KR102255619B1 - 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.]It provides an active energy ray-curable resin composition capable of forming a spacer for a display device and a color filter protective film having excellent heat transparency, flatness, flexibility, and toughness, and a spacer for a display device and a color filter protective film. The resin composition of the present invention contains a reactive polycarboxylic acid compound (A), a reactive compound other than the compound (A) (B), a photopolymerization initiator (C), and an organic solvent (D), and the compound (A) The polybasic acid anhydride (d) is further reacted with the reaction product of at least an epoxy resin (a) represented by the following general formula (1) and a compound (b) having at least one polymerizable ethylenically unsaturated group and at least one carboxyl group It is obtained by doing.

[In the formula, R _{1 to R 8} represent a hydrogen atom or the like, and G represents a glycidyl group.]

Description

An active energy ray-curable resin composition, and a spacer for a display element and/or a color filter protective film using the same TECHNICAL FIELD

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.

A resin composition comprising a binder polymer, a photopolymerizable monomer, and a photopolymerization initiator has been used as a material for a display device. Recently, as a material for display devices "LCD, EL, PDP, FED (SED), rear projection display, electronic paper, or digital camera, especially display elements, materials around display elements", for example, color Liquid crystal displays (LCDs) are rapidly spreading. In general, a color liquid crystal display device has a structure in which a color filter and an electrode substrate such as a TFT substrate are opposed to each other to form a gap of about 1 to 10 μm, a liquid crystal compound is filled in the gap, and the periphery is sealed with a sealing material. have.

The color filter is a black matrix layer formed in a predetermined pattern to shield the boundary between pixels on a transparent substrate, and usually red (R), green (G), and blue (B) are arranged in a predetermined order to form each pixel. One colored layer, a protective film, and a transparent electrode film are stacked in this order from the side close to the transparent substrate. Further, an alignment film is formed on the inner surface side of the color filter and the electrode substrate facing the color filter. In addition, in order to keep the cell gap between the color filter and the electrode substrate constant and uniform in the gap, pearls having a certain particle diameter are dispersed as spacers, or a columnar or stripe-shaped spacer having a height corresponding to the cell gap is formed. Has been. Then, a color image is obtained by controlling the light transmittance of the liquid crystal layer behind each of the pixels colored in each color. Such color filters are not limited to color liquid crystal display devices, but are also used in other display devices such as EL and rear projection displays.

The colored layer, the protective film, and the spacer may be formed using a resin. The colored layer needs to be formed in a predetermined pattern for each pixel of each color. It is preferable that the protective film can cover only a region in which the colored layer is formed on the transparent substrate in consideration of the adhesion and hermeticity of the sealing portion. In addition, the spacer needs to be accurately formed in the black matrix layer formation region, that is, in the non-display region. For this reason, a colored layer, a protective film, and a columnar spacer are formed using a curable resin that can easily define a region to be cured with a photomask.

In addition, when developing with an organic solvent after exposing the coated surface of the curable resin to form a colored layer, protective film or columnar spacer, it is cumbersome in terms of handling and waste liquid treatment, and the economy and stability are insufficient, so that the curable resin is acidic. A curable resin has been developed that introduces a group and allows it to be developed with an aqueous alkali solution after exposure. For these applications, a high temperature (at 200-260°C or higher) is applied to the formation of the alignment film and the transparent electrode, so it is required to have very high heat resistance and excellent heat resistance and coloring resistance, especially for color resists and spacers. have.

In Patent Document 1, a photosensitive resin capable of neutralizing an acid-modified epoxy acrylate of a cresol novolac epoxy resin with a primary amino compound is used as a polymer component of the photosensitive resin composition for photo spacers and color filters. However, in a composition containing a salt or water of such a primary amino compound, coating properties and flatness are inferior, and it cannot be said that the suitability for a device such as a slit coater is sufficient.

In addition, in Patent Document 2, as a polymer component of the photosensitive resin composition for photo spacers, a cresol novolac epoxy resin or an acid-modified epoxy acrylate of a phenol novolac epoxy resin is used. However, there was a problem in that the radiation sensitivity and developability were poor, and the level was not sufficiently satisfactory.

In Patent Document 3, a reaction product obtained by adding acrylic acid and dimethylolpropionic acid to a cresol novolac epoxy resin as a polymer component of a protective film of a color filter or a resist ink composition for a flexible printed wiring board was modified with caprolactone and further modified with tetrahydrophthalic anhydride. A line-curable resin is used. The polymer component, which is the main component of the composition, is excellent in developability and flexibility, but there is a problem in that the elastic recovery rate required as a photo spacer is inferior.

Patent Document 4 discloses the use of a resin composition containing an epoxy carboxylate compound as an optical material, but does not describe any spacer for a display element or a protective film for a color filter.

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

The present invention is an active energy ray-curable resin composition having good developability, curability, and high-speed coating by improving the problems of the prior art, and providing a spacer for a display device and a color filter protective film excellent in heat transparency, flatness, flexibility, and toughness. It is aimed at.

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

That is, the present invention,

(1) A spacer for a display element containing a reactive polycarboxylic acid compound (A), a reactive compound other than the reactive polycarboxylic acid compound (A) (B), a photopolymerization initiator (C), and an organic solvent (D), or As an active energy ray-curable resin composition for a color filter protective film,

The reactive polycarboxylic acid compound (A) is an epoxy resin (a) represented by the general formula (1), a compound (b) having at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in one molecule, and if necessary Therefore, the active energy ray, which is a reactive polycarboxylic acid compound (A) obtained by further reacting a polybasic acid anhydride (d) with a reactant (E) of a compound (c) having at least two hydroxyl groups and one or more carboxyl groups in one molecule. It relates to a curable resin composition.

(In the formula, R _{1 to R 8} may be the same or different, respectively, and represent a hydrogen atom, a C1 to C4 alkyl group, or a halogen atom. G represents a glycidyl group.)

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

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

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

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

(Effects of the Invention)

The active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention has excellent developability, high radiation sensitivity, and excellent heat 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 an epoxy resin (a) represented by the general formula (1) and a compound (b) having at least one polymerizable ethylenically unsaturated group and at least one carboxyl group per molecule. ), and if necessary, a polybasic acid anhydride (d) is further reacted with a reaction product of a compound (c) having at least two hydroxyl groups and one or more carboxyl groups in one molecule.

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

In the present invention, the features of the present invention are exhibited by introducing an ethylenically unsaturated group and a hydroxyl group into the molecular chain by an epoxy carboxylation reaction.

_{R 1} to _{R 8} in the general formula (1) as the epoxy resin (a) may be the same or different, respectively, and are suitably selected from a hydrogen atom, a C1 to C4 alkyl group, or a halogen atom. Examples of the C1-C4 alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, and the like, and halogen atoms include chlorine atom, bromine atom, And iodine atom. In the present invention, it _{is preferable that R 1 to R 8} are hydrogen atoms.

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

(In the formula, R _{1 to R 8} may be the same or different, respectively, and represent a hydrogen atom, a C1 to C4 alkyl group, or a halogen atom.)

It can be obtained by glycidylating a phenol compound containing 80 mol% or more of the compound represented by. For example, Japanese Patent Application Laid-Open No. 2005-200527 describes a method for manufacturing it, and it is possible to manufacture according to the method. That is, in the condensation reaction of glyoxal with phenol, C1-C4 alkyl group substituted phenol, or halogeno-substituted phenol, the phenol resin of general formula (2) is synthesized, and by epoxidating this, the epoxy resin of general formula (1) (a) Can be obtained.

Further, as a commercial item, it is possible to obtain GTR-1800 (product of Nippon Kayaku Co., Ltd.) or JER1031S (product of Japan epoxy resin) in which all _{of R 1} to _{R 8 in} the general formula (1) are hydrogen atoms.

The epoxy compound (a) used in the present invention has a melting point or softening point of 100°C or higher. Further, 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 at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in one molecule is reacted in order to impart reactivity to active energy rays. There is no limitation as long as there is at least one ethylenically unsaturated group and one carboxyl group in the molecule. Examples of these include monocarboxylic acid compounds and polycarboxylic acid compounds.

Examples of monocarboxylic acid compounds having one carboxyl group in one molecule include (meth)acrylic acids, crotonic acid, α-cyanocinic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and a monoglycidyl compound containing an unsaturated group. Can be mentioned. In the above, examples of (meth)acrylic acids include (meth)acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth)acrylic acid dimer, saturated or unsaturated dibasic acid anhydride, and one hydroxyl group per molecule. And half-esters as a sugar-molar reaction product with the (meth)acrylate derivative possessed, and half-esters as a sugar-molar reaction product of a saturated or unsaturated dibasic acid and a mono-glycidyl (meth)acrylate derivative.

In addition, polycarboxylic acid compounds having two or more carboxyl groups in one molecule include (meth)acrylate derivatives having a plurality of hydroxyl groups in one molecule and half-esters that are sugar-molar reactants, saturated or unsaturated dibasic acids, and glycerol having plural epoxy groups. And half esters, which are sugar-molar reactants of cidyl (meth)acrylate derivatives.

Among these, (meth)acrylic acid, a reaction product of (meth)acrylic acid and ε-caprolactone, or cinnamic acid are most preferred from the viewpoint of sensitivity when used as an active energy ray-curable resin composition. It is preferable that the compound (b) does not have a hydroxyl group in the compound.

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

As a specific example of the compound (c) having at least two hydroxyl groups and one or more carboxyl groups in one molecule used as necessary in the present invention, for example, dimethylol propionic acid, dimethylol butanoic acid, dimethylol acetic acid, dimethylol butyric acid And polyhydroxy-containing monocarboxylic acids such as dimethylolvaleric acid and dimethylolcaproic acid. As a particularly preferable thing, dimethylolpropionic acid etc. are mentioned, for example.

Among these, considering 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, and monocarboxylic acids and poly Even when carboxylic acid is used together, it is preferable that the value represented by the total molar amount of monocarboxylic acid/the total molar amount of polycarboxylic acid is 15 or more.

In this reaction, the ratio of the total amount of carboxylic acids of the epoxy resin (a) and the compound (b) and the compound (c) used as necessary should be appropriately changed depending on the application. That is, when all the epoxy groups are carboxylated, the unreacted epoxy groups do not remain, so the storage stability as a reactive epoxy carboxylate compound is high. In this case, only the reactivity by the introduced double bond is used.

On the other hand, by deliberately reducing the input amount of the carboxylic acid compound to leave unreacted residual epoxy groups, the reactivity by the introduced unsaturated bonds and the reaction by the remaining epoxy groups, for example, polymerization or thermal polymerization by photocationic catalysts. It is also possible to use in combination. However, in this case, attention should be paid to the storage of the reactive epoxy carboxylate compound (E) and examination of the production conditions.

In the case of preparing a reactive epoxy carboxylate compound (E) that does not retain an epoxy group, the total amount of the compound (b) and the compound (c) used as necessary is 90 to 120 equivalents based on 1 equivalent of the epoxy resin (a). It is preferably %. In this range, production under relatively stable conditions is possible. In the case where the total amount of compound (b) and compound (c) to be used as necessary is larger than this, since excess compound (b) and compound (c) remain, it is not preferable.

In addition, when the epoxy group is intentionally left, it is preferable that the total amount of the compound (b) and the compound (c) is 20 to 90 equivalent% based on 1 equivalent of the epoxy resin (a). When it deviates from this range, further reaction by an epoxy group does not fully advance. In this case, sufficient attention must be paid to the gelation during the reaction and the aging stability of the reactive epoxy carboxylate compound (E).

In the case of using compound (b) and compound (c), the ratio of compound (b): compound (c) to 95:5 to 5:95, and 95:5 to 40: A range of 60 is preferred. In this range, the sensitivity to active energy rays is good, and sufficient hydroxyl groups can be introduced in order to react the polybasic acid anhydride (d) with the reactive epoxy carboxylate compound (E).

The carboxylation reaction may be reacted with no solvent, or may be reacted by diluting with a solvent. The solvent usable here is not particularly limited as long as it is an inate solvent with respect to the carboxylation reaction.

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

Specifically, for example, 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, and solvent naphtha Etc., ester solvents, ether solvents, ketone solvents, and the like.

Ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butylrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl Mono 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 Polycarboxylic acid alkyl esters such as dialkyl glutarate, dialkyl succinate and dialkyl adipic acid.

As ether solvents, alkyl ethers such as diethyl ether and ethyl butyl ether, 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, cyclic ethers, such as tetrahydrofuran, etc. are mentioned.

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 compounds (B) described later. In this case, when it is used as a curable composition, since it can be used directly as a composition, it is preferable.

During the reaction, it is preferable to use a catalyst to accelerate the reaction, and the amount of the catalyst is the reactant, i.e., the epoxy resin (a), the carboxylic acid compound (b), the compound (c) used as necessary, and in some cases Accordingly, it is usually 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the reactant to which the solvent is added. The reaction temperature at that 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, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstyrene, methyltriphenylstyrene. , Known general basic catalysts such as chromium octanoate and zirconium octanoate.

In addition, it is recommended to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4hydroxytoluene, etc. as a thermal polymerization inhibitor. desirable.

This reaction takes as the end point when the acid value of the sample becomes 5 mgKOH/g or less, preferably 3 mgKOH/g or less while appropriately sampling.

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

When it is smaller than this molecular weight, the toughness of the cured product is not sufficiently exhibited, and when it is too large than this, the viscosity becomes high, making it difficult to apply.

Next, the acid addition process will be described in detail. The acid addition step is performed for the purpose of introducing a carboxyl group into the reactive epoxy carboxylate compound (E) obtained in the preceding step to obtain a reactive polycarboxylic acid compound (A). That is, by adding a polybasic acid anhydride (d) to the hydroxyl group produced by the carboxylation reaction, a carboxyl group is introduced through an ester bond.

As a specific example of the polybasic acid anhydride (d), for example, any compound having an acid anhydride structure in the molecule can be used, but succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, which are excellent in developability, heat resistance, hydrolysis resistance, etc. of an aqueous alkali solution, Particularly preferred are hexahydro phthalic anhydride, itaconic anhydride, 3-methyl-tetrahydro phthalic anhydride, 4-methyl-hexahydro phthalic 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 carboxylate reaction solution. The amount of addition should be appropriately changed according to the application.

The amount of polybasic acid anhydride (d) added is, for example, when the reactive polycarboxylic acid compound (A) of the present invention is to be used as an alkali developing resist, a reactive polycarboxylic acid compound that is finally obtained polybasic acid anhydride (d). It is preferable to put a calculated value such that the solid content acid value of (A) (according to JISK 5601-2-1:1999) is 40 to 120 mg·KOH/g, more preferably 60 to 120 mg·KOH/g. When the solid acid value at this time is within this range, the developability of the aqueous alkali solution of the photosensitive resin composition of the present invention exhibits good developability. That is, the good patterning property and the management range for hyperphenomena are wide, and there is no excess acid anhydride remaining.

During the reaction, it is preferable to use a catalyst to accelerate the reaction, and the amount of the catalyst is the reactivity obtained from the reactants, that is, the epoxy compound (a), the carboxylic acid compound (b), and the compound (c) used as necessary. The epoxy carboxylate compound (E), and polybasic acid anhydride (d), in some cases, is usually 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the reactant to which other than a solvent is added. The reaction temperature at that 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, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstyrene, methyltriphenylstyrene. , Chromium octanoate, zirconium octanoate, and the like.

This acid addition reaction can also be reacted with no solvent, or can be made to react by diluting with a solvent. The solvent usable here is not particularly limited as long as it is an inate solvent with respect to the acid addition reaction. In addition, when a solvent is used in the preceding step, the carboxylation reaction, the solvent may be directly subjected to the next step, the acid addition reaction, provided that it is an inate for both reactions. The solvent that can be used may be the same one that can be used in the carboxylation reaction.

The amount of the solvent used should be appropriately adjusted according to the viscosity and use of the resin to be obtained, but is preferably used so that it may be 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 it is used as a curable composition, since it can be used directly as a composition, it is preferable.

Moreover, it is preferable to use the same thing as an example in the said carboxylation reaction as a thermal polymerization inhibitor.

This reaction is set as the end point with the point where the acid value of the reactant is within the range of ±10% of the set acid value while sampling appropriately.

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

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

Examples of the reactive compound (B) usable in the present invention include so-called reactive oligomers such as radical-reactive acrylates, cation-reactive epoxy compounds, and vinyl compounds responsive to both.

Examples of radical-reactive acrylates include monofunctional (meth)acrylate, bifunctional (meth)acrylate, trifunctional or higher (meth)acrylate, polyester (meth)acrylate, urethane (meth)acrylate. Oligomers, polyester (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, and the like.

Examples of monofunctional (meth)acrylates include acryloylmorpholine; Hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Cyclohexane-1,4-dimethanol mono (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth) )Acrylate, aliphatic (meth)acrylate such as dicyclopentenyloxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenyl (poly)ethoxy (meth)acrylate, p-cumylphenoxy Ethyl (meth)acrylate, tribromophenyloxyethyl (meth)acrylate, phenylthioethyl (meth)acrylate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, phenylphenol (poly) And aromatic (meth)acrylates such as oxy(meth)acrylate and phenylphenol epoxy(meth)acrylate.

As bifunctional (meth)acrylate, 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,9-nonanedioldi(meth)acrylate, tricyclodecanedi Methanol (meth)acrylate, bisphenol A (poly) ethoxydi (meth) acrylate, bisphenol A (poly) propoxydi (meth) acrylate, bisphenol F (poly) ethoxydi (meth) acrylate, ethylene glycol di (Meth)acrylate, (poly)ethylene glycol di(meth)acrylate, di(meth)acrylate of the ε-caprolactone adduct of neopentyl glycol hydroxybivalate (for example, manufactured by Nippon Kayaku Co., Ltd. , KAYARAD HX-220, HX-620, etc.), etc. are mentioned.

As polyfunctional (meth)acrylates having 3 or more functionalities, dimethylolpropane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethyloloctane tri(meth)acrylate, trimethylolpropane(poly)ethoxytri Methylols such as (meth)acrylate, trimethylolpropane (poly)propoxytri(meth)acrylate, and trimethylolpropane (poly)ethoxy(poly)propoxytri(meth)acrylate; Pentaerythritol tri(meth)acrylate, pentaerythritol(poly)ethoxytetra(meth)acrylate, pentaerythritol(poly)propoxytetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra Pentaerythritols such as (meth)acrylate, dipentaerythritol penta (meth)acrylate, and dipentaerythritol hexa (meth)acrylate; Tris[(meth)acryloyloxyethyl]isocyanurate, caprolactone-modified tris[(meth)acryloyloxyethyl]isocyanurate, etc.; Succinic acid-modified pentaerythritol triacrylate and succinic acid-modified dipentaerythritol pentaacrylates are mentioned.

Examples of (poly) ester (meth) acrylate oligomers include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, (poly) ethylene glycol, (poly) propylene. Glycols such as glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1, Linear or branched alkyldiols such as 5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, and cyclohexane-1,4-di A diol compound such as alicyclic alkyldiol such as methanol, bisphenol A (poly) ethoxydiol, or bisphenol A (poly) propoxydiol, and a (poly) ester diol which is a reaction product of the dibasic acid or anhydride thereof, and (meta ) A reactant of acrylic acid, etc. are mentioned.

Examples of urethane (meth)acrylate oligomers include diol compounds (e.g. ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, neopentyl glycol, 1 ,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 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 polyethoxydiol, bisphenol A polypropoxy Diol, etc.) or a reaction product of these diol compounds and dibasic acids or anhydrides thereof (for example, succinic acid, adipic acid, azelaic acid, dimer acid, isophthalic acid, terephthalic acid, phthalic acid, or anhydrides thereof), and organic polyisocyanates (For example, chain saturated hydrocarbon isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, nor Cyclic saturated hydrocarbon isocyanates such as bornane diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, and 2,4-tolylenedi Isocyanate, 1,3-xylylenediisocyanate, p-phenylenediisocyanate, 3,3'-dimethyl-4,4'-biphenylenediisocyanate, 6-isopropyl-1,3-phenyldiisocyanate, 1,5 -Aromatic polyisocyanates such as naphthalene diisocyanate) are reacted, followed by addition of a hydroxyl group-containing (meth)acrylate, and the like.

Examples of the epoxy (meth)acrylate oligomer include a compound having an epoxy group and a carboxylate compound of (meth)acrylic acid. For example, phenol novolak type epoxy (meth) acrylate, cresol novolak type epoxy (meth) acrylate, trishydroxyphenylmethane type epoxy (meth) acrylate, dicyclopentadienephenol type epoxy (meth) acrylic Rate, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, biphenol type epoxy (meth) acrylate, bisphenol-A novolak type epoxy (meth) acrylate, naphthalene skeleton-containing epoxy ( Meth)acrylate, glyoxal type epoxy (meth)acrylate, heterocyclic epoxy (meth)acrylate, and the like.

Vinyl ethers, styrene, and other vinyl compounds are mentioned as vinyl compounds. Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of styrenes include styrene, methyl styrene, and ethyl styrene. Examples of other vinyl compounds include triallyl isocyanurate and trimetaallyl isocyanurate.

In addition, there is no particular limitation as long as it is a compound having an epoxy group generally as a cationic reactive monomer. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4 ,-Epoxycyclohexanecarboxylate (Cyracure UVR manufactured by Union Carbide, etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide ("ELR- by Union Carbide") 4206", etc.), limonene dioxide (such as "Celoxide 3000" manufactured by Daicel Chemical Industry Co., Ltd.), allylcyclohexene dioxide, 3,4,-epoxy-4-methylcyclohexyl-2-propylene oxide, 2-(3, 4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl) adipate (``Cyracure UVR-6128'' by Union Carbide Co., Ltd. Etc.), bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxycyclohexyl) ether, bis(3,4-epoxycyclohexylmethyl) ether, bis(3,4-epoxycyclo Hexyl) diethylsiloxane, etc. are mentioned.

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

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) used 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 based on 100 parts by weight of the reactive polycarboxylic acid compound (A). When the amount of the reactive compound (B) used is 30 parts by weight to 250 parts by weight, the sensitivity of the composition, heat resistance, and elastic properties such as a spacer for a display element obtained are more favorable.

As the photoinitiator (C) of the present invention, an active species capable of initiating polymerization of a reactive polycarboxylic acid compound (a) and a reactive compound (B) other than the reactive polycarboxylic acid compound (A) in response to active energy rays It is an ingredient that generates. As such a photoinitiator (C), an O-acyloxime compound, an acetophenone compound, a biimidazole compound, etc. are mentioned.

As an O-acyloxime compound, for example, ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 1-[ 9-ethyl-6-benzoyl-9H-carbazol-3-yl]-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole- 3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one Oxime-O-benzoate, ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime ), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone- 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9- Ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime), etc. Can be mentioned. Among these, ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl -6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) or ethanone-1-[9-ethyl-6-{ 2-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 acetophenone compounds include α-aminoketone compounds and α-hydroxyketone compounds.

As an α-aminoketone compound, for example, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1 -(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and the like.

As an α-hydroxyketone compound, for example, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropane-1 -One, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, etc. are mentioned.

Among these acetophenone compounds, α-aminoketone compounds are preferable, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one or 2-dimethylamino-2-(4- Methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one is more preferred.

As a biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimi Dazole, 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 And'-tetraphenyl-1,2'-biimidazole. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichloro Phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5, 5'-tetraphenyl-1,2'-biimidazole is preferred, and 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2' -Biimidazole is more preferable.

As the photoinitiator (C), a commercial item may be used. For example, 2-methyl-1-(4-methylthiophenyl))-2-morpholinopropan-1-one (Ilgacure 907, 2-(4 -Methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)-butan-1-one (Ilgacure 379), ethanone-1-[9-ethyl-6-(2-methyl Benzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (Ilgacure OXE02) (above, Chiba Specialty Chemicals Co., Ltd.), and the like.

In the photosensitive resin composition of the present invention, the amount of the component (C) 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% by weight. It is 7% by weight or less.

In addition, the photopolymerization initiator (C) may be used in combination with a curing accelerator (F). Examples of curing accelerators that can be used in combination include amines such as triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethylbenzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid isoamyl ester, and EPA. And hydrogen donors such as 2-mercaptobenzothiazole. When the solid content of the resin composition of the present invention is 100% by weight, the amount of these curing accelerators is usually 0% by weight or more and 5% by weight or less.

As the organic solvent (D), one that dissolves or disperses each component uniformly and does not react with each component is preferably used. As such an organic solvent (D), in addition to the above aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and mixtures thereof such as petroleum ether, white gasoline, solvent naphtha, ester solvents, ether solvents, ketone solvents, 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, amides, and ketones. These may be used alone or in combination of two or more.

Specifically, examples of the organic solvent (D) include alcohols such as benzyl alcohol; Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, and diethylene glycol monobutyl ether acetate; Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether; Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, and dipropylene glycol monobutyl ether acetate; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, and isoamyl lactate; Ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Methyl propionate, 3-ethoxy ethylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl 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; Ketones, such as N-methylpyrrolidone and γ-butyrolactone, etc. are mentioned. These may be used alone or in combination of two or more.

The solid content concentration 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 setting the solid content concentration of the composition in the above range, it is possible to effectively suppress the improvement of coating properties, improvement of film thickness uniformity, and occurrence of uneven coating.

The viscosity at 25°C of the composition is usually 1.0 mPa·s or more and 1,000 mPa·s or less. Preferably, they are 2.0 mPa·s or more and 100 mPa·s or less. By setting the viscosity of the composition in the above range, it is possible to achieve a good balance of viscosity to a degree that can be spontaneously uniform even when uneven coating occurs while maintaining film thickness uniformity.

As the alkali-soluble resin (G) used as needed in the photosensitive resin composition of the present invention, for example, 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, etc. It can be produced by copolymerizing a monomer having a hydroxyl group, a monomer having a sulfonic acid group, other monomers, and the monofunctional (meth)acrylate described above.

Specific examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. , 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, neopentyl glycol mono (meth)acrylate, 3-chloro-2 -Hydroxypropyl (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, etc. are mentioned.

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-norbornene anhydride-2,3-dicarboxylic acid. , 3,4,5,6-tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-ylsuccinic anhydride, and the like.

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, or salts thereof.

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

As a monomer having a phenolic hydroxyl group, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, etc. are mentioned. Moreover, at least one hydrogen atom of these benzene rings is an alkyl group such as a methyl group, an ethyl group, and an n-butyl group; Alkoxy groups such as methoxy group, ethoxy group, and n-butoxy group; Halogen atom; A haloalkyl group in which at least one hydrogen atom of the alkyl group is substituted with a halogen atom; Nitro group; Cyano group; And monomers substituted with an amide group or the like.

As a monomer having a sulfonic acid group, vinylsulfonic acid, styrenesulfonic acid, (meth)allyloxypropanesulfonic acid, 2-hydroxy-3-(meth)allyloxypropanesulfonic acid, (meth)acrylic acid-2-sulfoethyl, (meth)acrylic acid-2-sulfo And propyl, 2-hydroxy-3-(meth)acryloxypropanesulfonic acid, and 2-(meth)acrylamide-2-methylpropanesulfonic acid.

Other monomers include hydrocarbon-based olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth)acrylic esters, (meth)acrylamides, aromatic vinyl compounds, chloroolefins. And conjugated dienes. These compounds may contain a functional group, and examples of the functional group include a carbonyl group and an alkoxy group. In particular, (meth)acrylic acid esters and (meth)acrylamides are preferable since the partition wall formed of the composition is excellent in heat resistance.

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

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

In the polymerization reaction for producing the alkali-soluble resin (G), a molecular weight modifier can be used to adjust the molecular weight. Examples of the molecular weight modifier 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 dimethyl xanthogen disulfide and diisopropyl xanthogen disulfide; Terpinolene, α-methylstyrene dimer, and the like.

The above-described monomer (e) having reactive groups such as 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 phenolic hydroxyl group, a monomer having a sulfonic acid group, etc. As the compound (f) having a functional group capable of bonding with a reactive group and an ethylenic double bond, the following combinations are exemplified.

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

(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 with respect to the monomer (e) having a carboxyl group,

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

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

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

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

As a specific example of the compound which has a hydroxyl group and an ethylenic double bond, the example of the monomer which has the above-mentioned hydroxyl group is mentioned.

As a specific example of the compound which has an epoxy group and an ethylenic double bond, the example of the monomer which has the above-mentioned epoxy group is mentioned.

As a specific example of the compound which has a carboxyl group and an ethylenic double bond, the example of the monomer which has the said carboxyl group is mentioned.

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

In addition, it is preferable to blend a polymerization inhibitor. As the polymerization inhibitor, a publicly known polymerization inhibitor can be used, and specifically, 2,6-di-t-butyl-p-cresol is exemplified.

Further, a catalyst or a neutralizing agent may be added. For example, when a copolymer having a hydroxyl group and a compound having an isocyanate group and an ethylenic double bond are reacted, a tin compound or the like can be used. Examples of the tin compound include dibutyltin diraulate, dibutyltin di (maleic acid monoester), dioctyltin diraulate, dioctyltin di (maleic acid monoester), dibutyltin diacetate, and the like.

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

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

In addition, surfactants, leveling agents, defoaming agents, fillers, ultraviolet absorbers, photostabilizers, antioxidants, polymerization inhibitors, crosslinking agents, adhesion aids, pigments, dyes, etc., are added to the photosensitive resin composition of the present invention as necessary. It is also possible to impart functionality. Leveling agents and antifoaming agents include fluorine compounds, silicone compounds, and acrylic compounds, UV absorbers include benzotriazole compounds, benzophenone compounds, and triazine compounds, and photostabilizers include hinderedamine compounds, benzoate compounds, and the like. Examples of the inhibitor include a phenolic compound, methoquinone, methylhydroquinone, and hydroquinone as a polymerization inhibitor, and the polyisocyanates and melamine compounds described above as a crosslinking agent.

Other resins that are not reactive to active energy rays (so-called inate polymers) include, for example, 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 may also be used. These are preferably used in the range of up to 40 parts by weight in the resin composition.

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

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

Spacers for display elements formed of the composition are preferably included in the present invention. The method of forming the spacer for the display element,

(1) the step of forming a coating film by applying the composition on a substrate,

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

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

(4) The process of heating the developed coating film

A method of forming a photo spacer and/or a color filter protective film by a photolithography method using the active energy ray-curable resin composition of the present invention will be described briefly. The active energy ray-curable resin composition of the present invention is uniformly applied onto a substrate by a known method such as roll coat, spin coat, spray coat, and slit coat, and is 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, a gravure coater, and a coma coater. Here, an example of forming on the transparent common electrode further formed on the colored layer is described.

If necessary, heat to dry (pre-baking). The drying temperature is preferably 50°C or higher, more preferably 70°C or higher, and preferably less than 150°C, and more preferably 120°C or lower. The drying time is preferably 30 seconds or more, more preferably 1 minute or more, further preferably 20 minutes or less, and more preferably 10 minutes or less.

Subsequently, the photosensitive resin composition layer is exposed with active energy rays through a predetermined photomask. In the case of the photosensitive resin composition of the present invention, a mask opening having a diameter of about 5 to 10 µm (area of about ^{20 to 100 µm 2} ) may have good precision, that is, it can be formed in a range of 6 to ^{12 µm (area of 30 to 120 µm 2)} have.

There is no restriction|limiting in particular as an active energy ray used for exposure as long as it can harden the photosensitive resin composition of this invention. The active energy ray-curable resin composition of the present invention is easily cured with an active energy ray. Specific examples of active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X rays, gamma rays, and laser rays, and particle rays such as alpha rays, beta rays, and electron rays. Considering the preferred use of the present invention, among these, ultraviolet rays, laser rays, visible rays, or electron rays are preferable. Although it does not specifically limit as an exposure amount, Preferably it is 20-1,000 mJ/cm<2>.

Subsequently, the unexposed portion is removed with a developer, and development is performed. Here, the developer used for development may use an organic solvent, but it is preferable to use an alkaline aqueous solution. Examples of the aqueous alkali solution that can be used as a developer include aqueous solutions of inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydrogen carbonate; And aqueous solutions of organic bases such as hydroxytetramethylammonium and hydroxytetraethylammonium. These may be used alone or in combination of two or more, and may be used by adding surfactants such as anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants, and water-soluble organic solvents such as methanol and ethanol. The concentration of alkali in the alkali aqueous solution is preferably 0.1 to 5% by weight from the viewpoint of obtaining appropriate developability. As the developing method, there are a dip method, a shower method, a puddle method, and a vibration immersion method, but a shower method is preferable. The temperature of the developer is preferably used at 25 to 40°C. The development time is suitably determined depending on the film thickness and the solubility of the resist.

In order to further ensure curing, heating (baking) may be performed as necessary. In the case of baking, the baking temperature is preferably 120 to 250°C. The bake time varies depending on the type of heating device, but may be, for example, 5 minutes to 30 minutes when the heating step is performed on a hot plate, and 30 minutes to 90 minutes when the heating step is performed in an oven. It is also possible to use a step bake method or the like in which two or more heating steps are performed.

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

The spacers formed in this forming method are spacers that have high flatness without uneven coating, are flexible, and have small plastic deformation. It can be suitably used for display elements, such as a liquid crystal display element and an organic EL display element.

As the color filter protective film, 0.5 µm to 100 µm is preferable, and 1 µm to 10 µm is more preferable.

Example

Hereinafter, the present invention will be described in more detail by examples, but the present invention is not limited by these examples. In addition, in Examples, unless otherwise specified, "part" represents parts by weight, and "%" represents weight%.

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

1) Epoxy equivalent: It was measured by the method according to JISK 7236:2001.

2) Softening point: It was 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)]

As the epoxy resin (a), GTR-1800 (manufactured by Nippon Kayaku; epoxy equivalent 170 g/eq) was used in Table 1, and acrylic acid (abbreviated as AA, Mw = 72) as compound (b) was used in Table 1, compound As (c), dimethylolpropionic acid (abbreviation DMPA, Mw=134) was added in the amount described in Table 1. 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content became 80% by weight of the reaction solution, and reacted at 100° C. for 24 hours to obtain a reactive epoxy carboxylate compound (E) solution. . Solid content acid value (AV:mgKOH/g) 5 or less was used as the reaction end point, and the next reaction proceeded. The acid value was measured with a reaction solution and converted into an acid value as a solid content.

Then, tetrahydrophthalic anhydride (abbreviated THPA) as a polybasic acid anhydride (d) was added to the reactive epoxy carboxylate compound (E) solution in a ratio of 65 parts by weight based on the amount described in Table 1 and 100 parts by weight of the solid content as a solvent. Ether monoacetate was added, and after heating to 100°C, an acid addition reaction was carried out 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, 1-2

[Preparation of a comparative reactive polycarboxylic acid compound]

Cresol novolak-type epoxy resin EOCN-103S (manufactured by Nippon Kayaku, epoxy equivalent 200 g/eq) in Table 1, acrylic acid as compound (b) in Table 1, dimethylolpropionic acid as compound (c) ( The abbreviation DMPA, Mw = 134) was added in the amount described in Table 1. 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content became 80% by weight of the reaction solution, and reacted at 100° C. for 24 hours to obtain a carboxylate compound solution. Solid content acid value (AV:mgKOH/g) 5 mgKOH/g or less was used as the reaction end point, and the reaction proceeded to the next reaction.

Subsequently, propylene glycol monomethyl ether monoacetate was added to the reactive epoxy carboxylate compound solution so that tetrahydro phthalic anhydride (abbreviated THPA) as a polybasic acid anhydride was 65 parts by weight based on the amount described in Table 1 and 100 parts by weight of the solid content as a solvent. Then, after heating at 100°C, an acid addition reaction was carried out 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 comparative reactive caprolactone-modified polycarboxylic acid compound]

Cresol novolak type epoxy resin EOCN-103S (manufactured by Nippon Kayaku, epoxy equivalent 200g/eq) 200g, acrylic acid 58g, dimethylolpropionic acid 40g, triphenylphosphine 3g as catalyst, propylene glycol monomethylethermono as solvent Acetate was added so that the solid content was 80% by weight of the reaction solution, and reacted at 100°C for 24 hours. Further, 68 g of ε-caprolactone was added and reacted for 8 hours. Then, 91 g of tetrahydro phthalic anhydride (abbreviated 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 solid content as a solvent, and heated to 100° C., followed by acid addition reaction. To obtain a comparative reactive caprolactone-modified polycarboxylic acid compound solution. The solid acid value (AV:mgKOH/g) was 70mgKOH/g.

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

In addition, 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) (Ilgacure OXE02, manufactured by BASF Corp. )

<Organic solvent (D)>

PGMEA: Propylene glycol monomethyl ether acetate DEGDM: Diethylene glycol dimethyl ether

<Other optional ingredients>

<Surfactant (H)>

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

<Preparation of the composition>

Example 2-1

In a solution containing an amount corresponding to 100 parts by weight (solid content) of the reactant obtained in Example 1-1 as a reactive polycarboxylic acid compound (A), 100 parts by weight of (B-1) as a reactive compound (B), and a photopolymerization initiator As (C), (C-1) 10 parts by weight, PGMEA and DEGDM as organic solvents were added to a desired solid content concentration, and (H-1) 0.3 parts by weight as surfactant (H) were mixed, and the pore diameter was 0.2 μm. The composition (S-1) was prepared by filtration with a membrane filter of. In addition, the numerical value of the organic solvent in Table 2 is the mass ratio of PGMEA and DEGDM.

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

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 kind and compounding amount of each component were as described in Table 2. In addition, the numerical value of the organic solvent in Table 2 is the mass ratio of PGMEA and DEGDM.

<Evaluation>

The following evaluation was performed on the compositions of Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3, and spacers formed from the coating films. The evaluation result is combined with Table 3 and shown.

(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 standardized on an aluminum dish, about 1 g of diethylene glycol dimethyl ether was added, and then dried on a hot plate at 175°C for 60 minutes, and the solid content concentration (mass%) in the composition was determined from the weight before and after drying. .

(Appearance of the coating film)

The composition is coated on a 100×100mm chromium-forming glass using a slit die coater (manufactured by Techno Machine Co., Ltd., Rica Die), dried under reduced pressure to 0.5 Torr, and prebaked on a hot plate at 100°C for 2 minutes to coat the film. Was formed and further exposed at an exposure dose 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 this coating film was observed with the naked eye under a sodium lamp. At this time, uneven streaks in the entire coating film (one or more straight spots occurring in the application direction or in a direction crossing it), mist spots (cloud-shaped spots), pin marks spots (points occurring on the substrate support pins) The appearance of irregularities in shape) was investigated. The case where all of these unevenness was hardly visible was judged as "(circle)", the case where any one was slightly visible was judged as "△ (slightly poor)", and the case where it was clearly visible was judged as "x (defective)".

(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 (Surcom, manufactured by Tokyo Seimits Co., Ltd.). The film thickness uniformity was calculated from the following equation by measuring the film thickness at nine measurement points. For the 9 measurement points, if the minor axis direction of the substrate is X and the major axis direction is Y, (X[mm], Y[mm]) is (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, it can be determined that the film thickness uniformity is 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 value of the film thickness at 9 measurement points, FT(X, Y)min is the minimum value of the film thickness at 9 measurement points, and FT(X, Y )avg. is the average value among the film thicknesses at nine measurement points.

(High-speed coating property)

Apply on a 100 mm × 100 mm alkali-free glass substrate using a slit coater, discharge the coating liquid from the nozzle so that the distance between the base and the nozzle is 150 μm and the film thickness after exposure is 2.5 μm as the coating conditions, and the moving speed of the nozzle is adjusted. It was varied in the range of 120 mm/sec. to 200 mm/sec., and the maximum speed at which streak-like unevenness due to liquid dropping did not occur was determined. At this time, if the streak-like unevenness does not occur even at a speed of 180 mm/sec. or more, it can be determined that it is possible to cope with high-speed application.

(Radiation sensitivity)

The composition was coated on a 100 mm×100 mm ITO sputtered glass substrate by a spin coating method, and then prebaked on a hot plate at 90° C. for 3 minutes to form a coating film having a thickness of 3.5 μm. Subsequently, exposure was performed using an ultraviolet light exposure apparatus (Oak Seisakusho Co., Ltd., Model HMW-680GW) through a photomask in which a circular pattern having a diameter of 12 µm was formed as an opening in the obtained coating film. Thereafter, development was performed at 25°C for 60 seconds with a 0.05% by mass potassium hydroxide aqueous solution, followed by washing with pure water for 1 minute, and post-baking for 30 minutes in an oven at 230°C 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 the film after post-baking × 100/film thickness after exposure (before post-baking)) was 90% or more was investigated, and this value was used as the sensitivity. When this value is 55mJ/cm2 or less, it can be said that the sensitivity is good.

(Development residue)

Further, the surface on the substrate was visually observed, and the presence or absence of a residue was confirmed. The evaluation criteria are as follows.

○… No residue.

△... Some residue.

×… Have a lot of residue

(Compression performance)

A spacer made of a columnar pattern was formed on the substrate by operating in the same manner as in the evaluation of radiation sensitivity except for setting the exposure amount as the 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 part after post-baking might become 20 micrometers. For this spacer, a micro-compression tester (Fischer Scope H100C, manufactured by Fisher Instruments Co., Ltd.) was used, and a flat indenter of 50 µm in width and length was used, and a compression test was performed with a load of 50 mN, and the change in the amount of compression displacement against the load. Was measured, and the recovery rate (%) was calculated from the displacement amount at the time of 50 mN load and the displacement amount at the time of removing the 50 mN load. In this case, when the recovery rate is 70% or more and the displacement at the time of 50 mN load is 0.15 µm or more, it can be said to be a spacer having compression performance having both high recovery rate and flexibility.

(Total light transmittance)

By applying a spin coater on a 50 mm × 50 mm alkali-free glass substrate, drying under reduced pressure to 0.5 Torr, prebaking on a hot plate at 100° C. for 2 minutes to form a coating film, and further exposing at an exposure amount of 200 mJ/cm 2. , A film having a film thickness of 4 µm was formed. The evaluation substrate having the cured coating film was measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., TC-H3DPK).

(Heat resistance and transparency)

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

As is clear from the above results, the active energy ray-curable composition containing the reactive polycarboxylic acid compound (A) in the present invention of Examples 2-1 to 2-3 was obtained from Comparative Examples 2-1 to 2-3. Compared with the composition, it became clear that developability and hardenability were good, and that heat-transparency, flatness, flexibility, and toughness were excellent. In addition, it was found that Example 2-1 and Example 2-2 in which DMPA (c) was used in the preparation of the reactive polycarboxylic acid (A) had better compression performance compared to Example 2-3.

Although the present invention has been described in detail with reference to specific embodiments, it is clear 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.

In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2013-246536) for which it applied on November 28, 2013, The whole is used by reference. Also, all references cited herein are incorporated as a whole.

(Industrial availability)

The active energy ray-curable composition of the present invention has good developability, curability, and high-speed coating property, and can form a spacer for a display device and a color filter protective film excellent in heat transparency, flatness, flexibility, and toughness. Therefore, the composition is preferable as a material for forming a liquid crystal display element, a spacer for display elements such as organic EL, and a color filter protective film.

Claims (6)

delete delete Reactive polycarboxylic acid compounds (A), reactive compounds other than reactive polycarboxylic acid compounds (A) (B), photopolymerization initiators (C), and color filters for display elements containing organic solvents (D) As an active energy ray-curable resin composition for a protective film,
The reactive polycarboxylic acid compound (A) is an epoxy resin (a) represented by the general formula (1) and a compound (b) having at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in one molecule, and one molecule. The active energy ray-curable resin, which is a reactive polycarboxylic acid compound (A) obtained by further reacting a polybasic acid anhydride (d) with a reactant (E) of a compound (c) having at least two hydroxyl groups and at least one carboxyl group in Composition.

[In the formula, R _{1 to R 8} may be the same or different, respectively, and represent a hydrogen atom, a C1 to C4 alkyl group, or a halogen atom. G represents a glycidyl group.] The method of claim 3,
An active energy ray-curable resin composition for a spacer for a display element or a color filter protective film, wherein _{R 1 to R 8 in} the general formula (1) are hydrogen atoms. A display element spacer formed of the active energy ray-curable resin composition according to claim 3 or 4. A color filter protective film formed of the active energy ray-curable resin composition according to claim 3 or 4.