives.

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 glycerin having a saturated or unsaturated dibasic acid and a plurality of epoxy groups And half-esters, which are reaction products of the cydyl (meth) acrylate derivative at a molar ratio.

Of these, the reaction product of (meth) acrylic acid, (meth) acrylic acid and epsilon -caprolactone or cinnamic acid is the most preferable in view of the sensitivity when the active energy ray-curable resin composition is used. 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 in the present invention reacts 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 to be used in the present invention include dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolacetic acid, dimethylolbutyric acid , Polyhydric alcohol-containing monocarboxylic acids such as dimethylolvaleric acid and dimethylolcaproic acid, and the like. Particularly preferred examples thereof 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, 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 group, the reactivity by the introduced unsaturated bond and the reaction by the remaining epoxy group, for example, the polymerization reaction by the photo- Can be used in combination. In this case, however, care must be taken to preserve the reactive epoxycarboxylate compound (E) and to examine the production conditions.

When the total amount of the compound (b) and the compound (c) to be used is 90 to 120 equivalents based on 1 equivalent of the epoxy resin (a) when the reactive epoxycarboxylate 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 this, the excessive amount of the compound (b) and the compound (c) remain undesirably.

When the epoxy group is intentionally left to remain, the total amount of the compound (b) and the compound (c) is preferably 20 to 90 equivalent% based on 1 equivalent of the epoxy resin (a). When deviating from this range, the reaction by the epoxy group does not sufficiently proceed. 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, and the ratio of the compound (b) to the carboxylic acid is 95: 5 to 40: 60 < / RTI > Within this range, the sensitivity to the active energy ray is good, and sufficient hydroxyl groups 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 with a solvent or by diluting with a solvent. The solvent usable herein 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 Etc., 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? -Butylolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl Monoacetate or polyalkylene glycol monoalkyl ether monoacetate such as ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate and the like, Polycarboxylic acid alkyl esters such as dialkyl glutaric acid, 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. 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 usually 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the reactants to which the solvent 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, , Chromium octanoate, zirconium octanoate, and the like.

It is also preferred to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenyl picrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4-hydroxytoluene or the like as a thermal polymerization inhibitor desirable.

The reaction is terminated when the acid value of the sample becomes 5 mgKOH / g or less, 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 500 to 50,000, more preferably 1,000 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 coating becomes difficult.

Next, the acid addition process will be described in detail. The acid addition process 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, addition reaction of the polybasic acid anhydride (d) to the hydroxyl group generated by the carboxylation reaction introduces a carboxyl group through an ester bond.

Specific examples of the polybasic acid anhydride (d) can be any of those having an acid anhydride structure in the molecule, but examples thereof include anhydrous succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and the like, which are excellent in developability in alkaline aqueous solution, heat resistance, 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 development type resist, for example, the amount of the polybasic acid anhydride (d) to be added is preferably such that the amount of the reactive polycarboxylic acid compound (d) It is preferable to add a calculated value of the solid acid value (in accordance with JIS K 5601-2-1: 1999) of 40 to 120 mg · KOH / g, more preferably 60 to 120 mg · KOH / g. When the acid value of the solid at this time is within this range, developability of the aqueous alkali solution of the photosensitive resin composition of the present invention is satisfactory. In other words, the patterning performance is good and the management of the phenomenon is wide, and the excess acid anhydride does 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 determined by the amount of the reactant, that is, the amount of the reactant (a) obtained from the epoxy compound (a), the carboxylic acid compound Is usually 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the epoxy resin (E), the polybasic acid anhydride (d) and, if desired, the reactants other than the solvent. 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, , Chromium octanoate, and zirconium octanoate.

The acid addition reaction may be carried out by reacting with a solvent or by diluting with a solvent. The solvent which can be used here is not particularly limited as far as the acid addition reaction is an inert solvent. When a solvent is used in the carboxylation reaction in the previous step, the solvent may be directly added to the acid addition reaction in the next step without removing the solvent, provided that the two reactions are imine. The solvent which can be used may be the same as that which can be used 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.

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

This reaction is to be the end point with the point that the acid value of the reactant is within ± 10% of the set acid value while properly sampling.

The preferred molecular weight range of the reactive polycarboxylic acid compound (A) is in the range of 500 to 50,000, more preferably 1,000 to 30,000, in terms of polystyrene reduced 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 acrylates include monofunctional (meth) acrylates, bifunctional (meth) acrylates, trifunctional or more (meth) acrylates, polyester (meth) acrylates, urethane Oligomers, polyester (meth) acrylate oligomers, and epoxy (meth) acrylate oligomers.

Examples of the monofunctional (meth) acrylate include 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, and phenylphenol epoxy (meth) acrylate.

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) ethoxydi (meth) acrylate, bisphenol A (poly) propoxydi (meth) acrylate, bisphenol F Di (meth) acrylate of? -Caprolactone adduct of (poly) ethylene glycol di (meth) acrylate hydroxypivaline acid neopentyl glycol (for example, , 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.

Examples of the (poly) ester (meth) acrylate oligomer include polyhydric alcohols such as 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- Diol, 2,4-diethyl-1,5-pentanediol and 2-butyl-2-ethyl-1,3-propanediol; and alicyclic diols such as cyclohexane-1,4-dimethanol (Poly) ester diol which is a reaction product of a diol compound such as an alicyclic alkyldiol, bisphenol A (poly) ethoxydiol, or bisphenol A (poly) propoxydiol and the above dibasic acid or its anhydride, 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, , 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 polypropoxyl Diol and the like) or a polyester diol which is a reaction product of these diol compounds with dibasic acids or anhydrides thereof (for example, succinic acid, adipic acid, azelaic acid, dimeric acid, isophthalic acid, terephthalic acid, phthalic acid or anhydrides thereof) and organic polyisocyanates (For example, tetramethylene diisocyanate, hexamethylene diisocyanate Chain saturated hydrocarbon isocyanates such as isocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, Cyclic saturated hydrocarbon isocyanates such as methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate and hydrogenated toluene diisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, aromatic polyisocyanates such as p-phenylenediisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-isopropyl-1,3-phenyldiisocyanate and 1,5-naphthalene diisocyanate) , Followed by addition of a hydroxyl group-containing (meth) acrylate.

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, trishydroxyphenyl methane type epoxy (meth) acrylate, dicyclopentadiene phenol type epoxy Containing epoxy (meth) acrylate, bisphenol A epoxy (meth) acrylate, bisphenol F epoxy (meth) acrylate, biphenol epoxy (Meth) acrylate, glyoxylated epoxy (meth) acrylate, and heterocyclic epoxy (meth) acrylate.

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-3,4 Epoxycyclohexanecarboxylate, vinylcyclohexanecarboxylate (manufactured by Union Carbide, " ELR-1 ", trade name, 4206 "), limonene dioxide (" Celloxide 3000 "manufactured by Daicel Chemical Industries, Ltd.), allylcyclohexene dioxide, 3,4, -epoxy-4-methylcyclohexyl- Epoxycyclohexyl) -5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate ("SAIRACURE UVR-6128" Etc.), bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) Bis (3,4-epoxycyclohexylmethyl) ether, and bis (3,4-epoxycyclohexyl) diethylsiloxane.

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 obtained spacer and 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) to be used is 30 parts by weight to 250 parts by weight, the sensitivity of the composition and the heat resistance and elasticity properties of the resulting spacer for a display element are improved.

As the photopolymerization initiator (C) of the present invention, an active species capable of initiating polymerization of the reactive polycarboxylic acid compound (a) and the reactive compound (B) other than the reactive polycarboxylic acid compound (A) ≪ / RTI > 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] -octane- 3-yl] -ethan- 1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H- Oxo-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H- ), Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol- 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol- Methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- . Of 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) - (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 and 1- (4-i-propylphenyl) (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, and the like.

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) Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis ) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4' '-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.

A commercially available product may be used as the photopolymerization initiator (C), and examples thereof include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (Irgacure 907, 2- 1- (9-ethyl-6- (2-methylpyridin-2-yl) methyl) Benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02) (all available from Ciba Specialty Chemicals).

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 the curing accelerator which can be used in combination include amines such as triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethylbenzoate, dimethylaminoacetophenone, p- dimethylaminobenzoic acid isoaminoester, , 2-mercaptobenzothiazole, and the like. The amount of these curing accelerators to be used is usually 0 wt% or more and 5 wt% or less when the solid content of the resin composition of the present invention is 100 wt%.

As the organic solvent (D), it is preferable that each component is uniformly dissolved or dispersed and does not react with each 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.

Specific 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 butyrate, 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. When the solid content concentration of the composition is within the above range, it is possible to effectively suppress the occurrence of unevenness of coating and improvement of coating property, improvement of film thickness uniformity.

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-mentioned range, it is possible to achieve a good balance of spontaneous uniformity even if coating unevenness occurs while maintaining film thickness uniformity.

Examples of the alkali-soluble resin (G) used in the photosensitive resin composition of the present invention include a 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 hydroxyl group, a monomer having a sulfonic acid group, other monomers, and the above 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-butene-1-malic cinnamic 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. And at least one hydrogen atom of these benzene rings is an alkyl group such as methyl group, ethyl group or 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 copolymerizing the alkali-soluble resin (G), it can be produced by radical polymerization of an unsaturated compound in a solvent in the presence of a polymerization initiator. These solvents may be used alone or in a mixture of two or more.

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'-azobisisobutylonitrile (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, 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) an acid anhydride (f) having an ethylenic double bond to the monomer (e) having a hydroxyl group,

(2) a compound (f) having an isocyanate group and an ethylenic double bond with respect to the monomer (e) having a hydroxyl group,

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

(4) a compound (f) having a hydroxyl group and an ethylenic double bond with respect to the acid anhydride (e) having an ethylenic double bond,

(5) a compound (f) having an epoxy group and an ethylenic double bond to 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) acryloyloxymethyl 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, publicly known polymerization inhibitors can be used, and specific examples thereof include 2,6-di-t-butyl-p-cresol.

A catalyst or neutralizing agent may also 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.

In the photosensitive resin composition of the present invention, a surface active agent, 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 functionality. Examples of the photo stabilizer include a hindered amine compound, a benzoate compound, and the like, as a photo-stabilizer, a fluorine compound, a silicon compound, and an acrylic compound as a defoaming agent, a benzotriazole compound, a benzophenone compound, and a triazine compound as ultraviolet absorbers, Examples of the inhibitor include phenol compounds. Examples of the polymerization inhibitor include methoquinone, methylhydroquinone and hydroquinone. Examples of the crosslinking agent include polyisocyanates and melamine compounds.

As other resins (so-called inate polymers) which do not exhibit reactivity with active energy rays, other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, Allyl 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) in an amount of usually 60 to 90% by weight, preferably 65 to 90% by weight, preferably 5 to 59% by weight, preferably 5 to 59% by weight and a photopolymerization initiator (C) To 85% by weight. And may contain other components in an amount of usually 0 to 80% by weight, if necessary.

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

The spacer for a display element formed from the composition is preferably included in the present invention. As a method of forming the spacer for a display element,

(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 apparatus, a known coating apparatus 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 of forming on the transparent common electrode formed on the colored layer is described.

If necessary, heat is applied and dried (pre-baking). The drying temperature is preferably 50 DEG C or higher, more preferably 70 DEG C or higher, and further preferably 150 DEG C or lower, more preferably 120 DEG C 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 more 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, 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 the preferable 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 with a developing solution, and development is performed. Here, the developing solution used in the development may be an organic solvent, but it is preferable to use an aqueous alkaline solution. Examples of the aqueous alkaline 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 hydrogencarbonate and the like; And an aqueous solution of an organic salt such as hydroxytetramethylammonium, hydroxytetraethylammonium and the like. These may be used alone 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 alkali in the aqueous alkaline solution is preferably 0.1 to 5% by weight from the viewpoint of obtaining 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 needed to more secure the curing. When baking is performed, the baking temperature is preferably 120 to 250 캜. 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 bake method in which a heating process is performed twice or more, 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 forming method is a spacer having a high degree of flatness without being uneven in coating, being flexible, and having a small plastic deformation. A liquid crystal display element, an organic EL display element, and 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. 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 K 7236: 2001.

2) Softening point: Measured by the method according to JISK 7234: 1986.

3) Acid value: Measured by the method according to JISK 0070: 1992

Examples 1-1 to 1-3

[Preparation of reactive polycarboxylic acid compound (A)

The amount of acrylic acid (abbreviated AA, Mw = 72) as the compound (b) in the amounts shown in Table 1 and the amount of acrylic acid (abbreviated AA, Mw = Dimethylolpropionic acid (abbreviated as DMPA, Mw = 134) was added as the component (c) in Table 1. 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added in an amount of 80% by weight based on the solid content of the reaction solution and reacted at 100 DEG C for 24 hours to obtain a solution of a 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 by measuring the reaction solution and calculating the acid value as a solid content.

Subsequently, tetrahydrophthalic anhydride (abbreviated as THPA) as a polybasic acid anhydride (d) was added to a solution of the reactive epoxycarboxylate compound (E) in an amount of 65 parts by weight based on 100 parts by weight of solid content as a solvent and propylene glycol monomethyl Ether monoacetate was added and heated to 100 占 폚, followed by acid addition reaction to obtain a reactive polycarboxylic acid compound (A) solution. 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 novolac epoxy resin EOCN-103S (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 200 g / eq) was used as the base material in Table 1, acrylic acid as the compound (b) in the amounts shown in Table 1, and dimethylolpropionic acid Quot; DMPA ", Mw = 134) 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 the reaction was carried out at 100 占 폚 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.

Next, propylene glycol monomethyl ether monoacetate was added to the reactive epoxycarboxylate compound solution so that the amount of tetrahydrophthalic anhydride (abbreviated as THPA) as a polybasic acid anhydride was 65 parts by weight based on 100 parts by weight of the solid content as shown in Table 1 , And the mixture was heated to 100 占 폚, followed by acid addition reaction 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 (manufactured by Nippon Kayaku, epoxy equivalent weight: 200 g / eq), 58 g of acrylic acid, 40 g of dimethylolpropionic acid, 3 g of triphenylphosphine as a catalyst and 3 g of propylene glycol monomethyl ether mono Acetate 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: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku)

≪ 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 manufactured by Dow Corning Toray Silicone Co., Ltd.)

&Lt; Preparation of the composition &

Example 2-1

100 parts by weight of (B-1) as a reactive compound (B), 100 parts by weight of a photopolymerization initiator (B) as a reactive polycarboxylic acid compound (A) , 10 parts by weight of (C-1) as a surfactant (C-1) and PGMEA and DEGDM as organic solvents were added to a desired solid concentration and 0.3 parts by weight of (H-1) To obtain a 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 from the coating films were evaluated as described below. The evaluation results are shown in Table 3.

(Viscosity)

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

(Solid concentration)

0.3 g of the composition was standardized on 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, and the solid content concentration (mass%) in the composition was obtained from the weight before and after drying .

(Appearance of coating film)

The composition was coated on a 100 x 100 mm chrome-deposited glass using a slit die coater (Rikadai Co., Ltd.), dried under reduced pressure to 0.5 Torr, and then pre-baked on a hot plate at 100 캜 for 2 minutes, And 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-forming glass. The appearance of the coating film was observed with naked eyes under a sodium lamp. At this time, the stripe unevenness (unevenness of the coating direction or one or a plurality of straight lines occurring in the direction crossing the same), fog unevenness (cloud-shaped unevenness), pin mark unevenness Shape dirt) was investigated. (Poor), and the case where it is clearly seen as &quot; x (defective) &quot;.

(Flatness)

The film thickness of the coating film on the chromium film-forming glass produced as described above was measured using a needle contact type measuring instrument (Surfcom Co., Ltd., Tokyo Seimitsu Co., Ltd.). 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}

FT (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 ) avg. is the average value of the film thickness at nine measurement points.

(High-speed coating property)

Using a slit coater on a 100 mm x 100 mm non-alkali glass substrate, the coating liquid was ejected from the nozzle so that the distance between the base and the nozzle was 150 mu m and the film thickness after the exposure was 2.5 mu m. The maximum speed at which stripe-shaped unevenness due to dropping of the liquid did not occur was obtained by varying the range from 120 mm / sec to 200 mm / sec. At this time, it can be judged that it is possible to cope with high-speed coating in the case where no stripe-shaped unevenness occurs even at a speed of 180 mm / sec.

(Radiation sensitivity)

The composition was coated on a 100 mm x 100 mm ITO sputtered glass substrate using a spin coating 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 resultant coating film was exposed through a photomask having a circular pattern with a diameter of 12 mu m as an opening portion, using an ultraviolet ray exposure apparatus (Oakish Sakusho, Model HMW-680GW). Thereafter, the resist film was developed with a 0.05 mass% aqueous solution of potassium hydroxide at 25 DEG C for 60 seconds, washed with pure water for 1 minute, and further baked in an oven at 230 DEG C for 30 minutes to form a spacer made of 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 investigated. When this value is 55 mJ / cm 2 or less, the sensitivity can be said to be good.

(Development residue)

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 small amount of residue.

× ... There is a lot of residue.

(Compression performance)

A spacer having a columnar pattern was formed on the substrate in the same manner as in the evaluation of the radiation sensitivity except that the exposure amount was an exposure amount 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 compressive test at a load of 50 mN using a micro compacting tester (Fisher Scope H100C, manufactured by Fisher Instruments, Inc.) and using a flat indenter of 50 mu m in width and 50 mu m, And the recovery rate (%) was calculated from the amount of displacement when the load of 50 mN was removed and the amount of displacement when the load of 50 mN was removed. At this time, when the recovery rate is not less than 70% and the displacement when the load of 50 mN is not less than 0.15 탆, it is a spacer having both a high recovery rate and flexibility.

(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 prebaked on a hot plate at 100 캜 for 2 minutes to form a coating film and 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 (TC-H3DPK, manufactured by Nippon Denshoku Kogyo Co., Ltd.).

(Heat resistance transparency)

The evaluation substrate having the cured coating film was subjected to heat treatment at 250 DEG C for 1 hour and the transmittance of the wavelength light of 400 nm and 540 nm was measured by 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 same composition as that of Comparative Examples 2-1 to 2-3 Compared with the composition, it has become clear that developability and curability are good, and excellent heat-resistant transparency, flatness, flexibility and toughness are obtained. Further, it was found that Examples 2-1 and 2-2 using DMPA (c) for the preparation of the reactive polycarboxylic acid (A) had better compression performance than those of Example 2-3.

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.

The present application is based on Japanese patent application (Japanese Patent Application No. 2013-246536) filed on November 28, 2013, which is incorporated by reference in its entirety. Also, all references cited herein are incorporated 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 preferable 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 (5)

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 the 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, The reactive polycarboxylic acid compound (A), which is obtained by further reacting a polybasic acid anhydride (d) with a reaction product (E) of a compound (c) having at least two hydroxyl groups and at least one carboxyl group in a molecule, Ray curable resin composition.

Wherein R ₁ to R ₈ may be the same or different and each represents a hydrogen atom, an alkyl group having ₁ to ₄ carbon atoms, or a halogen atom. And G represents a glycidyl group. 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, Which is a reactive polycarboxylic acid compound (A) obtained by further reacting a polybasic acid anhydride (d) with a reaction product (E) of a compound (c) having at least two hydroxyl groups and at least one carboxyl group, Active energy ray curable resin composition for a filter protective film. 3. The method according to claim 1 or 2,
The active energy ray-curable resin composition for a spacer for a display element or the color filter protective film in which R ₁ to R _{8 in} the general formula (1) are hydrogen atoms. A spacer for a display element formed from the active energy ray-curable resin composition according to any one of claims 1 to 3. A color filter protective film formed from the active energy ray-curable resin composition according to any one of claims 1 to 3.