WO2007135909A1

WO2007135909A1 - Thermosetting resin composition and cured product thereof

Info

Publication number: WO2007135909A1
Application number: PCT/JP2007/060024
Authority: WO
Inventors: Naofusa Miyagawa; Yoshihiro Kawata; Chie Umeyama; Ryuji Uehara; Masato Ando
Original assignee: Nippon Kayaku Kabushiki Kaisha
Priority date: 2006-05-18
Filing date: 2007-05-16
Publication date: 2007-11-29
Also published as: TW200801063A; JP5524480B2; JPWO2007135909A1

Abstract

Disclosed is a thermosetting resin composition containing (A) a homocondensate of a compound represented by the formula (1) below and/or a co-condensate of a compound represented by the formula (1) below and a compound represented by the formula (2) below, (B) a compound having two or more carboxyl groups, and (C) a solvent. A cured product of a coating film obtained from the composition is excellent in transparency and planarization ability, while having especially high heat resistance and yellowing resistance. This cured coating film is suitable as a protective film for optical devices, in particular as a protective film for a functional film such as a colored resin film in a color filter or the like. (1) (2) (In the formulae, X represents a C2-C5 alkylene group, R1 and R2 independently represent a C1-C4 alkyl group, and Z represents a methyl group of a phenyl group.)

Description

Specification

Thermosetting resin composition and cured product thereof

Technical field

The present invention relates to a thermosetting resin composition suitable for forming a protective film and a cured product thereof.

More specifically, the present invention relates to an epoxy thermosetting resin composition suitable as a protective film provided on a functional film (for example, a colored resin film such as a color filter) formed on the surface of a glass substrate or the like, and a cured product thereof. .

Background art

[0002] A color filter in a liquid crystal display element is immersed in a solvent, an acid, an alkaline solution, or the like during the manufacturing process, and the element surface is localized by sputtering when forming an ITO (Indium Tin Oxide) layer. Exposed to high temperatures. In order to prevent deterioration and damage of the device from such severe conditions, it is generally performed to protect the surface of the device with a protective film having resistance to these treatments. In addition, when the liquid crystal display element is required to have high performance such as a high viewing angle and a high-speed response, the flatness of the color filter is important. Therefore, it is necessary to provide a protective film with high flatness. Needed. Further, in such a liquid crystal display element, after the protective film is formed, ultraviolet rays (usually accompanied by generation of ozone) are used to oxidize and remove impurities such as organic substances on the surface, followed by further high-temperature treatment. May be. In such a high temperature treatment, there is often a phenomenon that the protective film is yellowed (discolored), and thus the protective film is required to have resistance against such yellowing. Furthermore, such a protective film has a low degree of liquid crystal contamination, excellent smoothness, adhesion to the surface of the functional film or base material protected by the protective film, and a grease on the protective film. When forming a layer, etc., the adhesion to the formed layer is good, the visible light transmittance is high so as not to reduce the brightness of the liquid crystal display, the protective film itself is colored, whitened, yellowed, etc. It is required to have no change with time, toughness that can withstand impact, strain, etc.

Conventionally, acrylic resin, melamine resin, polyimide resin, and the like have been proposed as materials for the protective film of the functional film. However, such a material satisfies all of the above required properties in a well-balanced manner. The present condition is that the material has not yet been found. For example, acrylic resin is visible light Although it has excellent transmittance, the heat resistance is insufficient, and there is a problem that wrinkles and cracks are generated on the film surface when forming an ITO film or the like. Melamine resin has good heat resistance but has extremely poor adhesion to glass substrates, and it is noisy on substrates and filters (a phenomenon that causes indentations and holes of about lmm on the protective film due to poor adhesion) There is a problem that it is easy to generate. Furthermore, while polyimide resin has high heat resistance, it is insufficient in transparency and lacks storage stability of resin, and organic solvents that have poor solubility are limited. Has problems such as dissolving the color filter (colored resin film) itself. Further, in Patent Document 1, a protective film using a polyhydric phenol type hardener having an epoxy resin and a terpene skeleton has been studied, but they have insufficient adhesion, or With the recent increase in processing temperature during ITO film formation, there is a problem when cracks occur during film formation or yellowing due to heat occurs. In addition, there is a problem that the protective film is yellowed even by the high temperature treatment performed after the ultraviolet irradiation accompanied by the generation of ozone. Attempts have also been made to use acid anhydrides as hardeners to resolve such yellowing. However, there are problems in storage stability due to its reactivity and hygroscopicity, and there are still other problems such as the limited organic solvent to be dissolved and the safety of the solvent. Yes.

[0004] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2004-315657

Disclosure of the invention

Problems to be solved by the invention

[0005] The present invention is intended to improve the above-mentioned drawbacks of the prior art and to provide a resin composition suitable for use as a protective film for a functional film, satisfying adhesion, visible light permeability, and the like. In addition, it can form a protective film with a high leveling ability and smoothness on the surface of the base material, and is suitable as a protective film for functional films, especially color filter colored resin films for liquid crystal displays. It is intended to provide a rosin composition having a protective film forming ability

Means for solving the problem

[0006] As a result of intensive studies to solve the above-mentioned problems, the present inventors include a condensate of a key compound having an epoxy group having a specific skeleton, a polycarboxylic acid, and a solvent. It has been found that a thermosetting resin composition having the above-mentioned problems can solve the above-mentioned problems, and the present invention has been completed.

That is, the present invention provides:

(1) (A) Self-condensate of a key compound having an epoxy group represented by the following formula (1), and a key compound having an epoxy group represented by Z or the following formula (1) and the following formula A co-condensate with an alkoxy-key compound represented by (2),

[Wherein, X represents a C2 to C5 alkylene group, R and R each independently represent Cl to

1 2

The alkyl group of C4, Z represents a methyl group or a phenyl group, respectively. ), (B) one or two or more selected from the group consisting of aliphatic, aromatic and alicyclic compounds having two or more carboxyl groups, and (C) a thermosetting A greave composition, (2) The aliphatic, aromatic or alicyclic compound having two or more carboxyl groups is a compound represented by the following formulas (3) to (8): Thermosetting resin composition,

[0011] (3) A functional film protective film agent comprising a thermosetting resin composition according to (1) or (2) above,

(4) The functional film protective film agent according to the above (3), wherein the functional film is a colored resin film,

(5) A cured resin film obtained by curing the protective film agent for functional film according to (3) or (4) above, (6) a color filter comprising a colored resin film having the resin cured film according to (5) above,

(7) A liquid crystal display device comprising the color filter according to (6) above,

(8) The thermosetting resin composition according to the above (1), wherein the alicyclic compound having two or more carboxyl groups in the component (B) is a compound represented by the following formula (9).

(9) The thermosetting according to the above (2), wherein the component (B) is at least one of the group forces that are also compound forces of the formula (3), the formula (5), the formula (7), and the formula (8). Natural rosin composition,

(10) Component (B) is an aliphatic compound substituted with 2 to 5 carboxyl groups and the aliphatic group has 2 to 8 carbon atoms, substituted with 2 to 4 carboxyl groups, and aromatic An aromatic compound having 6 to 14 carbon atoms in the group, and an alicyclic group substituted with 2 to 4 carboxyl groups or carboxymethyl groups, and the alicyclic group having 6 to 10 carbon atoms. The thermosetting resin composition according to the above (1), which is at least one selected from the group force as compound strength,

(11) The above component (B) is a C2 to C8 aliphatic compound substituted with 2 to 4 carboxyl groups, or a C6 alicyclic compound substituted with 2 to 4 carboxyl groups The thermosetting resin composition according to (1),

(12) The thermosetting resin composition according to (10) or (11) above, wherein the aliphatic compound of component (B) is 1, 2, 3, 4 butanetetracarboxylic acid,

(13) The component (A) is a cocondensate of a key compound having an epoxy group of the formula (1) and an alkoxy key compound represented by the formula (2), and Z in the formula (2) The thermosetting resin composition according to any one of (1), (2), (8) to (12),

(14) Co-condensate is 2— (3, 4 epoxycyclohexyl) etheryl (C1-C4) alcohol The thermosetting resin composition according to the above (13), which is a cocondensate of xylsilane and ferrtri (C1-C4) alkoxysilane,

(15) An optical device protective film agent comprising the thermosetting resin composition according to any one of (1), (2), and (8) to (14),

About.

The invention's effect

The epoxy thermosetting resin composition of the present invention, when used as a protective film, is excellent in transparency and flatness, has particularly high heat resistance, and has high stability at high temperatures. It has an appropriate hardness and is advantageous for protecting colored resin films. In particular, by providing the protective film of the present invention on a color filter used in a liquid crystal display device, the reliability of the color filter can be improved.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

First, component (A) used in the present invention, that is, a self-condensate of a key compound having an epoxy group represented by the following formula (1) (hereinafter also simply referred to as an epoxy-containing key compound), and

A co-condensate of a silicon compound having an epoxy group represented by Z or formula (1) and an alkoxy compound represented by the following formula (2) will be described.

[0014]

RiO- Z

(1) (2)

[In the formula, X represents a C2 to C5 alkylene group, R and R each independently represent Cl to

1 2

An alkyl group of C4, Z represents a methyl group or a full group, respectively. )

Specific examples of the C2-C5 alkylene group in X include ethylene, propylene, butylene, and pentylene, with ethylene being preferred. A plurality of R and R may be the same or different. Usually the same is preferred. R and R

Specific examples of the C1-C4 alkyl group in 2 1 2 include methyl, ethyl, propyl, or butyl. A til is mentioned, Preferably it is a methyl or an ethyl.

Specific examples of the epoxy-containing silicon compound of the formula (1) include 2- (3,4 epoxy cyclohexyl) ethyl trimethoxysilane, 2- (3,4 epoxy cyclohexyl) ethyl triethoxysilane, and the like. Can be mentioned. Of these, 2- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane is preferred.

[0017] Specific examples of the alkoxycarbene compound of formula (2) include phenyltrimethoxysilane, methyltrimethoxysilane, phenyltriethoxysilane, and methyltriethoxysilane. Of these, preference is given to phenoltrimethoxysilane and methyltrimethoxysilane, with the former being more preferred.

The key compounds represented by the above formulas (1) and (2) are easily available from the market.

[0018] The condensate in the component (A) used in the present invention may be a self-condensate of the epoxy-containing key compound of the above formula (1) and the epoxy-containing key compound of the formula (1) It may be a co-condensate with the alkoxykeene compound of the above formula (2) or a mixture of both. In the present invention, the above-mentioned cocondensates are usually preferred. In the co-condensate, R and R may be the same or different, and usually the same thing is preferable.

1 2

R and R are all preferably methyl or ethyl, more preferably all are methyl.

1 2

Most preferred. In this cocondensate, X is preferably ethylene, and z is preferably phenol.

The ratio (molar ratio) of the partial structures derived from the epoxy-containing key compound of formula (1) and the alkoxy-key compound of formula (2) above in this cocondensate is usually the epoxy-containing key of formula (1). The partial structure derived from the elemental compound is at least 20%, more preferably at least 25%, and the upper limit may be up to 100% with respect to the number of moles of all the key compounds in the entire cocondensate. The following is preferably 75% or less, and the remainder is a partial structure derived from the alkoxycaine compound of the above formula (2), and may be zero, but a range of usually 20% or more and less than 80% is preferable. More preferably, it is about 25% to 75%.

In addition, the condensate in component (A) includes a self-condensate of an epoxy-containing key compound of formula (1), an epoxy-containing key compound of formula (1), and an alkoxy key compound of formula (2). A co-condensate can be used in combination.

[0019] The self-condensate or co-condensate can be easily obtained by the method disclosed in WO2004 / 072150 A1 or the like or a method analogous thereto. For example, it can be obtained by heating and hydrolyzing and condensing the raw material compound or a mixture of the raw material compounds in the presence of alkali and water. The amount of water used in this condensation reaction is usually 0.1 to 1.5 mol, preferably 0.2 to 1.2 mol, per 1 mol of the alkoxy group in the entire reaction system. Any alkali can be used as the alkali used in the condensation as long as it is a basic compound in water. Specific examples of alkalis that can be used include sodium hydroxide, potassium hydroxide, alkali metal hydroxides such as lithium hydroxide or cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate. Or inorganic bases such as alkali metal carbonates such as potassium hydrogen carbonate; ammonia; organic bases such as triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine or tetramethylammonium hydroxide Can be used. Among these, the use of an inorganic base or ammonia is preferable because it can be easily removed from the reaction product. The amount of these alkalis added is usually from 0.001 to 7.5% by weight, preferably from 0.01 to 5% by weight, based on the total weight of the raw material silicon compound in the reaction system.

[0020] The condensation reaction can be carried out without a solvent, but is preferably carried out in a solvent. As the solvent, any solvent that can dissolve the raw material silicon compound can be used without any particular limitation. Specific examples of the solvent include aprotic polar solvents such as dimethylformamide, dimethylacetamide, tetrahydrofuran, methylethylketone and methylisobutylketone, and aromatic hydrocarbons such as toluene and xylene. Of these, aprotic polar solvents are preferred. The amount of the solvent used is not particularly limited, but it is usually preferably 50 to 900 parts by weight, preferably about 150 to 500 parts by weight with respect to 100 parts by weight of the total weight of the raw material silicon compound.

[0021] The reaction temperature in the condensation reaction is usually 20 to 160 ° C, preferably 40 to 140 ° C, although it depends on the type and amount of alkali. The reaction time is usually 1 to 12 hours. The Mw (weight average molecular weight) of the reaction product (condensate) can be measured by GPC (gel permeation chromatography). When the reaction is complete, stop heating and remove the solvent and water. The organic layer is separated and the solvent is removed under reduced pressure to obtain the desired condensate. If necessary, the obtained condensate can be purified by gel filtration or the like.

[0022] The condensate (A) obtained in the above manner is considered to be a polymer compound having a repeating unit represented by the following formula (10). . The molecular weight of the condensate used in the present invention is not particularly limited as long as the object of the present invention can be achieved, but is usually about 500 to 10,000, preferably about 1,000 to 5,000, more preferably <1,000 to 3,000. Degree.

[0023]

(Wherein X and Z have the same meaning as in formula (1) or formula (2).)

[0025] In the present invention, the selected group force of aliphatic, aromatic or alicyclic compound having two or more carboxyl groups as component (B) is one or two or more selected compounds. It works as a curing agent and reacts with the condensate of the component (A) to form a transparent cured film having excellent heat resistance. Preferred examples of the component (B) include an aliphatic compound having 2 to 8 carbon atoms substituted with 2 to 5 carboxyl groups, a substituent with 2 to 4 carboxyl groups, and an aromatic group. Group power consisting of an aromatic compound having 6 to 14 carbon atoms and an alicyclic compound substituted with 2 to 4 carboxyl groups or carboxymethyl groups and having an alicyclic group having 6 to: LO Mention may be made of at least one compound selected. Among these, a linear aliphatic group in which 2 to 4, preferably 3 to 4 carboxyl groups are substituted and the aliphatic group has 2 to 4 carbon atoms, preferably 3 to 4 carbon atoms, is more preferable. Compound, or C6 alicyclic compound (more preferably cyclohexane) substituted with 2 to 4, preferably 2 to 3 carboxyl groups, or substituted with 2 carboxyl groups or carboxymethyl groups Can be mentioned.

Specific examples of the component (B) include the following. (a) aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid;

(b) phthalic acid, isophthalic acid, terephthalic acid, 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6- Naphthalenedicarboxylic acid, 9, 10-anthracene dicarboxylic acid, 4, 4, monobenzophenone dicanolevonic acid, 2, 2'-bipheninoresitivity norebonic acid, 3, 3'-bipheninoresiency rubonic acid, 4, 4 ' —Aromatic dicarboxylic acids such as biphenyl dicarboxylic acid, 3, 3, -biphenyl ether dicarboxylic acid, 4, 4, -biphenyl ether dicarboxylic acid, 4, 4, -binaphthyl dicarboxylic acid;

(c) cycloaliphatic dicarboxylic acids such as hexahydrophthalic acid, 1,3-adamantane diacetic acid, 1,3-adamantane dicarboxylic acid, 1,3-cyclohexanedicarboxylic acid;

(d) tetrahydrophthalic acid, 2,3-norbornene dicarboxylic acid;

(e) aromatic tricarboxylic acids such as hemmellitic acid, trimellitic acid, trimesic acid, 1,2,4-naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid;

(D1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, alicyclic tricarboxylic acid such as 1,2,3-cyclohexanetricarboxylic acid;

(g) an aliphatic tricarboxylic acid such as 1,2,3-propanetricarboxylic acid;

(h) isocyanuric tricarboxylic acids such as tris (2-carboxyethyl) isocyanurate, tris (3-carboxypropyl) socynanurate;

(0 melophanoic acid, plate acid, pyromellitic acid, 3, 3, 4, 4, monobenzophenone tetracarboxylic acid, 2, 2, 3, 3, monobenzophenone tetracarboxylic acid, 2, 3 , 3 ', 4, monobenzophenone tetracarboxylic acid, 3, 3' 4, 4, -biphenyltetracarboxylic acid, 2, 2 ', 3, 3, biphenyl tetracarboxylic acid, 2, 3, 3 ', 4, -biphenyltetracarboxylic acid, 4,4, monooxydiphthalic acid, 3,3' 4,4, -diphenylmethanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1, 2, 5, 6-naphthalene tetracarboxylic acid, 2, 3, 6, 7-naphthalene tetracarboxylic acid, aromatic tetracarboxylic acid such as anthracene tetracarboxylic acid; (j) 1, 2, 4, 6— Cycloaliphatic tetracarboxylic acids such as cyclohexanetetracarboxylic acid; (k) 1,2,3,4,5,6-cyclohexanehexacarboxylic acid and other alicyclic Kisakarubon acid;

(1) 1, 2, 3 aliphatic tricarboxylic acid such as propanetricarboxylic acid;

(m) Aliphatic tetracarboxylic acids such as 1, 2, 3, 4 butanetetracarboxylic acid;

One or two or more of these compounds can be appropriately selected and used.

Among these, hexahydrophthalic acid (3) represented by the following formula, because it is particularly excellent in transparency and heat resistance and is easily dissolved in the solvent used in the present invention described later, Phthalic acid (4), Tetrahydrophthalic acid (5), 1,3 Adamantanediacetic acid (6), 1, 2, 4 Cyclohexanetricarboxylic acid (7), 1, 2, 3, 4 Butanetetracarboxylic acid ( Preferred examples include 8) and 1,3 cyclohexanedicarboxylic acid (9). Most preferred are hexahydrophthalic acid, tetrahydrophthalic acid, 1,3 cyclohexanedicarboxylic acid and 1,2,3,4-butanetetracarboxylic acid.

[0029] Next, the solvent (C) used in the present invention will be described. As the solvent used in the thermosetting resin composition of the present invention, those having a high solubility in the component (A) and the component (B) and showing no reactivity with these components. If! / Any of them can be used without limitation. Specific examples of the solvent that can be used include alcohols such as methanol, ethanol, propanol, and butanol, preferably lower alcohols having 1 to 4 carbon atoms; ethylene glycol monomethyl ether, ethylene glycol monoethylenoate, ethylene glycol monobutyrate. Glycol ethers such as Noleyatenole, propylene glycolanol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, preferably a lower ether having 1 to 4 carbon atoms of alkylene glycol having 1 to 4 carbon atoms; Ethylene glycol monoethyl ether acetate, ethylene glycol monobutenoate ethere acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-me Alkylene glycol ether carboxylates such as toxibutyl acetate, 3-methyl-3-methoxybutyl acetate and ethylethoxypropiolate, preferably lower ethers of 1 to 4 carbon atoms of alkylene glycols. Acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone and 4-hydroxy-4-methyl-2 pentanone; methyl acetate, ethyl acetate, plutol acetate , Butyl acetate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxyethyl acetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, butyl lactate, 3-hydroxypropion Methyl acid, 3-hydroxy Ethyl cypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3 propyl methylbutanoate, methoxyethyl ethyl acetate, propyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxy acetate, ethoxy Butyl acetate, Methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, Butyl 2-methoxypropionate, Methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, 2-Ethoxypropionate Propionate, butyl 2-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3-ethoxypropionate Le, 3-ethoxypropionate Echiru, 3 Esters such as propyl ethoxypropionate and butyl 3-ethoxypropionate, preferably a hydroxy group, and optionally substituted with a lower alkyl group having 1 to 4 carbon atoms. 4 alkyl esters; cyclic ethers such as tetrahydrofuran; and the like.

[0030] Among these, in view of solubility in the components (A) and (B), concentration over time due to volatilization, toxicity to the human body, and the like, propylene glycol monomethyl ether acetate, propylene glycol monoethyl C1-C4 lower ether acetate of C2-C3 alkylene glycol such as ether acetate and ethylene glycol monobutyl ether acetate; propylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol or the above-mentioned esters Is a good example. More preferable examples include lower ether acetates having 1 to 4 carbon atoms of alkylene glycols having 2 to 3 carbon atoms.

[0031] The thermosetting resin composition of the present invention preferably has at least one of the above (A) component, the above (B) component, and the (C) component. A thermosetting resin composition using a thermosetting resin, and more preferable one is either two or more preferably three, or a combination of things or more preferably a combination of things. It is a composition.

For example, the component (A) is a cocondensate (more preferably, Z in the formula (2) is a full group) of an epoxy-containing silicon compound of the formula (1) and an alkoxy cage compound of the formula (2). An aliphatic compound in which component (B) is substituted with 2 to 5 (more preferably 3 to 4) carboxyl groups and the aliphatic group has 2 to 8 (more preferably 3 to 4) carbon atoms, An aromatic compound substituted with 2 to 4 carboxyl groups and an aromatic group having 6 to 14 carbon atoms, and substituted with 2 to 4 carboxyl groups, and the alicyclic group has a carbon number of Group power is an alicyclic compound having 6 to 10 and is at least one selected, and the solvent of component (C) is a C 1-4 alkylene glycol having 1 to 4 carbon atoms, lower ether having 1 to 4 carbon atoms, C 1-3 lower ether acetates and esters of alkylene glycols of 2 to 3, more preferably hydroxy groups or carbon Substituted with C1-4 lower alkyl groups, it also, the union is at least one selected the group force consisting also alkyl esters force having a carbon number of 1 to 4 fatty acid having 2 to 4 carbon atoms You can list the cases. In this combination, any one of the components is converted into a more preferable component, for example, 2- (3,4 epoxy cyclohexyl) etheryltri (C1 to C4) alkoxysilane and phenol (C1 to C4) It is more preferable to use a cocondensate with alkoxysilane. Similarly, in the above combination, as component (B), propane or butane substituted with 3 to 4 carboxyl groups, or C6 alicyclic compound substituted with 2 to 4 carboxyl groups It is better if you use. Further, it is more preferable to use a C6 alicyclic compound substituted with 1, 2, 3, 4 butanetetracarboxylic acid or 2 to 4 carboxyl groups as the component (B). The C6 alicyclic compound means a 6-membered alicyclic compound consisting of 6 carbons.

[0032] In the thermosetting resin composition of the present invention, the condensate of component (A), component (B) (carboxylic acid compound having two or more carboxyl groups), and component (C) of the solvent The content ratio of (A) component is 5 to 50% by weight, (B) component 0.5 to 30% by weight, and (C) component balance (preferably 30 to 90% by weight), preferably (A ) Component 10-25% by weight, optionally 10-20% by weight, (B) Component 1-15% by weight, more preferably 1-10% by weight, (C) Component remainder (preferably 70-80% by weight) %). In the present invention, the ratio of the component (B) to the component (A) is about 4 to 40 parts by weight, more preferably about 5 to 30 parts by weight with respect to 100 parts by weight of the component (A). Is preferred.

[0033] The thermosetting resin composition of the present invention, if necessary, within the range where the physical properties such as transparency, heat resistance, chemical resistance, flatness and yellowing resistance are not substantially lowered. An epoxy resin other than the component (A) can be added. Usually, it does not need to contain epoxy resin other than component (A).

[0034] Examples of epoxy resins other than component (A) include, for example, epoxy resins that are glycidyl ethers of phenolic compounds, epoxy resins that are glycidyl ethers of various novolac resins, and alicyclic Epoxy resin, aliphatic epoxy resin, heterocyclic epoxy resin, glycidinoresestenolic epoxy resin, glycidinoleamine epoxy resin, glycidyl Examples thereof include epoxied epoxy resin.

[0035] Among the above, epoxy resin, which is a glycidyl etherified product of a phenol compound, is 2— [4— (2,3 epoxypropoxy) phenol] — 2— [4— [1,1-bis] [Four- ( 2,3 hydroxy) phenol] phenyl] phenol] propane, bisphenol A, bisphenol A, bisphenol S, 4, 4'-biphenol, tetramethylbisphenol A, dimethylbisphenol eight, tetramethylbis Phenol F, dimethylbisphenol? , Tetramethylbisphenol S, dimethylbisphenol 3, tetramethyl-4,4'-biphenol, dimethyl-1,4'-biphenol, 1— (4 hydroxyphenol) 2— [4— (1, 1—bisone (4Hydroxyphenyl) ethyl) phenyl] propane, 2,2'-methylene monobis (4-methyl-6-tert butylphenol), 4,4'-butylidene-bis (3-methyl-6-tert-ert- Butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phlorogricinol, phenols having a diisopropylidene skeleton, phenols having a fluorene skeleton such as 1,1-hydroxy-4-hydroxyfluorene, phenolization Examples thereof include epoxy resin, which is a glycidyl ether compound of a polyphenol compound such as polybutadiene.

[0036] In addition, epoxy resins that are glycidyl ethers of various novolak resins include phenol, talesols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, and bisphenol. Novolak resin from various phenols such as bisphenols such as S or naphthols, phenol novolac resin containing xylylene skeleton, phenol novolac resin containing dicyclopentagen skeleton, phenol novolac resin containing biphenol skeleton And glycidyl ethers of various novolac resins such as fluorene skeleton-containing phenol nopolac resin.

[0037] Further, as the alicyclic epoxy resin, an alicyclic epoxy resin having an aliphatic ring skeleton such as cyclohexane, as the aliphatic epoxy resin, 1, ₄ butanediol, 1, 6- Polyglycol glycidyl ethers such as xanthdiol, polyethylene glycol or pentaerythritol, and heterocyclic epoxy resins include heterocyclic epoxy resins having a heterocyclic ring such as isocyanuric ring or hydantoin ring, glycidyl ester type Epoxy resins include carboxylic acid esters such as hexahydrophthalic acid diglycidyl ester, and glycidylamine-based epoxy resins include amines such as arlin or toluidine. Epoxy resin and halogenated phenols glycidylated epoxy resin are brominated bisphenols. Nord A, brominated bisphenol F And epoxy resin obtained by glycidylation of halogenated phenols such as brominated bisphenol s, brominated phenol novolak, brominated cresol novolac, chlorinated bisphenol S or chlorinated bisphenol A.

[0038] Of these epoxy resins, considering heat resistance and transparency, 2- [4— (2,3 epoxypropoxy) phenol] — 2— [4— [1, 1-bis [4- (2,3 Hydroxy) phenol] ethyl] phenol] propane; bisphenol A or fluorene skeleton-containing phenol novolak resin; alicyclic epoxy resin having an aliphatic ring skeleton such as cyclohexane Or glycidyl ethers of polyhydric alcohols such as pentaerythritol are preferred. The other epoxy resin as described above is added in an amount of 0 to L0 part by weight, if necessary, with respect to 100 parts by weight of the thermosetting resin composition of the present invention.

[0039] Furthermore, the thermosetting resin composition of the present invention includes a curing accelerator, a coupling agent, a surfactant, an oxidation stabilizer, a light stabilizer, a moisture resistance improver, a thixotropy, if necessary. Additives such as an imparting agent, an antifoaming agent, other various types of resin, a tackifier, an antistatic agent, a lubricant and / or an ultraviolet absorber can also be blended. These are added to the thermosetting resin composition of the present invention by a method known per se. Usually, these addition amounts are within the range of 0 to 20% by weight.

[0040] For example, any curing accelerator that can be used in the present invention can be used as long as it has a function of accelerating the condensation reaction between an epoxy compound and a compound having two or more carboxyl groups. Examples thereof include a system curing accelerator, a phosphine system curing accelerator, an ammonium system curing accelerator, and a Lewis acid system curing accelerator. In the present invention, it is particularly preferable to use an imidazole curing accelerator. Specific examples of imidazole curing accelerators that can be used include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenolimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2- 1-benzyl-2-phenol imidazole, 1-benzyl-2-phenol imidazole, 1-benzylimidazole, 1-cyanethyl-2, -methylimidazole, 1-cyanethyl-2-phenol-imidazole, 1-cyanethyl-2 Ndecylimidazole, 2, 3 Dihydro 1H Pyroguchi [1,2, a] benzimidazole, 2,4 Diamino-6 (2,1-methylimidazole (1,)) ethyl s-triazine, 2, 4 —Diamino 6 (2, -undecylimidazole (1,)) ethyl-s triazine, 2, 4 Diamino 6 (2,1 ethyl, 4-methylimidazole (1,)) ethyl s triazine, 2, 4 — Diamino 6 (2, 1-methylimidazole (1,)) ethyl s-triazine and isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2 phenol imidazole with isocyanuric acid Various imidazole compounds such as potassium, 2 phenol 3,5 dihydroxymethyl imidazole, 2 phenol 4 methyl 5 hydroxymethyl imidazole or 1 cyanoethyl 2 phenol 3,5-dicyanoethoxymethylimidazole are available. Can be mentioned. Among these, 2,3 dihydro-1 1H pyro [1-, 2-a] benzimidazole or 2-ferro-4-methylimidazole are particularly preferable examples. Specific examples of coupling agents that can be used include 3 glycidoxypropyltrimethoxysilanemethoxysilane, 2- (3,4 epoxy cyclohexyleno) ethinoretrimethoxysilane, N- (2 aminoethyl) 3 Minopropylmethyldimethoxysilane, N— (2 aminoethyl) 3-aminominomethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N— ( 2- (vinylbenzylamino) ethyl) 3-silane cups such as 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, and 3-propylpropyltrimethoxysilane Ring agent, isopropyl (N-ethylaminoethylamino) Titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate, neoalkoxy tri (p—N— (β-aminoethyl) aminophenol) Titanium coupling agents such as titanate, Zr-acetylylacetonate, Zr-metatalylate, Zr-pionate pionate, neoalkoxy zirconate, neoalkoxy tris neodecanol zirconate, neoalkoxy tris (dodecanol) benzenesulfur For zirconate, neoalkoxytris (ethylenediaminoethyl) zirconate, neoalkoxytris (m-aminophenol) zirconate and ammonium zirconium carbonate, or A1-acetylacetate And zirconium or aluminum coupling agents such as Nate, A1-metatalylate and A1-propionate. Among these, silane coupling A silane coupling agent having an epoxy group that is preferred by the agent is more preferred. By using the coupling agent, the adhesion to the substrate is improved and a protective film having excellent moisture resistance reliability can be obtained.

[0042] The curing accelerator may be omitted in the present invention! However, when added, the thermosetting resin composition of the present invention containing (A), (B) and (C). The amount is 0.1 to 3 parts by weight, preferably 0.1 to 0.3 parts by weight, based on 100 parts by weight.

In addition, a coupling agent may be omitted in the present invention, but when added, the amount used is 100 wt.% Of the thermosetting resin composition of the present invention containing (A), (B) and (C). The amount is 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight.

[0043] Similarly, the surfactant is added to improve the applicability of the thermosetting resin composition. Specific examples of the surfactant that can be used include silicon surfactants, fluorine surfactants, and organic surfactants. For example, BM-1000, BM-1 100 (manufactured by BMCHEMIE), MegaFace ^R ™ F470, F472, BL-20, R-08, R-30, R-90 (Dainippon Ink Chemical ( ), FLORAD FC-135, FC-170C, FC-430, FC-431 (Sumitomo 3EM), Surflon ^RTM S-112, S-113, S-131, Same S-141, Same S-145, Same S-381, Same S-382, Same SC-101, Same SC-102, Same SC-103, Same SC-104, Same SC-105, Same SC-106, KH-40 (Asahi Glass Co., Ltd.), Ftop ^RTM EF301, 303, 352 (Shin-Akita Kasei Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF- 8428, DC-57, DC-190 (manufactured by Toray Silicone Co., Ltd.), PolyFOXPF-636, PF-651, PF-652, PF-3320 (OMNOVA), Granore 400, Granore 420, Granole 440, Talen ^RTM KY—5020, Floren ^RTM DOPA—15BHF S, DOPA17HF, DOPA-33, DOPA-44, TG-720W, TG-750W, Polyflow KL-245, KL-260, KL-500, KL-600, WS-30 ( Silicone interfaces such as Kyoeisha Igaku Co., Ltd.), Dudyne ^RTM DS-403, DS-451, NS-1602, NS-1603, NS-1605 (Daikin Industries, Ltd.) An activator, a fluorosurfactant or an organic surfactant is appropriately used. Usually, a fluorosurfactant is preferred. The superscript “RTM” means a registered trademark. The amount added is usually 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the thermosetting resin composition of the present invention containing the components (A), (B) and (C). The amount is preferably 0.08 to 0.3 parts by weight.

[0044] The thermosetting resin composition of the present invention comprises the condensate of the component (A), the carboxylic acid compound having two or more carboxyl groups of the component (B), the solvent of the component (C), and the necessity. Depending on the above, it can be obtained as a varnish by uniformly dissolving the above-mentioned various additives. In this case, it is preferable to adjust the solid content concentration to usually 15 to 50% by weight, preferably 20 to 40% by weight. Moreover, the thermosetting resin composition of the present invention obtained as described above may be subjected to microfiltration using, for example, a filter of 0.05 to 1111 as necessary.

[0045] The cured film (protective film) of the coating film formed by the thermosetting resin composition of the present invention obtained in this way is various substrates or substrates such as glass, wood, metal, plastic, etc. The cured film has excellent adhesion to the functional film placed on it, and is excellent in smoothness, heat-resistant yellowing resistance, transparency and toughness, and has an appropriate hardness. Is a cured film (high visible light transmittance coating film) for protecting optical devices that require high visible light transmittance, such as organic EL elements, plasma display panels, and liquid crystal display color filters. Since the thermosetting resin composition and its cured film do not contaminate the liquid crystal, it is useful for protecting functional films such as colored resin films of liquid crystal display power filters. Therefore, the thermosetting resin composition of the present invention is suitable as a protective film agent for such an optical device, particularly as a protective film agent for a functional film such as a colored resin film of a color filter for liquid crystal display.

In the present invention, the most preferred functional film provided on the substrate is a colored resin film of a color filter for liquid crystal display.

In order to form a protective film on the functional film using the resin composition as a protective film agent, the resin composition is usually formed on the functional film by a spin coating method or the like. It is only necessary to apply and form a coating film and to thermally cure the coating film. The film thickness is usually applied under the condition of 0.1 to 10 m, preferably 0.5 to 8 m after heat curing. At this time, in order to efficiently perform the coating operation, the viscosity at 25 ° C. of the thermosetting resin composition or the functional film protective film of the present invention is 2 to 30 mPa · s, preferably 3 to: LOmPa · It is preferable to adjust to s. [0047] Drying and curing conditions after coating are preferably appropriately selected according to the composition ratio of the composition, the type of solvent, and the like. Usually 70 ~: Pre-beta at LOO ° C to remove the solvent, then post-beta at 150-250 ° C for 10 minutes to 1.5 hours to cure. The curing temperature need not be constant. For example, curing may be performed while raising the temperature. Solvent removal by pre-beta and curing by post-beta can be performed using an oven or a hot plate.

[0048] The functional film on which the protective film of the present invention is formed as described above is used for the preparation of various equipment according to each film.

[0049] Next, a case where the functional film is a colored resin film of a color filter will be described in detail. A normal color filter used for a liquid crystal display element is a red 'blue' on a transparent substrate such as a glass substrate. A colored transparent pattern such as green is regularly arranged. For the formation of a colored transparent pattern, a photolithographic method using a color resist having a color, a binder resin, a reactive diluent, a photopolymerizer and a solvent is widely used. In the photolithographic method, after applying the resist on a substrate, the resist is exposed through a photomask having a predetermined pattern, and then unnecessary portions are developed and removed. This process is performed at least for red, blue, and green. A colored resin film that is patterned three times for each colored pattern is produced. By providing the protective film of the present invention on the patterned colored resin film by the above-described method, a color filter having a cured film of the resin composition of the present invention can be obtained.

[0050] An ordinary liquid crystal display device generally includes a part of a color filter (ITO film formation, ITO pattern Jung is applied as necessary), a liquid crystal part, a knock light part, and a polarizing film part force. By using a color filter in which the protective film of the present invention is applied to a part of the color filter, the liquid crystal display device of the present invention can be obtained.

[0051] The thermosetting resin composition of the present invention is excellent in transparency, has a particularly high heat-resistant temperature, and is a protective film for a functional film such as a colored resin film having high stability at high temperatures. In particular, it can be suitably used as a protective film for a color filter. In a liquid crystal display device using a color filter provided with such a protective film, its reliability can be improved. it can.

Example

[0052] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following, “parts” means parts by weight, and “%” means percent by weight.

[0053] Synthesis Example 1

Synthesis of cocondensates (A-1) of the key compounds of formula (1) and formula (2)

2- (3,4 Epoxycyclohexyl) ethyltrimethoxysilane (compound represented by the above formula (1), manufactured by Shin-Etsu Chemical Co., Ltd.) 58.5 parts, phenol trimethoxysilane (the above formula (2 ) 99.9 parts and 339 parts of methylisobutylketone were charged into a reaction vessel, and the liquid temperature was raised to 80 ° C. After raising the temperature, 19.5 parts of a 0.5% aqueous potassium hydroxide solution were continuously added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was reacted at 80 ° C for 5 hours under reflux.

After completion of the reaction, 80 parts of methylisobutyl ketone and 200 parts of water were added to the reaction liquid, liquid separation was performed, the organic layer was separated, and washing with water was repeated until the washing liquid became neutral. Subsequently, the solvent was removed from the organic layer under reduced pressure to obtain 106 parts of a cocondensate (A-1). The obtained epoxy compound had an epoxy equivalent of 507 gZeq and Mw = 1500.

[0054] Synthesis Example 2

Synthesis of cocondensate (A-2) of the key compound of formula (1) and formula (2)

2 -— (3,4 Epoxycyclohexyl) ethyltrimethoxysilane 117.0 parts, phenyltrimethoxysilane 62.8 parts, and methylisobutyl ketone 339 parts were charged into a reaction vessel and the liquid temperature was raised to 80 ° C. Warm up. After raising the temperature, 10.5 parts of a 0.5% aqueous potassium hydroxide solution was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was reacted at 80 ° C for 5 hours under reflux.

After completion of the reaction, 80 parts of methylisobutyl ketone and 200 parts of water were added to the reaction solution, liquid separation was performed, the organic layer was separated, and washing with water was repeated until the washing solution became neutral. Next, the solvent was removed from the base layer under reduced pressure to obtain 113 parts of a cocondensate (A-2). The epoxy equivalent of the obtained cocondensate was 272 gZeq, Mw = 1500.

[0055] Examples 1 to 6, Comparative Example 1 Each component shown in Table 1 is mixed and dissolved at the composition ratio shown in the same table to obtain a uniform solution (solvent: propylene glycol monomethyl ether acetate).

25% of the thermosetting resin composition of the present invention was obtained. This thermosetting resin composition had a viscosity of V and a deviation of 5 to 7 mPa · s (measured under the conditions of lOrpm with an R-type viscometer manufactured by Toki Sangyo Co., Ltd.).

Also for Comparative Example 1, comparative thermosetting resin compositions were obtained in the same manner as in Examples 1 to 6 with the components and composition ratios shown in Table 1.

[Table 1] Composition table (unit: parts)

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Co-compound (A-1) (Note) 100 1 00 100 1 00 100

Co-compound (A-2) (Note 2) 100

Epoxy resin (Note 3) 1 00

Curing (CB-1) (Note 4) 9. 9

Curing ¾ CB-2) (Note 5) 1 0. 1

Curing ¾ [B-3] (Note 6) 1 0. 3

Curing (CB-4) (Note 7) 7.0

Hardener (B—5) (Note 8) 21. 6

Hardener (B 6) (Note 1 3) 1 0. 3

Cured rice cake (Note 9) 74.2

0) 1. 0 Surfactant (Note 1 1) 1. 0 1. 0 1. 0 1. 0 1. 0 1. C) 1. 0 Port ft (Note 1 2) 333 333 334 324 368 33 '1 -529

Note 1 Key compound (A-1): Key compound having an epoxy group obtained in Synthesis Example 1. Note 2 Key compound (A-2); Key compound having an epoxy group obtained in Synthesis Example 2 Note 3 Epoxy resin represented by the following formula (11) (epoxy equivalent: 220 gZeq epoxy resin described in Examples of Patent Document 1)

[0059] Note 4 Curing agent (B-1); phthalic acid

Note 5 Curing agent (B-2); Tetrahydrophthalic acid

Note 6 Curing agent (B-3) \ Xahydrophthalic acid

Note 7 Curing agent (B-4) 2, 4 Cyclohexanetricarboxylic acid

Note 8 Curing agent (B-5) 2, 3, 4 Butanetetracarboxylic acid

Note 9 Curing agent: Epicure MP402FPY (Novolak terpene skeleton-containing phenol resin, manufactured by Nippon Epoxy Resin Co., Ltd.)

Note 10 Curing accelerator; 2, 3 Dihydro-1H-pyrrolo [1, 2— a] benzimidazole Note 11 Surfactant; MegaFac F470 (Fluorosurfactant, manufactured by Dainippon Ink Co., Ltd.)

)

Note 12 Solvent: Propylene glycol monomethyl ether acetate

Note 13 Curing agent (B-6); l, 3 cyclohexanedicarboxylic acid

[0060] Examples 7 to 12, Comparative Example 2

Each of the thermosetting resin compositions according to the present invention and the comparative examples obtained in Examples 1 to 6 and Comparative Example 1 was cured on a glass substrate having a thickness of 0.7 mm using a spin coater. Apply the film thickness to 1.5 m (however, in the ITO sputter resistance test, the film thickness is 2 m), pre-beta at 85 ° C for 2 minutes, then 230 ° C for 40 minutes. Heat curing was performed under conditions to obtain the cured films for comparison with the present invention.

[0061] Evaluation test

For each of these cured films, an evaluation test was conducted for each of the following items. Results are shown.

(1) Transparency

The transmittance at 400 to 800 nm was measured with a spectrophotometer (U-3310, manufactured by Hitachi, Ltd.). The lowest transmittance value was shown in Table 2. The transmittance is preferably 95% or more over the entire range of 400 to 800 nm.

(2) Heat resistant transparency (Coating yellowing test)

The glass substrate provided with each cured film was allowed to stand in an oven at 250 ° C. for 60 minutes, and the transmittance at 400 to 800 nm was measured. The lowest transmittance value was shown in Table 2. It is preferable that the transmittance is 95% or more in the entire range of 400 to 800 nm! /.

(3) Ozone resistance (resistance to ozone generated during UV irradiation)

Each cured film was cleaned for 90 seconds with an UV cleaner (UVD-25U03 made by Nippon UV Machine Co., Ltd.), then left in an oven at 250 ° C for 60 seconds, and the transmittance at 400-80 Onm. The minimum transmittance value is shown in Table 2. It is preferable that the transmittance is 95% or more over the entire range of 400 to 800 nm! / ヽ.

(4) ITO sputtering properties

Each thermosetting resin composition is coated on a glass substrate so as to have a cured film thickness of 2 μm, pre-beta is applied at 85 ° C. for 2 minutes, then 230 ° C. for 40 minutes. Thermal curing was performed under the conditions described above. On these cured films, the state of the cured film was observed visually at 240 ° C. when ITO was sputtered to a film thickness of 2500 A and a sheet resistance value of 5.7 Q / cm ² . The evaluation was made according to the following criteria.

○: No change in appearance

△: Partial occurrence of wrinkles or cracks

X: Wrinkles, cracks or white turbidity is generated on the entire cured film

(5) Solvent resistance

The degree of decrease of each cured film after immersing the glass substrate provided with each cured film obtained above in each solvent of isopropyl alcohol, N-methylpyrrolidone, γ-petit-mouth rataton at 40 ° C for 45 minutes. It was measured with a stylus type surface roughness meter (P-15 manufactured by Tencor Co., Ltd.). If the degree of decrease was 5% or less when immersed in any solvent, it was evaluated as ◯. (6) Flatness

Place a 1.5 micron blue colored resin film with a cavity on the glass substrate, and apply each thermosetting resin composition on the glass substrate to a cured film thickness of 1.5 microns. After applying the pre-beta at 85 ° C for 2 minutes and then thermosetting at 230 ° C for 40 minutes, the surface flatness was measured with the stylus type surface roughness meter. It was measured. Table 2 shows the maximum step values.

[0063] Evaluation results

Table 2 shows the results obtained in each of the above evaluation tests.

[Table 2] Evaluation test results

Example 7 Example 8 Example 9 Example 1 0 Example 1 1 Example 1 2 Comparative Example 2

Composition Example NO (Example 1) (Example 2) (Example 3) (Example 4) (Example 5) (Example ί 3) (Comparative Example 1) Transparency (%) 9 9 9 9 9 9 9 9 Θ 9 9 9 9 6 Heat resistance transparency (%) 9 9 9 9 9 9 9 9 9 9 9 9 8 4 Ozone resistance (¾>) 9 7 9 7 9 8 9 8 9 7 9 8 7 6

1 T O Sputter resistance O O O ○ Ο Ο X Solvent resistance o O O O Ο ο ο Flatness (M m) 0. 2 0. 1 0. 0 9 0. 2 0. 5 0. 0 S »0.6

[0064] Further, when the cured film of the present invention having a film thickness of 1.5 μm obtained as described above was measured by the “strengthening hardness (pencil method)” of JIS K5600-5-4, a comparative example was obtained. The force with pencil hardness B in 1 was pencil hardness of 3H to 5H in the examples of the present invention.

[0065] As can be seen from the results shown in Table 2, the protective film obtained with the thermosetting resin composition strength of the present invention is excellent in transparency and has a particularly high heat-resistant temperature, and is stable at high temperatures. In addition, it has excellent solvent resistance and flatness. It is also excellent in yellowing resistance in high-temperature treatment performed after ultraviolet cleaning with ozone generation.

Therefore, the thermosetting resin composition of the present invention is useful as a protective film agent for a colored resin film, and particularly used as a protective film for a colored resin film used in a color filter for a liquid crystal display device. As a result, the performance and reliability of the color filter can be improved.

Claims

Claims (A) Self-condensate of a key compound having an epoxy group represented by the following formula (1), and a key compound having an epoxy group represented by Z or the following formula (1) and the following formula ( 2) a cocondensate with an alkoxycarbene compound represented by

(In the formulas (1) and (2), X is a C2-C5 alkylene group, R and R are C1-C4

1 2

Z represents a methyl group or a phenyl group. ) (B) one or more selected from the group consisting of an aliphatic compound having two or more carboxyl groups, an aromatic compound and an alicyclic compound, and (C) a thermosetting comprising a solvent. Sexual resin composition.

[2] The aliphatic compound, aromatic compound and alicyclic compound having two or more carboxyl groups as the component (B) are compounds represented by the following formulas (3) to (8): Thermosetting rosin composition

[3] A protective film for a functional film comprising the thermosetting resin composition according to claim 1 or 2.

[4] The protective film agent for functional film according to [3], wherein the functional film is a colored resin film.

[5] A resin cured film obtained by curing the functional film protective film agent according to claim 3 or 4.

[6] A color filter comprising a colored resin film having the resin cured film according to claim 5.

[7] A liquid crystal display device comprising the color filter according to claim 6.

[8] The thermosetting resin composition according to [1], wherein the alicyclic compound having two or more carboxyl groups in component (B) is a compound represented by the following formula (9).

(9)

[9] The thermosetting according to claim 2, wherein the component (B) is at least one selected from the group force consisting of compounds of the formula (3), the formula (5), the formula (7) and the formula (8). A rosin composition.

[10] The component (B) is substituted with 2 to 5 carboxyl groups, and the aliphatic group has 2 to

An aliphatic compound that is substituted with 2 to 4 carboxyl groups, and an aromatic compound that has 6 to 14 carbon atoms in the aromatic group, and 2 to 4 carboxyl groups or carboxymethyl groups 2. The thermosetting resin composition according to claim 1, wherein the alicyclic group has 6 to 10 alicyclic groups and has a combined force.

[11] The component (B) is a C2 to C8 aliphatic compound substituted with 2 to 4 carboxyl groups or a C6 alicyclic compound substituted with 2 to 4 carboxyl groups. 1. The thermosetting resin composition according to 1.

12. The thermosetting resin composition according to claim 11, wherein the C2 to C8 aliphatic compound substituted with 2 to 4 carboxyl groups is 1, 2, 3, 4-butanetetracarboxylic acid.

[13] The component (A) is a cocondensate of a silicon compound having an epoxy group of the formula (1) and an alkoxy compound represented by the formula (2), and Z in the formula (2) is Claims 1 and 2 which are-group The thermosetting resin composition according to any one of 8 to 12, wherein the deviation is one.

[14] The co-condensate is a co-condensate of 2- (3,4-epoxycyclohexyl) ethyltri (C1-C4) alkoxysilane and ferrtri (C1-C4) alkoxysilane. The following thermosetting resin composition.

[15] A protective film agent for optical devices, which also has the thermosetting resin composition power according to any one of claims 1, 2, and 8-12.