JP3152038B2 - Thermosetting composition for forming protective film for color filter and protective film for color filter - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a thermosetting composition,
The present invention relates to a thermosetting composition for a color filter, which is excellent in various physical properties of a coating film as a coating film forming material, and particularly excellent in flattening performance of a base.

[0002]

2. Description of the Related Art In general, in order to prevent deterioration or damage of the surface of a substrate of various articles, it is widely practiced to form a protective coating on the surface of the substrate. In such a protective coating, the adhesiveness to the substrate is high, the coating is smooth and tough, it does not undergo deterioration such as discoloration over a long period of time, and it has excellent water resistance and solvent resistance. Performance is required.

In recent years, various types of color liquid crystal display elements (LCD) incorporating a color filter have been announced. The color filter of the color liquid crystal display device is formed on a transparent substrate such as glass by a method such as a dyeing method, a printing method, a vapor deposition method, and a resist method. The color filter formed by these methods usually has a protective film formed on the surface for the purpose of preventing the subsequent steps from adversely affecting the color filter. In particular, in the dyeing method, an anti-staining protective film for each hue is required in order to prevent color mixture other than on the surface. Therefore, the protective film is required to have properties such as adhesion, smoothness, toughness, heat resistance, transparency, weather resistance, solvent resistance, water resistance, and dye resistance. In addition, recently, due to a tendency to reduce the weight of LCDs, the protective film is also being made thinner. For this reason,
The ability to flatten micron-order irregularities between color hues, and the color filter and surrounding areas, which was not so much of a problem in the past, prevents step lines when forming a transparent electrode on a color filter. From this point of view, it has become very important. A similar situation is becoming more prominent in the field of on-chip color light receiving elements (CCD).

Conventionally, lamination using a thermoplastic resin such as polystyrene or polycarbonate is known as one of the coating film forming materials. However, these coating films are said to have low adhesion to substrates, heat resistance, and solvent resistance. Has disadvantages.
Also, melamine resins are known as another coating film forming material, but these resins are hard and brittle, so that they are easily cracked and have low transparency and low solvent resistance. Further, thermosetting acrylic resin is known as a coating film forming material, but the coating film has low adhesion to a substrate, low solvent resistance, and poor storage stability of the system. Further, any of the systems is unsuitable for the above-mentioned flattening performance.

[0005]

SUMMARY OF THE INVENTION In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to improve the adhesiveness, toughness, heat resistance, transparency, weather resistance, solvent resistance, water resistance and dyeing resistance. Excellent,
Another object of the present invention is to provide a thermosetting composition having excellent flattening performance of a base. Still other objects and advantages of the present invention are:
It will be clear from the description below.

[0006]

The above objects and advantages of the present invention are as follows: (1) a resin containing an epoxy group , a curing agent and a hydroxycarboxylic acid ester, an alkoxycarboxylic acid ester, a propylene glycol monoalkyl ester,
And the protective film forming thermosetting composition for a color filter characterized in that it contains at least one solvent selected from the group consisting of propylene glycol ether esters. (2) The thermosetting composition according to claim 1, wherein the resin containing an epoxy group is a resin containing 30% by weight or more of a unit represented by the general formula (I) or (II).

[0007]

Embedded image

(Wherein R ₁ is a hydrogen atom or a group having 1 to 1 carbon atoms)
An alkyl group of 5, n is an integer of 1 to 10, and R ₂ has the following structure. ) R ₂ : —COO—

[0009]

Embedded image

[0010]

Embedded image

(In the formula, m is an integer of 1 to 5.)

[0012]

Embedded image

Wherein R ₁ is a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 10 carbon atoms, a haloalkyl group or an aryl group. R ₂ is a hydrogen atom, an alkyl group or an aryl group having 1 to 5 carbon atoms. And m is an integer of 0 to 3;
Represents an integer of 1 to 4, and m + n ≦ 4. )

[0014] The solvent is at least one solvent selected from ethyl lactate, 3-methoxymethyl propionate, 3-ethoxyethyl propionate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. Is achieved by the thermosetting composition according to item 1.
Hereinafter, the components of the present invention will be described.

[0015] 1. Epoxy Group-Resin Resin The epoxy group-containing resin used in the present invention may specifically be the following. 1-1 30 units of the unit represented by the general formula (I)
The polymer containing 30% by weight or more of the unit represented by the general formula (I) (hereinafter, referred to as “polymer I”) includes a compound having an epoxy group and an ethylenically unsaturated bond ( Hereinafter, referred to as “compound I”), a copolymer comprising two or more compounds I, and a copolymer comprising one or more compounds I and other monomers.

Specific examples of compound I include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid-3,4 -Epoxybutyl, 3,4-epoxybutyl methacrylate, 4,5-epoxypentyl methacrylate, -6,7-epoxyheptyl acrylate, -6,7-epoxyheptyl methacrylate, α-ethylacrylic acid- (Meth) acrylates such as 6,7-epoxyheptyl; o-vinylphenylglycidyl ether, m-
Vinylphenyl glycidyl ether, p-vinylphenyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p
Vinyl glycidyl ethers such as vinylbenzyl glycidyl ether; 2,3-diglycidyloxystyrene, 3,4-diglycidyloxystyrene, 2,4-diglycidyloxystyrene, 3,5-diglycidyloxystyrene, 2, 6-diglycidyloxystyrene, 5
-Vinylpyrogallol triglycidyl ether, 4-vinylpyrogallol triglycidyl ether, vinyl phloroglysinol triglycidyl ether, 2,3-dihydroxymethylstyrene diglycidyl ether, 3,4
-Dihydroxymethylstyrene diglycidyl ether,
2,4-dihydroxymethylstyrene diglycidyl ether, 3,5-dihydroxymethylstyrene diglycidyl ether, 2,6-dihydroxymethylstyrene diglycidyl ether, 2,3,4-trihydroxymethylstyrene triglycidyl ether, 1,3 , 5-trihydroxymethylstyrene triglycidyl ether. Among these compounds, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, p-vinylphenyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether are preferred.

The unit of the general formula (I) in the polymer I is
It is preferably at least 30% by weight, more preferably from 40 to 100% by weight. If the unit of the general formula (I) in the polymer I is less than 30% by weight, the adhesion between the composition and the substrate may be insufficient.

Other monomers that can be used to form polymer I include, for example, olefins such as butadiene, isoprene, chloroprene, styrene, or α-, o-, m-, p-alkyl of styrene. , Alkoxy, halogen, haloalkyl, nitro, cyano, amide, ester-substituted, methacrylic acid, acrylic acid, methacrylic acid or acrylic acid methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl,
ter-butyl, pentyl, neopentyl, isoamyl, hexyl, cyclohexyl, adamantyl, isobornyl, allyl, propargyl, phenyl, naphthyl, anthracenyl, anthraquinonyl, piperonyl, salicyl, cyclohexyl, benzyl, phenesyl, cresyl, 2-hydroxyethyl, 1,1 , 1-trifluoroethyl, perfluoroethyl, perfluoro-n-propyl, perfluoro-i-propyl, triphenylmethyl, dicyclopentanyl, cycyclopentaoxyethyl, cumyl, 3- (N, N-dimethyl Amino) propyl, 3- (N, N-dimethylamino) ethyl, furyl,
Furfuryl ester, anilide, amide of methacrylic acid or acrylic acid, or N, N-dimethyl, N, N-
Diethyl, N, N-dipropyl, N, N-diisopropyl, anthranilamide, acrylonitrile, acrolein, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, Maleic anhydride, itaconic anhydride, citraconic anhydride, N-phenylmaleimide, N- (4-hydroxyphenyl) maleimide, N
-Methacryloyl phthalimide, N-acryloyl phthalimide and the like.

Of these, butadiene, styrene, methacrylic acid, acrylic acid and styrene α-, o-, m
-, P-alkyl, alkoxy, halogen, haloalkyl, nitro, cyano, amide, ester substituted, butadiene, methacrylic acid, α-haloalkyl of acrylic acid, alkoxy, halogen, nitro, cyano substituted, methyl, ethyl, n -Propyl, n-butyl, ter-
Butyl, dicyclopentanyl, adamantyl and the like are preferably used.

1-2 Uni-unit represented by the general formula (II)
Polymer containing 30% by weight or more of a polymer The polymer containing 30% by weight or more of the unit represented by the general formula (II) (hereinafter, referred to as “polymer II”) includes phenol, cresol, hydroquinone, resorcinol Catechol, pyroganol, phloroglicinol, naphthol, xylenol, trimethylphenol, bisphenol A, glycidyl ether of bisphenol A, pisphenol F and bisphenol AF. As a commercially available resin, Epicoat 152, 15
4 [made by Yuka Shell Epoxy Co., Ltd.], EPPN201,
Phenol novolak resin type epoxy resin commercial products such as 202 [manufactured by Nippon Kayaku Co., Ltd.], EOCN-102, 10
Cresol novolak type epoxy resins such as 3S, 104S, 1020, 1025, and 1027 (manufactured by Nippon Kayaku Co., Ltd.) and Epicoat 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd.) can be used.

The molecular weight of the polymer I or II is not particularly limited as long as the composition of the present invention can be applied as a uniform film.
It is from 00 to 300,000, and can be appropriately selected depending on conditions such as the thickness of the coating film to be formed and the coating method.

The present invention further relates to an epoxy resin other than the polymers I and II, for example, Epicoat 101, 1002,
1003, 1004, 1007, 1009, 1010,
Bisphenol A-type epoxy resin such as 828 (manufactured by Yuka Shell Epoxy), bisphenol F-type epoxy resin such as Epicoat 807 (manufactured by Yuka Shell Epoxy), CY-175, 177, 179 [CIBA-G
EIGY A. G), ERL-4234, 4299,
4221 and 4206 [U. C. Company C], Shodyne 509 (Showa Denko KK), Aldarite CY-18
2, 192, 184 (CIBA-GEIGY AG
Manufactured), Epicron 200, 400 [Dainippon Ink Co., Ltd.
Cyclic epoxy resins such as Epicoat 871 and 872 [Yukaka Epoxy Co., Ltd.] and ED-5661 and 5662 [Celanese Coating Co., Ltd.];
Evolite 100MF (Kyoeisha Yushi Chemical Industry Co., Ltd.)
Polyglycidyl ethers such as EPIOL TMP (manufactured by Nippon Oil & Fats Co., Ltd.) and the like can also be used in combination with polymers I and II.

[0023] 2. Curing Agent The composition of the present invention contains a polycarboxylic anhydride or a polycarboxylic acid as a curing agent. Specific examples of the polycarboxylic anhydride include phthalic anhydride, itaconic anhydride,
Aliphatic or alicyclic dicarboxylic acids such as succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hymic anhydride, nadic anhydride, etc. Anhydrides; aliphatic polycarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride;
Aromatic polycarboxylic anhydrides such as pyromellitic anhydride, trimellitic anhydride, and benzophenonetetracarboxylic anhydride; and ester group-containing anhydrides such as ethylene glycol bistrimellitate and glycerin tristrimellitate. Particularly preferred are aromatic polycarboxylic anhydrides. Further, a commercially available epoxy resin curing agent composed of a carboxylic acid anhydride can also be suitably used. As a specific example, Adeka Hardener E
H-700 (made by Asahi Denka Kogyo Co., Ltd.), Rikka Seed H
H, MH-700 (manufactured by Shin Nippon Rika Co., Ltd.), Epikinia 126, YH-306, and DX-126 (manufactured by Yuka Shell Evoxy Co., Ltd.).

Specific examples of the polycarboxylic acid used in the present invention include aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid and itaconic acid; Phthalic acid,
Aliphatic polycarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, and phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, Examples thereof include aromatic polycarboxylic acids such as 1,4,5,8-naphthalenetetracarboxylic acid and benzophenonetetracarboxylic acid, and preferably include aromatic polycarboxylic acids. These polycarboxylic anhydrides and polycarboxylic acids may be used alone or in combination of two or more.
Mixtures of more than one species can also be used.

The compounding amount of the curing agent used in the present invention is in the range of 1 to 100 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the epoxy group-containing resin.
If the amount of the curing agent is less than 1 part by weight, curing will be insufficient and a tough coating film cannot be formed. Also,
If the amount of the curing agent exceeds 100 parts by weight, the adhesion of the coating film to the substrate is poor, and a uniform and smooth coating film cannot be formed.

[0026] 3. Other Additives 3-1 Adhesion Aid The composition of the present invention can contain a functional silane coupling agent as an adhesion aid for the purpose of improving the adhesion to the substrate. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glucidoxypropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned. These silane coupling agents may be used alone or in combination of two or more.

The compounding amount of the adhesion aid in the composition of the present invention is 0.1 to 100 parts by weight of the epoxy group-containing resin.
It is in the range of 30 to 30 parts by weight, preferably 0.5 to 20 parts by weight. If the amount of the adhesion aid is less than 0.1 part by weight, the smoothness of the formed coating film and the adhesion to the substrate may be insufficient. Further, when the amount is more than 30 parts by weight, the toughness of the coating film is lost.

3-2 Surfactant A surfactant may be added to the composition of the present invention for the purpose of suppressing coating unevenness such as striation. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene aryl such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether Ethers; nonionic surfactants such as polyeletin glycol dialkyl esters such as polyethylene glycol dilaurate and polyethylene glycol distearate; F-top EF
301, 303, 352 (manufactured by Shin-Akita Chemical Co., Ltd.), Megafac F171, 172, 173 (manufactured by Dainippon Ink Co., Ltd.), Florado FC430, 431 (manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC-101, 102, 103, 10
4, 105, 106 (manufactured by Asahi Glass Co., Ltd.); fluorine-based interfacial lubricant; organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); acrylic acid-based or methacrylic acid-based (co) polymer polyflow No. 4; 57, 95 (manufactured by Kyoei Yushi Kagaku Kogyo KK) and the like. These interfacial lubricants may be used alone or in combination of two or more.

The amount of the surfactant in the composition of the present invention may be in the range of 0.1 to 100 parts by weight of the epoxy group-containing resin.
The range is from 0.01 to 10 parts by weight, preferably from 0.03 to
1.0 part by weight. If the amount of the surfactant is less than 0.01 part by weight, uneven coating may not be suppressed. Further, when the amount is more than 10 parts by weight, the toughness of the coating film is lost.

3-3 Epoxy Curing Accelerator The composition of the present invention may contain an amine curing accelerator for the purpose of lowering the curing temperature of the epoxy resin or improving the curing speed. Specifically, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, indole, indazole, quinoline, isoquinoline, benzimidazole, isocyanuric acid, imidazole, 2-methylimidazole, 2,4-dimethylimidazole, 2-heptadecylimidazole, 4 -Methyl-2-phenylimidazole, 1-pentyl-2-methylimidazole, 2-
Ethyl-4-methyl-1- (2'-cyanoethyl) imidazole, 2-ethyl-4-methyl-1- [2'-
(3 ", 5" -diaminotriazinyl) ethyl] imidazole. These curing accelerators may be used alone or in combination of two or more.

The amount of the curing accelerator in the composition of the present invention is 0.1 to 100 parts by weight of the epoxy group-containing resin.
The range is from 0.1 to 10 parts by weight, preferably from 0.1 to 10 parts by weight.
5.0 parts by weight. If the amount of the vulcanization accelerator is less than 0.01 parts by weight, it may not be possible to expect a decrease in the curing temperature of the epoxy resin or an increase in the curing speed. Further, when the amount is more than 10 parts by weight, storage stability in a solution state is deteriorated, coloring of a coating film, embrittlement of a cured coating film, and the like are caused.

3-4 Polyvalent Acrylic Oligomer The composition of the present invention may contain a polyvalent acrylic oligomer for the purpose of improving the toughness of the resin containing an epoxy group and the adhesion to a substrate. Specifically, Alonix M-210, M-240, M-6200, M-309,
M-400, M-405, M-450, M-7100,
M-8030, M-8060 [Toa Gosei Chemical Industry Co., Ltd.
KAYARAD HDDA, HX-220, R-
604, TMPTA, DPCA-20, DPCA-3
0, DPCA-60, DPCA-120, V-295,
V-300, V-360, V-GPT, V-3PA, V
-400 [manufactured by Nippon Kayaku Co., Ltd.]. These polyacrylic oligomers may be used alone or in combination of two or more.

The amount of the polyhydric acrylic oligomer in the composition of the present invention is in the range of 1 to 200 parts by weight, preferably 5 to 100 parts by weight, per 100 parts by weight of the epoxy group-containing resin.
-30 parts by weight. If the compounding amount of the polyvalent acrylic oligomer is less than 1 part by weight, it may not be possible to expect improvement in the toughness of the epoxy group-containing resin and the adhesion to the substrate. Further, when the amount is more than 100 parts by weight, the storage stability in a solution state is deteriorated.

In the composition of the present invention, in addition to the above-mentioned components 3-1 to -4, additives such as an antioxidant, an ultraviolet absorber and an antifoaming agent can be appropriately used as needed. When transparency is not required depending on the purpose of the coating film, pigments, dyes, fillers and the like can be blended.

The composition of the present invention is obtained by dissolving the above components in at least one solvent selected from hydroxycarboxylic acid esters, alkoxycarboxylic acid esters, propylene glycol monoalkyl ethers and propylene glycol ether esters. . Specifically, methyl hydroxyacetate, ethyl hydroxyacetate, propyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxy Hydroxycarboxylic esters such as propyl propionate and butyl 3-hydroxypropionate; methyl methoxyacetate;
Ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, butoxyacetic acid Ethyl, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate,
Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2
-Methyl ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, 2-
Butyl ethoxypropionate, methyl 2-propoxypropionate, ethyl 2-propoxypropionate, 2-
Propyl propoxypropionate, butyl 2-propoxypropionate, methyl 2-butoxypropionate, 2
-Ethyl butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3-
Methyl methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3-ethoxy Butyl propionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropion Carboxylic acid esters such as propyl acrylate and butyl 3-butoxypropionate; propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether Propylene glycol monoalkyl ethers such as propylene glycol butyl ether; propylene glycol methyl ether acetate,
Propylene such as propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate Glycol alkyl ether esters and the like can be mentioned. These solvents may be used alone or in combination of two or more.

Of these solvents, ethyl lactate, 3-methoxymethyl propionate, 3-ethoxyethyl propionate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are preferred because of their good solubility and flattening property. Therefore, it is particularly preferably used in the composition of the present invention.

The order of mixing when the composition of the present invention is adjusted by melt mixing is not particularly limited.
A solution of the composition of the present invention may be prepared by dissolving all components in a solvent at the same time, or each component may be separately dissolved in the same or different solvent to form two or more solutions, if necessary. May be mixed to prepare a solution of the composition of the present invention.

The concentration of the composition solution is not particularly limited and can be appropriately selected depending on the purpose of use, but is generally used at about 5 to 50% by weight. A required coating film can be obtained by applying the solution of the composition of the present invention prepared as described above to the surface of the substrate and curing by heating. The method of applying the solution of the composition of the present invention to the substrate surface is not particularly limited, and various methods such as a spray method, a roll coating method, and a spin coating method can be used.

The thermosetting conditions of the composition of the present invention vary depending on the mixing ratio of each component of the composition and the like.
15 minutes to 10 hours at 250 ° C. The thus-obtained coating film of the composition of the present invention has a high light transmittance in a wide range of wavelengths from ultraviolet to visible light, exhibits excellent transparency, and exhibits glass and metal. It exhibits excellent adhesion to substrates made of various materials such as plastics. This coating is smooth and tough,
In particular, it is excellent in flattening performance of a micro-order step structure. Furthermore, it does not discolor even after long-term use, and is excellent in water resistance and solvent resistance.

Next, the present invention will be described in detail with reference to Synthesis Examples and Examples, but the present invention is not limited to these Examples and the like. In addition,% shows weight% unless there is particular notice.

1. Synthesis Example 1-1 of Polymer I Synthesis Example 1 of Polymer I In a separable flask equipped with a cooling pipe, a stirrer, a nitrogen introduction pipe, and a thermometer, the amounts of the monomers, the solvent, and the polymerization initiator shown in Table 1 were measured. , And reacted under the conditions shown in the same table to synthesize a resin (hereinafter, referred to as “resins 1 to 5”). The reaction rate was calculated from the solid concentration of the obtained resin, and the product was further subjected to GPC chromatography HL-8020 manufactured by Toyo Soda.
Was used to determine the weight average molecular weight in terms of polystyrene.

1-2 Synthesis Example 2 of Polymer I Hydrogenated polyhydroxystyrene (trade name, PHM-C) 120.15 g, epichlorohydrin 92.53 g, tetrabutylammonium bromide 32.24 g, manufactured by Maruzen Petrochemical Co., Ltd. Was dissolved in 500 ml of dimethylformamide and reacted at 60 ° C. for 24 hours. Subsequently, 40 g of sodium hydroxide was added to this solution and reacted for 24 hours. After completion of the reaction, the mixture was filtered to remove salts, and
Poured into liter of methanol. The resulting precipitate was washed twice with tetrahydrofuran (THF) / methanol, THF /
It was purified by reprecipitation once with n-hexane and dried at 50 ° C. overnight. The obtained polymer (hereinafter referred to as “resin 6”)
^The glycidyl group introduction rate determined from the ¹ H-NMR spectrum was 90 mol%.

2. The solutions of Examples Example 1 Resin 1-a was diluted to a solid concentration of 14% by MMP, the resin solid content of 100 parts by weight, 10 parts by weight of trimellitic acid, .gamma.-glycidoxypropyltrimethoxysilane 5 parts by weight of trimethoxysilane was added and stirred to obtain a uniform solution. The composition solution of the present invention was prepared by filtration through a filter having a pore size of 0.2 μm. The obtained solution was formed into a film under the conditions shown in Table 3, and evaluated and observed. The results are shown in Table 2.

Examples 2 to 10 and Comparative Examples 1 and 2 Evaluations were performed in the same manner as in Example 1 except that the resins, compounds and solvents shown in Table 2 were used. See Table 2 for results
Summarized in

[0045] 3. Coating Performance 3-1 Film Formation Conditions and Evaluation Items The coating conditions of the composition solution of the present invention were set as follows. Resin on glass substrate (Corning 7059)
A composition solution of the present invention comprising a curing agent, an additive, a solvent and the like is spin-coated so as to have a thickness of 1.0 μm.
The composition was cured by heating in an oven at 0 ° C. for 1 hour. The following evaluation was performed about the obtained cured film.

Light transmittance: 3 on the substrate after heat curing.
The light transmittance of 50 to 800 nm was measured. When the minimum value of the measured values was 95% or more, it was evaluated as ○, and when it was less than 95%, it was evaluated as x. Adhesiveness: Base test by peeling tape (JIS-K54)
00) was performed after heat curing, after boiling water treatment, and after toluene heating treatment (treatment time: 5 hours), and the number of peeled pieces was examined. Heat resistance: heat cured substrate in oven at 200 ° C for 20
After heating for 0 hour, the coating film was examined for cracks and light transmittance. Flatness: The composition solution of the present invention was applied to form a film on a substrate having a color filter with a maximum step height of 1.0 μm, and the maximum step height after film formation was examined. Pencil hardness: The surface hardness of the coating film is determined by the pencil hardness method (JIS-K5
400).

[0047]

According to the present invention, the adhesion to the substrate is high, the coating film is smooth and tough, does not discolor over a long period of time, has excellent water resistance and solvent resistance, and has a flattening performance of steps on the order of microns. , A thermosetting composition having a high value can be obtained.

[Table 1]

[Table 2]

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI (C08K 5/04 5:06 5:10) (56) References JP-A-60-216307 (JP, A) JP-A-3-188153 ( JP, A) JP-A-4-53879 (JP, A) JP-A-4-300942 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 63/00-63/10 C08K 5/06 C08K 5/10 C09D 163/00-163/10 G02B 5/20 G02F 1/13

Claims (4)

(57) [Claims] 1. A resin containing an epoxy group , a curing agent and a hydroxycarboxylic acid ester, an alkoxycarboxylic acid ester, a propylene glycol monoalkyl ester,
Characterized in that at least one contains a solvent selected and propylene glycol ether esters
A thermosetting composition for forming a protective coating of a color filter . 2. The thermosetting composition according to claim 1, wherein the resin containing an epoxy group is a resin containing 30% by weight or more of a unit represented by the general formula (I) or (II). Embedded image (In the formula, R1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n is an integer of 1 to 10, and R2 has the following structure.) R2: -COO- Embedded image (In the formula, m is an integer of 1 to 5.) (Wherein, R1 is a hydrogen atom, a hydroxyl group or a C1-10
An alkyl group, a haloalkyl group or an aryl group of
2 is a hydrogen atom, an alkyl group or an aryl group having 1 to 5 carbon atoms, m is an integer of 0 to 3, n is an integer of 1 to 4, and m + n ≦ 4. ) 3. The solvent is at least one solvent selected from ethyl lactate, 3-methoxymethyl propionate, 3-ethoxyethyl propionate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. The thermosetting composition according to claim 1. 4. The heat according to claim 1, wherein
Protective coating for color filter formed from curable composition
film.