JP3360546B2 - Thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful thermosetting resin composition, and more particularly, to a thermosetting resin composition suitable for a protective film of a color filter used in a liquid crystal display device or a photographic device. About.

[0002]

2. Description of the Related Art A liquid crystal display element and a solid-state imaging element are formed by laminating a driving electric wiring, a switching element, a color filter for color separation, a photoelectric conversion element, and the like on a glass or silicon substrate. In such an element,
An organic coating layer called a protective film is formed for the purpose of electrically insulating or flattening and preventing physical destruction of the element due to external factors.

[0003] For this protective film, transparency, adhesion,
Smoothness, spatter resistance, toughness, heat resistance, light resistance, water resistance, and chemical resistance are required, and in order to further form the protective film, it is generally applied as a solution. In some cases, a spin coating method using a spin coater is used to form a coating film, and the required performance is also considered to be suitable for this coating method.

Conventionally, a (meth) acrylic resin (for example, JP-A-60-216307) has been used as one of the protective film forming materials.
Japanese Patent Application Laid-open No. Hei.
No. 2, JP-B-3-8652), and polyimide resins (for example, JP-A-1-229203) have been studied. Among these resins, (meth) acrylic resins have some problems in balancing physical properties such as adhesion, spatter resistance and heat resistance. Many proposals have been made to remedy these drawbacks.

[0005]

For example, Japanese Patent Application Laid-Open No.
JP-A-216307 and JP-A-4-97102 disclose a method of mixing a polycarboxylic acid anhydride with an epoxy group-containing polymer and heating to form a crosslinked and cured film. And the polyvalent carboxylic acid anhydride were inferior in compatibility and applicability. Also,
Japanese Patent Publication No. 3-8652 discloses a method of forming a cured film by mixing a polycarboxylic acid anhydride and / or a polyvalent carboxylic acid and a functional silane coupling agent with an epoxy group-containing polymer, followed by heating and crosslinking similarly. Although disclosed, there was difficulty in storage stability after compounding.

For this reason, the epoxy resin has excellent properties inherent to epoxy resin, excellent storage stability, excellent coating workability, glossiness, adhesion to a substrate, flatness and surface. There has been a demand for an epoxy-based thermosetting resin composition capable of easily obtaining a cured coating film having excellent smoothness.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have obtained a thermosetting resin composition comprising a polymer containing a compound having a specific epoxy group. As a result, they found that the performance required for the protective film was satisfied, and completed the present invention.

That is, the present invention provides the following general formula:

[0009]

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Wherein R ₁ is hydrogen or a methyl group;
R ₂ is a lower alkyl group, and n is an integer of 1 to 5. Monomer unit (I) consisting of the compound represented by
(A) containing at least 30% by weight of a compound (A), at least one compound (B) selected from the group consisting of polycarboxylic acids and anhydrides thereof, and a silane coupling agent (C). Characterized by a thermosetting resin composition,

Further, there is provided a thermosetting resin composition wherein the lower alkyl group of R _{2 in} the monomer unit (I) represented by the above general formula is a methyl group.

The polymer (A) comprises 1 to 100 parts by weight per 100 parts by weight of the polymer (A), comprising at least one compound (B) selected from the group consisting of polyvalent carboxylic acids and anhydrides thereof. It is a thermosetting resin composition.

Further, a thermosetting resin composition comprising the silane coupling agent (C) in an amount of 0.1 to 30 parts by weight per 100 parts by weight of the polymer (A),

The polymer (A) further has the following general formula:

[0015]

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Wherein R ₁ is hydrogen or a methyl group;
R ₃ is a group consisting of an aliphatic, alicyclic and aromatic hydrocarbon having 6 or more carbon atoms. The present invention is a thermosetting resin composition which is a polymer comprising a monomer unit (II) comprising the compound represented by the formula (1).

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION As the compound represented by the monomer unit (I) used in the present invention, the lower alkyl group of R ₂ is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, etc. An acrylate or methacrylate in which R ₁ is a hydrogen atom or a methyl group. Each of these compounds can be used alone or in combination of two or more compounds, but methyl glycidyl acrylate or methyl glycidyl methacrylate in which R ₂ is a methyl group is preferred.

The content of the compound represented by the monomer unit (I) in the polymer (A) must be at least 30% by weight, preferably at least 50% by weight. It is preferably at least 80% by weight.

When the content of the compound is less than 30% by weight, the curability of the thermosetting resin composition according to the present invention is poor,
Further, the adhesion to the substrate becomes insufficient, and the desired purpose cannot be achieved. Further, the thermosetting resin composition having a content of the compound of 70% by weight or more has excellent curability and exhibits excellent adhesion to various substrates.

The compound represented by the monomer unit (I) can be used after being copolymerized with another polymerizable monomer copolymerizable with the compound. The following are typical examples of other polymerizable monomers. (1) The number of carbon atoms of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octadecyl acrylate, docosyl acrylate, etc. Acrylic acid ester having an alkyl group of 1 to 22 or methacrylic acid ester having the same alkyl group as described above; (2) acrylic acid having a hydroxyalkyl group such as hydroxyethyl acrylate, hydroxypropyl acrylate and glycerol acrylate Esters or methacrylic acid esters or lactone-modified hydroxyethyl acrylates or hydroxyethyl methacrylates having the same hydroxyalkyl group as above,

(3) acrylates having a polyalkylene glycol group such as polyethylene glycol acrylate and polypropylene glycol acrylate or methacrylates having the same polyalkylene glycol group as described above; (4) glycidyl acrylate, α -Glycidyl ethyl acrylate, α-n-propyl glycidyl acrylate, α
Glycidyl n-butyl acrylate, acrylic acid-3,
Glycidyl such as 4-epoxybutyl, acrylate-4,5-epoxypentyl, acrylate-6,7-epoxypentyl, acrylate-6,7-epoxypentyl, α-ethylacrylate-6,7-epoxypentyl (5) dicyclopentenyloxyethyl acrylate, acrylate of tetrahydrofurfuryl alcohol and ε-caprolactone adduct, benzoyloxyethyl acrylate Other acrylates such as phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, or methacrylate having a functional group similar to the above,

(6) unsaturated dicarboxylic acid esters such as dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, dibutyl itaconate, methyl ethyl fumarate, methyl butyl fumarate and methyl ethyl itaconate; Styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene (8) Diene compounds such as butadiene, isoprene, piperylene, and dimethylbutadiene; (9) Halogen such as vinyl chloride, vinyl bromide, vinyl fluoride, and vinylidene fluoride (10) unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone; (11) vinyl esters such as vinyl acetate and vinyl butyrate; and (12) vinyl ethers such as methyl vinyl ether and butyl vinyl ether. ) Acrylonitrile, methacrylonitrile, vinyl cyanide such as vinylidene cyanide, (14) acrylamide and their alkyd substituted amides, (15) N- phenyl maleimide, etc. N- substituted maleimides such as N- cyclohexyl maleimide.

The other polymerizable monomers copolymerizable with the compound represented by the monomer unit (I) can be used alone or in combination of two or more compounds. In particular, by introducing the compound represented by the monomer unit (II) into the polymer (A), the adhesiveness to a substrate and the heat resistance are further improved.

The typical compounds represented by the monomer unit (II) will be exemplified below. (1) Hexyl acrylate, hepsyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, acryl Dodecyl acid, tetradecyl acrylate, hexadecyl acrylate, stearyl acrylate, octadecyl acrylate, acrylate having an alkyl group having 6 or more carbon atoms such as docosyl acrylate, or methacrylate having the same alkyl group as described above, Polyethylene glycol acrylate, acrylic acid ester having a polyalkylene glycol group such as polypropylene glycol acrylate or methacrylate ester having the same polyalkylene glycol as described above,

(2) acrylic acid esters having an alicyclic alkyl group such as cyclohexyl acrylate and isobornyl acrylate, or methacrylic acid esters having the same alicyclic alkyl group as described above; (3) acrylic acid Acrylic esters having an aromatic ring such as benzyl, and methacrylic esters having an aromatic ring similar to those described above are exemplified.

The content of the polymerizable monomer and / or monomer unit (II) copolymerizable with the compound represented by the monomer unit (I) is 70% by weight of the polymer (A). It is desirable that the range is not exceeded. If their content is 70
If the weight is exceeded, the curability of the thermosetting resin composition according to the present invention decreases, and further, the adhesion to the substrate decreases.

The copolymer form of the copolymer using the compound represented by the monomer unit (I) is not particularly limited.
Any of random copolymers, block copolymers, and the like by addition polymerization may be used, and the copolymerization method may be any of a solution polymerization method, an emulsion polymerization method, and the like.

The molecular weight of the polymer (A) obtained by the above method is not particularly limited as long as the thermosetting resin composition of the present invention can be applied to a substrate as a uniform coating.
Normally, the weight average molecular weight in terms of polystyrene is 3000 to 30
000, which can be appropriately selected according to the purpose and conditions of the coating film formation, such as the thickness of the coating film to be formed and the coating method.

The thermosetting resin composition of the present invention contains, together with the polymer (A), at least one compound (B) selected from the group consisting of polycarboxylic acids and acid anhydrides thereof.

Typical examples of the polycarboxylic acids used in the present invention are as follows: (1) Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid and itaconic acid. (2) alicyclic polycarboxylic acids such as hexahydrophthalic acid, 1,2-cyclohexanecarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, and cyclopentanetetracarboxylic acid, and phthalic acid, isophthalic acid, Terephthalic acid, trimellitic acid, pyromellitic acid, 1,4,5,8-
Examples include naphthalenetetracarboxylic acid and benzophenonetetracarboxylic acid.

The following are typical examples of polycarboxylic anhydrides: (1) phthalic anhydride, itaconic anhydride, succinic anhydride,
Fatty acid dicarboxylic anhydrides such as citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and hymic anhydride (2) 1,2,3,4- Aliphatic polycarboxylic dianhydrides such as butanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride (3) pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride (4) Acid anhydrides containing ester groups such as ethylene glycol bis trimellitate and glycerin tristrimate may be mentioned.

As the carboxylic anhydride, a commercially available epoxy resin curing agent composed of a colorless acid anhydride can also be suitably used. As a specific example, Adeka Hardener E
H-700 [Product name (the same applies hereinafter) Asahi Denka Kogyo Co., Ltd.
RIC-HH, MH-700 [manufactured by Shin Nippon Rika Co., Ltd.], Epikini 126, YH-306, DX
-126 [manufactured by Yuka Shell Epoxy Co., Ltd.] and the like.

Further, the polycarboxylic acid or its anhydride may be a resin having two or more carboxyl groups or its anhydride in the molecule, and those known per se may be used. Among them, if particularly representative examples are shown, for example, having a carboxyl group, urethane resin, acrylic resin, polyester resin, lactone modified polyester resin, polyester amide resin, alkyd resin, polyether resin, modified polyether resin,
Examples thereof include a polythioether resin, a polycarbonate resin, a polyacetal resin, a polyolefin resin, an epoxy-modified resin, a silicone resin, and a fluororesin.

Among these, aromatic polycarboxylic anhydrides are particularly preferred in view of compatibility and workability. The polycarboxylic acids and polycarboxylic anhydrides described above can be used alone or in combination of two or more.

The compounding amount of the compound (B) in the thermosetting resin composition of the present invention depends on the amount of the polymer 10 as the component (A).
It is in the range of 1 to 100 parts by weight per 0 parts by weight, preferably 5 to 50 parts by weight. If the blending amount of the component (B) is less than 1 part by weight, the curability of the thermosetting resin composition of the present invention is insufficient, so that a tough coating film cannot be formed, and 100 parts by weight. Exceeding the portion lowers the adhesiveness of the coating to the substrate and makes it difficult to form a uniform and smooth coating by spin coating.

The thermosetting resin composition of the present invention contains a silane coupling agent as the component (C). Here, the silane coupling agent refers to a silane coupling agent having a reactive substituent such as an amino group, a methacryloyl group, an epoxy group, a mercapto group, a vinyl group, a carboxy group, and an isocyanate group. If you stop by example things,

(1) γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl)
Aminopropylmethyldimethoxysilane, (2) γ-methacryloxypropyltrimethoxysilane, (3) γ-
Glycidoxypropyltrimethoxysilane, β- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, (4) γ-mercaptopropyltrimethoxysilane (5) vinyltriacetoxysilane, vinyltrimethoxysilane, (6) trimethoxysilylbenzoic acid (7) γ-isocyanatopropyltri Examples include ethoxysilane and the like, and oligomers and polymers composed of these silane coupling agents.

Among them, silane coupling agents having an epoxy group such as γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are particularly excellent for various substrates. It is preferable in that it provides smoothness, adhesion, water resistance and solvent resistance. These silane coupling agents can be used alone or in combination of two or more.

The amount of the silane coupling agent as the component (C) in the resin composition of the present invention is in the range of 0.1 to 30 parts by weight per 100 parts by weight of the polymer as the component (A). Preferably it is 0.5 to 20 parts by weight. The amount of component (C), which is a silane coupling agent, is 0.1
If the amount is less than 10 parts by weight, the smoothness of the coating film formed and the adhesion to the substrate, water resistance and solvent resistance are insufficient, and if it exceeds 30 parts by weight, the improvement of the adhesion is no longer expected. This is not preferred because the curability of the formed coating film decreases.

The thermosetting resin composition of the present invention contains a compound represented by the monomer unit (I) in the polymer (A) to form a glycidyl acrylate or glycidyl methacrylate monomer. Storage stability after blending a polycarboxylic acid and / or its anhydride (B) as a curing agent and a silane coupling agent (C) as compared with a polymer using a monomer, Further, by introducing the monomer unit (II) into the polymer (A), the heat resistance and the storage stability are markedly improved.

The thermosetting resin composition of the present invention comprises the above-mentioned components (A) to (C) as essential components.
If necessary, various additives such as a stabilizer such as an antioxidant and an ultraviolet absorber and a leveling agent can be added to such an extent that the transparency is not impaired. When transparency is not required depending on the purpose of the coating film, a pigment, a paint, a filler, and the like can be blended.

The thermosetting resin composition of the present invention can be obtained by uniformly mixing the above components. As a method for mixing these components, a solvent mixing method for dissolving and mixing these components in an appropriate solvent is usually preferable. The solvent used for solvent mixing is not particularly limited as long as it dissolves each of the above components and does not react with these components, and various solvents can be used. Just to illustrate,

(1) Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, methyl-n-hexyl ketone, diethyl ketone, ethyl-n -Butyl ketone,
Ketone solvents such as di-n-propyl ketone, diisobutyl ketone, cyclohexanone, and holon (2) ethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane , Ether solvents such as tetrahydrofuran, etc. (3) ethyl formate, propyl formate, n-butyl formate,
Ethyl acetate, n-propyl acetate, isopropyl acetate,
Examples thereof include ester solvents such as n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate.

The order of mixing when preparing the thermosetting resin composition of the present invention by solvent mixing is not particularly limited. For example, all the components are simultaneously dissolved in a solvent to prepare a solution of the present composition. Alternatively, if necessary, each component may be separately dissolved in the same or different solvent to form two or more solutions, and these solutions may be mixed to prepare a solution of the thermosetting composition of the present invention. Good.

For example, by preparing a solution of the component (B) and a solution of the remaining other components in advance and mixing them at a desired ratio immediately before use, the storage stability of each component over a long period of time can be improved. By simply improving or changing the mixing ratio of the two solutions, it is possible to easily change the coating film performance according to the purpose.

The concentration of the thermosetting resin composition solution of the present invention is not particularly limited and can be appropriately selected depending on the purpose of use, but is generally 5 to 50% by weight.
Use degree.

The desired coating film can be obtained by applying the solution of the resin composition of the present invention prepared as described above to the surface of the substrate and curing it by heating.

The method of applying the solution of the thermosetting resin 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. One of the features of the present invention is that the thermosetting resin composition of the present invention is also suitable for the spin coating method. The thermosetting conditions of the thermosetting resin composition of the present invention are as follows. Although it is appropriately selected depending on the mixing ratio and the like, it is usually at 80 to 250 ° C. for about 15 minutes to 10 hours.

Thus, the coating film obtained from the thermosetting resin composition of the present invention has a high light transmittance in a wide wavelength range from ultraviolet to visible and has excellent transparency. And exhibits excellent adhesion to various substrates. Examples of the substrate include glass, metal, and plastic.

The coating film is smooth, tough, excellent in light resistance and heat resistance, does not undergo deterioration such as discoloration even after long-term use.
It is also excellent in solvent resistance and stain resistance, and has high hardness.

Due to these features, the coating film formed by the thermosetting resin composition of the present invention is useful not only as a protective coating film on the substrate surface of various articles, but also as a protective coating layer for a color separation filter. It is extremely suitable as a surface protective layer and the like, and a highly reliable color separation filter having excellent color clarity and brightness can be obtained.

[0052]

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the following, all parts and percentages are by weight unless otherwise specified.

<Synthesis of Polymer (A)> Synthesis Example 1 In a nitrogen atmosphere, propylene glycol monomethyl ether acetate (hereinafter referred to as PGMA) was placed in a 2000 ml flask.
C.) and heated to 115 ° C. with stirring, and then methyl glycidyl methacrylate (hereinafter abbreviated as M-GMA) 500.0 parts and perbutyl O [Nippon Oil & Fats Co., Ltd.] And 25.0 parts of organic peroxide t-butylperoxy-2-ethylhexanate. After the dropwise addition, the mixture was kept at 115 ° C. for 1 hour, and then was added to Perbutyl Z [manufactured by NOF Corporation.
0.3 parts of [organic peroxide t-butylperoxybenzoate] was added, and the mixture was further reacted at the same temperature for 6 hours. The resin solution obtained had a non-volatile content (residual resin weight% after drying at 150 ° C. for 1 hour) of 49.2% and a Gardner viscosity of I-
In J, the number average molecular weight in terms of polystyrene was 4,200. Hereinafter, this polymer is abbreviated as A-1.

Synthesis Example-2 In Synthesis Example-1, 350.0 parts of M-GMA and 150.0 parts of styrene were used in place of 500.0 parts of M-GMA, and 25.0 parts of perbutyl O were further used. In the same manner as in Synthesis Example 1 except that the
A resin solution having 9.4%, viscosity of MN and number average molecular weight of 10,000 was obtained. Hereinafter, this polymer is abbreviated as A-2.

Synthesis Example 3 Same as Synthesis Example 1 except that M-GMA 250.0 parts and styrene 250.0 parts were used instead of M-GMA 500.0 parts. And the non-volatile content is 4
A resin solution having a 9.6% viscosity, FG and a number average molecular weight of 4,400 was obtained. Hereinafter, this polymer is abbreviated as A-3.

Synthetic Example-4 Same as Synthetic Example-1, except that in place of 500.0 parts of M-GMA, 150.0 parts of M-GMA and 350.0 parts of styrene were used. And the non-volatile content is 4
A resin solution having a 9.8% viscosity, a viscosity of EF and a number average molecular weight of 4600 was obtained. Hereinafter, this polymer is abbreviated as A-4.

Synthesis Example-5 In Synthesis Example-1, 200.0 parts of M-GMA, 50.0 parts of styrene, and 25.0 parts of glycidyl methacrylate were used instead of 500.0 parts of M-GMA. Except that the nonvolatile content was 49.5%,
A resin solution having a viscosity of KL and a number average molecular weight of 4,500 was obtained. Hereinafter, this polymer is abbreviated as A-5.

Synthesis Example-6 In Synthesis Example-1, 350.0 parts of M-GMA, 100.0 parts of styrene, and 50.0 parts of stearyl methacrylate were used in place of 500.0 parts of M-GMA. Except that the nonvolatile content was 49.2%,
A resin solution having a viscosity of GH and a number average molecular weight of 4,400 was obtained. Hereinafter, this polymer is abbreviated as A-6.

Synthesis Example-7 In Synthesis Example-1, 200.0 parts of M-GMA, 100.0 parts of styrene and 150.0 parts of stearyl methacrylate were used instead of 500.0 parts of M-GMA. Except that the non-volatile content was 49.7.
%, A resin solution having a viscosity of BC and a number average molecular weight of 4600 was obtained. Hereinafter, this polymer is abbreviated as A-7.

Synthesis Example -8 In Synthesis Example-1, 350.0 parts of M-GMA and 150.0 parts of stearyl methacrylate were used in place of 500.0 parts of M-GMA, and 250.0 parts of perbutyl O were further used. 0
A resin solution having a nonvolatile content of 49.3%, a viscosity of GH and a number average molecular weight of 12,000 was obtained in the same manner as in Synthesis Example 1 except that the parts were changed to 10.0 parts. Hereinafter, this polymer is referred to as A
Abbreviated as -8.

Synthesis Example-9 In Synthesis Example-1, 350.0 parts of M-GMA, 100.0 parts of styrene and 500.0 parts of dicyclopentenyloxyethyl methacrylate were used in place of 500.0 parts of M-GMA. Except for using 0 part, in the same manner as in Synthesis Example-1, the nonvolatile content was 49.2%, the viscosity was IJ and the number average molecular weight was 4
A resin solution of 700 was obtained. Hereinafter, this polymer is abbreviated as A-9.

Synthesis Example-10 In Synthesis Example-1, 350.0 parts of M-GMA, 100.0 parts of styrene and 50.0 parts of isobornyl methacrylate were used instead of 500.0 parts of M-GMA. Except that the nonvolatile content was 49.4.
%, A resin solution having a viscosity of HI and a number average molecular weight of 4600 was obtained. Hereinafter, this polymer is abbreviated as A-10.

Synthesis Example 11 The procedure of Synthesis Example 1 was repeated, except that 500.0 parts of glycidyl methacrylate was used instead of 500.0 parts of M-GMA. .9%,
A resin solution having a viscosity of LM and a number average molecular weight of 4400 was obtained. Hereinafter, this polymer is abbreviated as A-11.

SYNTHETIC EXAMPLE-12 Same as Synthetic Example-1, except that in place of 500.0 parts of M-GMA, 350.0 parts of glycidyl methacrylate and 150.0 parts of styrene were used. Thus, a resin solution having a nonvolatile content of 49.8%, a viscosity of JK and a number average molecular weight of 4600 was obtained. Hereinafter, this polymer is referred to as A-
Abbreviated as 11.

Example 1 30.0 parts of the polymer A-1 obtained in Synthesis Example 1 was weighed into a glass container, and 24.7 parts of PGMAC and 0 parts of γ-glucidoxypropyltrimethoxysilane were weighed. 9.9 parts were mixed and stirred at room temperature, and then 10.5 parts of a trimellitic anhydride solution dissolved at 20% in dimethyldiglycol (hereinafter abbreviated as DMDG) was added to the resulting solution. And mixed until The viscosity of the resin solution thus obtained was 11 cps. The product was prepared with a pore size of 0.2 μm.
And then spin-coated at 700 rpm on a glass plate using a spin coater. After the application, the glass plate was preliminarily dried at 100 ° C. for 2 minutes, and then heat-treated in a constant temperature bath at 230 ° C. for 30 minutes to cure the coating. The surface of the obtained coating film was extremely smooth, and the film thickness was 3.2 μm.

With respect to the coating film prepared as described above,
The following tests were performed. First, the absorption spectrum of the glass plate applied and cured by the above method was measured based on the used glass plate itself. The light transmittance was 95% or more in the entire region from 350 nm to 800 nm.

Next, a peeling test using a cellophane adhesive tape was performed to examine the adhesiveness of the coating film applied and cured on the glass plate. As a result, no peeling was observed. After the glass plate was treated in boiling water at 100 ° C. for 10 minutes, a peeling test was conducted in the same manner, but no peeling was observed.

Further, the above glass plate was placed at 40 ° C. at 10% by weight.
No peeling was observed in a peeling test after treatment in an aqueous hydrochloric acid solution for 30 minutes. Further, no peeling was observed in a peeling test after treating the glass plate in a 2% by weight aqueous solution of sodium hydroxide at 40 ° C. for 30 minutes.

When the above glass plate was treated in N-methyl-2-pyrrolidone at 23 ° C., no peeling was observed. Further, as a result of heat-treating the glass plate with a coating film formed in the same manner as above at 250 ° C. for 2 hours, no crack or the like was observed in the coating film, and no change in the absorption spectrum was observed.

Further, the above-prepared resin solution was heated at 40 ° C.
Was stored for one month.
It only increased from 1 cps. To 17 cps. From the above results, the resin composition of the present invention has excellent storage stability, and the cured coating film obtained from the resin composition has transparency,
It is clear that the adhesiveness, water resistance, acid resistance, alkali resistance and solvent resistance are extremely excellent.

Example 2 A resin composition was obtained in the same manner as in Example 1, except that the following substances were used.

Using 30.0 parts of polymer A-2, 29.3 parts of PGMAC, 0.9 part of γ-glucidoxypropyltrimethoxysilane, 7.4 parts of TMA (20% DMDG solution) The resin solution was prepared. The viscosity of the obtained resin solution was 12 cps.

Next, a 3.9 μm-thick cured film was formed on a glass plate by spin coating in the same manner as in Example 1. The surface of the coating was very smooth. Table 1 shows the results of performing the same test as in Example 1 on the obtained coating film.
It was shown to.

Example 3 A resin composition was obtained in the same manner as in Example 1 except that the following substances were used.

Using 30.0 parts of polymer A-3, 29.5 parts of PGMAC, 0.9 part of γ-glucidoxypropyltrimethoxysilane, 5.3 parts of TMA (20% DMDG solution) The resin solution was prepared. The viscosity of the obtained resin solution was 10 cps.

Then, a 2.9 μm-thick cured film was formed on a glass plate by spin coating in the same manner as in Example 1. The surface of the coating was very smooth. Table 1 shows the results of performing the same test as in Example 1 on the obtained coating film.
It was shown to.

Example 4 A resin composition was obtained in the same manner as in Example 1 except that the following substances were used.

Using 30.0 parts of polymer A-4, 27.5 parts of PGMAC, 0.9 part of γ-glucidoxypropyltrimethoxysilane 3.2 parts of TMA (20% DMDG solution) The resin solution was prepared. The viscosity of the obtained resin solution was 13 cps.

Then, a 2.8 μm-thick cured film was formed on a glass plate by spin coating in the same manner as in Example 1. The surface of the coating was very smooth. Table 1 shows the results of performing the same test as in Example 1 on the obtained coating film.
It was shown to.

Example-5 A resin composition was obtained in the same manner as in Example-1, except that the following substances were used.

Using 30.0 parts of polymer A-5, 34.6 parts of PGMAC, 0.9 part of γ-glucidoxypropyltrimethoxysilane, 10.0 parts of TMA (20% DMDG solution). The resin solution was prepared. The viscosity of the obtained resin solution was 11 cps.

Next, a 3.0 μm-thick cured film was formed on a glass plate by spin coating in the same manner as in Example 1. The surface of the coating was very smooth. Table 1 shows the results of performing the same test as in Example 1 on the obtained coating film.
It was shown to.

Example-6 A resin composition was obtained in the same manner as in Example 1, except that the following substances were used.

Using 30.0 parts of polymer A-6, 31.5 parts of PGMAC, 0.9 part of γ-glucidoxypropyltrimethoxysilane, 7.4 parts of TMA (20% DMDG solution) The resin solution was prepared. The viscosity of the obtained resin solution was 10 cps.

Next, a 3.4 μm-thick cured film was formed on a glass plate by spin coating in the same manner as in Example 1. The surface of the coating was very smooth. Table 1 shows the results of performing the same test as in Example 1 on the obtained coating film.
It was shown to.

Example-7 A resin composition was obtained in the same manner as in Example 1, except that the following substances were used.

Using 30.0 parts of polymer A-7, 27.3 parts of PGMAC, 0.9 part of γ-glucidoxypropyltrimethoxysilane 5.3 parts of TMA (20% DMDG solution) The resin solution was prepared. The viscosity of the obtained resin solution was 13 cps.

Next, a 3.6 μm-thick cured film was formed on a glass plate by spin coating in the same manner as in Example 1. The surface of the coating was very smooth. Table 1 shows the results of performing the same test as in Example 1 on the obtained coating film.
It was shown to.

Example-8 A resin composition was obtained in the same manner as in Example 1, except that the following substances were used.

Using 30.0 parts of polymer A-8, 37.2 parts of PGMAC, 0.9 part of γ-glucidoxypropyltrimethoxysilane, 7.4 parts of TMA (20% DMDG solution) The resin solution was prepared. The viscosity of the obtained resin solution was 11 cps.

Next, a 3.8 μm thick cured film was formed on a glass plate by a spin coating method in the same manner as in Example 1. The surface of the coating was very smooth. Table 1 shows the results of performing the same test as in Example 1 on the obtained coating film.
It was shown to.

Example 9 A resin composition was obtained in the same manner as in Example 1, except that the following substances were used.

Using 30.0 parts of polymer A-9, 29.0 parts of PGMAC, 0.9 part of γ-glucidoxypropyltrimethoxysilane, 7.4 parts of TMA (20% DMDG solution) The resin solution was prepared. The viscosity of the obtained resin solution was 12 cps.

Next, a coating film having a cured thickness of 3.0 μm was formed on a glass plate by a spin coating method in the same manner as in Example-1. The surface of the coating was very smooth. Table 1 shows the results of performing the same test as in Example 1 on the obtained coating film.
It was shown to.

Example 10 A resin composition was obtained in the same manner as in Example 1, except that the following substances were used.

30.0 parts of polymer A-10, PGMAC
And 30.9 parts of γ-glucidoxypropyltrimethoxysilane and 7.4 parts of TMA (20% DMDG solution) were used to prepare a resin solution. The viscosity of the obtained resin solution was 13 cps.

Next, a 3.2 μm-thick cured film was formed on a glass plate by spin coating in the same manner as in Example 1. The surface of the coating was very smooth. Table 1 shows the results of performing the same test as in Example 1 on the obtained coating film.
It was shown to.

Example 11 A resin composition was obtained in the same manner as in Example 1 except that the following substances were used.

Using 30.0 parts of polymer A-6, 22.7 parts of PGMAC, 0.9 part of γ-glucidoxypropyltrimethoxysilane, 22.1 parts of TMA (20% DMDG solution) The resin solution was prepared. The viscosity of the obtained resin solution was 12 cps.

Next, in the same manner as in Example 1, a 2.9 μm-thick cured film was formed on a glass plate by a spin coating method. The surface of the coating was very smooth. Table 1 shows the results of performing the same test as in Example 1 on the obtained coating film.
It was shown to.

Example 12 A resin composition was obtained in the same manner as in Example 1, except that the following substances were used.

Using 30.0 parts of polymer A-6, 19.2 parts of PGMAC, 0.9 part of γ-glucidoxypropyltrimethoxysilane, 11.0 parts of TMA (20% DMDG solution) The resin solution was prepared. The viscosity of the obtained resin solution was 13 cps. Then, a 2.7 μm-thick cured film was formed on a glass plate by a spin coating method in the same manner as in Example-1.
Was formed. The surface of the coating was very smooth. Table 1 shows the results of the same test as in Example 1 performed on the obtained coating film.

Example 13 A resin composition was obtained in the same manner as in Example 1, except that the following substances were used.

30.0 parts of polymer A-6, 29.0 parts of PGMAC, 0.9 part of γ-glucidoxypropyltrimethoxysilane 5 of pyromellitic anhydride (20% γ-butyrolactone solution) The resin solution was prepared using .5 parts. The viscosity of the obtained resin solution was 11 cps.

Then, a 3.2 μm-thick cured film was formed on a glass plate by spin coating in the same manner as in Example-1. The surface of the coating was very smooth. Table 1 shows the results of performing the same test as in Example 1 on the obtained coating film.
It was shown to.

Example 14 A resin composition was obtained in the same manner as in Example 1, except that the following substances were used.

30.0 parts of polymer A-6 and 3 parts of DMDG
A resin solution was prepared using 1.5 parts of 0.9 part of γ-methacryloxypropyltrimethoxysilane and 7.4 parts of TMA (20% DMDG solution). The viscosity of the obtained resin solution was 13 cps.

Next, a cured film having a thickness of 3.1 μm was formed on a glass plate by a spin coating method in the same manner as in Example-1. The surface of the coating was very smooth. Table 1 shows the results of performing the same test as in Example 1 on the obtained coating film.
It was shown to.

Example 15 A resin composition was obtained in the same manner as in Example 1, except that the following substances were used.

A resin solution was prepared using 30.0 parts of polymer A-6, 26.8 parts of PGMAC, and 0.9 parts of vinyltriacetoxysilane, 7.4 parts of TMA (20% DMDG solution). . The viscosity of the obtained resin solution was 12 cps.

Next, a cured film having a thickness of 3.3 μm was formed on a glass plate by a spin coating method in the same manner as in Example-1. The surface of the coating was very smooth. Table 1 shows the results of performing the same test as in Example 1 on the obtained coating film.
It was shown to.

Comparative Example 1 A resin composition was obtained in the same manner as in Example 1, except that the following substances were used.

Using 30.0 parts of polymer A-11, 27.6 parts of DMDG, 0.9 part of γ-glycidoxypropyltrimethoxysilane, 11.5 parts of TMA (20% DMDG solution) The resin solution was prepared. The viscosity of the obtained resin solution was 11 cps. Next, a cured film thickness of 3.4 μm was formed on a glass plate by spin coating in the same manner as in Example-1.
Was formed. The surface of the coating was very smooth. Table 1 shows the results of the same test as in Example 1 performed on the obtained coating film.

Comparative Example 2 A resin composition was obtained in the same manner as in Example 1, except that the following substances were used.

30.0 parts of polymer A-12, PGMAC
And 20.9 parts of γ-glycidoxypropyltrimethoxysilane and 8.1 parts of TMA (20% DMDG solution) were used to prepare a resin solution. The viscosity of the obtained resin solution was 13 cps.

Next, a 3.6 μm-thick cured film was formed on a glass plate by spin coating in the same manner as in Example 1. The surface of the coating was very smooth. Table 1 shows the results of performing the same test as in Example 1 on the obtained coating film.
It was shown to.

[0117]

[Table 1]

[0118]

The present invention has excellent storage stability and excellent heat resistance, transparency, adhesiveness, water resistance, acid resistance, alkali resistance, and solvent resistance, and has good coating workability and surface smoothness. It is possible to provide a thermosetting resin composition that can easily form a cured coating film having excellent heat resistance.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-6-281801 (JP, A) JP-A-5-78453 (JP, A) JP-A-60-217230 (JP, A) JP-A-7- 126352 (JP, A) JP-A-5-93047 (JP, A) JP-A-4-133001 (JP, A) JP-A-3-188153 (JP, A) JP-A-61-252225 (JP, A) (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 59/20-59/32 C08G 59/42 C08K 5/541-5/5435 C08L 63/00 G02B 5/20

Claims (5)

(57) [Claims] [Claim 1] The following general formula: (Wherein, R ₁ is hydrogen or a methyl group, R ₂ is a lower alkyl group, and n is an integer of 1 to 5). Characterized in that it comprises a polymer (A) containing at least 1% by weight, at least one compound (B) selected from the group consisting of polycarboxylic acids and anhydrides thereof, and a silane coupling agent (C).
A thermosetting resin composition. 2. A general lower alkyl group R ₂ in the formula is a methyl group, according to claim 1 thermosetting resin composition. 3. A polycarboxylic acid and one or more compounds selected from the group consisting of anhydride (B), comprising the polymer (A) 1 to 100 parts by weight per 100 parts by weight
The thermosetting resin composition according to claim 1, wherein Wherein the silane coupling agent (C), those comprising the polymer (A) 0.1 to 30 parts by weight per 100 parts by weight, the heat of any one of claims 1 to 3 Curable resin composition. 5. The polymer (A) further has the following general formula: (Wherein, R ₁ is hydrogen or a methyl group, and R ₃ is a group consisting of an aliphatic, alicyclic, and aromatic hydrocarbon having 6 or more carbon atoms). The thermosetting resin composition according to any one of claims 1 to 4, which is a polymer comprising a unit (II).