JP2003160711A - Thermosetting resin composition, protective film material for optical device, resin cured product and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition excellent in coating workability, hardly causing unevenness in the coated face and capable of giving a cured coating excellent in heat resistance, and free from discoloration or weight reduction by heating, to provide a protective film material for an optical device, and further to provide a resin cured product and a color filter made by using these composition and material. <P>SOLUTION: This thermosetting resin composition comprises a copolymer (A) obtained by polymerising an ethylenic unsaturated monomer (a1) having an epoxy group, an ethylenic unsaturated monomer (a2) having a blocked carboxy group and another copolymerizable ethylenic unsaturated monomer (a3), by using these monomers in the proportion of 45 to 75 wt.% (a1), 10 to 40 wt.% (a2) and 5 to 45 wt.% (a3). The resin cured product is obtained by curing the composition. The protective film material for an optical device comprises the composition. The color filter has a cured film comprising the protective film material for the optical device as the surface protective film. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel and useful thermosetting resin composition, a protective film material for an optical device comprising the thermosetting resin composition, and a thermosetting resin composition cured. The present invention relates to a color filter having, as a surface protective film, a resin cured product and a cured film composed of the protective film material for an optical device. More specifically, the present invention relates to a protective film material for an optical device suitable for manufacturing a color filter of a display element such as a liquid crystal display (LCD), and a color filter using the protective film material.

[0002]

2. Description of the Related Art A liquid crystal display device or a photographing device is formed by laminating electric wiring for driving, a switching device, a color filter for color separation, a photoelectric conversion device, etc. on a substrate such as glass, silicon or plastic. It A protective film is formed on such an element for the purpose of electrically insulating, planarizing the colored layers of red, green, blue, and preventing physical destruction of the element due to external factors.

Such a protective film has transparency, flatness,
It is required to have excellent adhesiveness to a base material, toughness, heat resistance, weather resistance, moisture resistance, water resistance, chemical resistance and the like. Further, in order to form the protective film uniformly, for example, coating suitability is required when a spin coating method using a spin coater is used. Further, it is also preferred that the cleaning property with an alkaline solution is good for removing the coating film when coating failure occurs.

As a protective film material having these characteristics improved, in JP-A-60-217230, an epoxy group-containing polymer is mixed with a polyvalent carboxylic acid anhydride and / or a polyvalent carboxylic acid and a silane coupling agent. What has been done is proposed. However, since this method is a two-pack type in which the epoxy group-containing polymer as the main component and the polyvalent carboxylic acid anhydride and / or the polyvalent carboxylic acid as the curing agent are mixed immediately before coating, the work is complicated. Yes, and must be used promptly.

Further, in Japanese Patent Application Laid-Open No. 06-157716, a one-pack type which may contain a silane coupling agent, which is obtained by dissolving a copolymer having a carboxyl group and an epoxy group in the molecule in an organic solvent. The thermosetting resin composition of No. 11-335510 further discloses a one-pack type thermosetting resin containing a coupling agent and a copolymer having a carboxysilane group and a glycidyl group in the molecule. Resin compositions have been proposed. However, in any of the above-mentioned methods, it is necessary to satisfy all the performances represented by coating properties and heat resistance, such as having a uniform and even coated surface and suppressing the decrease in coloring and film thickness due to heating. Was difficult.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that an ethylenically unsaturated monomer (a1) having an epoxy group and a blocked carboxyl group are contained. Ethylenically unsaturated monomer (a
2) and other copolymerizable ethylenically unsaturated monomer (a3), (a1) is 45 to 75% by weight,
2) is 10 to 40% by weight and (a3) is 5 to 45
% By weight [however, the total of (a1), (a2) and (a3) is 100% by weight. ] The thermosetting resin composition containing the copolymer (A) polymerized by using the following ratio, preferably a part or all of the ethylenically unsaturated monomer (a1) having an epoxy group. Is a thermosetting resin composition in which is an ethylenically unsaturated monomer (a12) having an alicyclic epoxy group, a protective film material for optical devices comprising the thermosetting resin composition, and a resin using the same It was found that the cured product and the color filter can solve the above problems, and the present invention has been completed.

That is, the present invention comprises an ethylenically unsaturated monomer (a1) having an epoxy group and an ethylenically unsaturated monomer (a2) having a blocked carboxyl group.
Other copolymerizable ethylenically unsaturated monomer (a3)
And an ethylenically unsaturated monomer having an epoxy group (a
1) is 45 to 75% by weight and the ethylenically unsaturated monomer (a2) having a blocked carboxyl group is 10 to 10%.
40% by weight and 5 to 45% by weight of the other copolymerizable ethylenically unsaturated monomer (a3) (provided that (a
The total of 1), (a2) and (a3) is 100% by weight. ] The thermosetting resin composition characterized by containing the copolymer (A) which is made to polymerize by using the following ratio.

Further, the present invention provides a protective film material for an optical device, which is characterized by comprising the above-mentioned thermosetting resin composition.

Furthermore, the present invention provides a cured resin product, characterized in that the thermosetting resin composition is cured.

Furthermore, the present invention provides a color filter having a cured film made of the protective film material for an optical device as a surface protective film.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
Examples of the epoxy group-containing ethylenically unsaturated monomer (a1) used in the present invention include the following general formula (1)

[Chemical 1] (In the formula, R ₁ and R ₂ may be the same or different and each is an alkyl group having 1 to 18 carbon atoms, a phenyl group, an allyl group or a hydrogen atom, and n is an integer of 1 to 5. .)
And the ethylenically unsaturated monomer (a12) having an alicyclic epoxy group.

The compound (a1) represented by the general formula (1)
As 1), for example, glycidyl (meth) acrylate, glycidyl α-methyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, glycidyl α-n-propyl (meth) acrylate, α-n- Glycidyl group-containing (meth) acrylic acid ester such as glycidyl butyl (meth) acrylate; (meth) acrylic acid-3,4
(Epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxypentyl, α-ethyl (meth) acrylic acid-6,7-epoxypentyl, etc. (meth)) Epoxy alkyl acrylate, etc., among others, containing glycidyl group (meth)
Acrylate esters are preferred, and glycidyl (meth) acrylate is particularly preferred.

Examples of the alicyclic epoxy group-containing ethylenically unsaturated monomer (a12) include (meth) acrylic acid-3,4-epoxycyclohexyl and lactone-modified (meth) acrylic acid-3. , 4-epoxycyclohexyl, etc. (meth) acrylic acid epoxycyclohexyl; vinylcyclohexene oxide, etc., vinylcycloalkyl oxide, etc., among which (meth) acrylic acid epoxycyclohexyl is preferable, and (meth)
Particularly preferred is 3,4-epoxycyclohexyl acrylate.

When the copolymer (A) used in the present invention is polymerized, the ethylenic unsaturated monomer (a1) having an epoxy group may be contained in the monomer composition either alone or in combination of two or more kinds. .

In a protective film material for an optical device, a transparent electrode represented by an oxide of indium and tin (ITO) may be formed on the protective film. Particularly when the sputtering method under high temperature and high vacuum is used, the sputtering resistance is required so as not to impair the performance as a protective film even in this environment. When the copolymer (A) used in the present invention is polymerized, an ethylenically unsaturated monomer having an epoxy group (a
It is preferable to use the alicyclic epoxy group-containing ethylenically unsaturated monomer (a12) as a part or all of 1) since a cured coating film having excellent sputtering resistance can be obtained. Among them, since a cured coating film having excellent sputtering resistance can be obtained without lowering the heat resistance, the ethylenically unsaturated monomer having an alicyclic epoxy group is contained in the ethylenically unsaturated monomer having an epoxy group (a1). It is more preferable that the saturated monomer (a12) is contained in the range of 5 to 60 mol%, and particularly preferable that the saturated monomer (a12) is contained in the range of 10 to 40 mol%. In addition, like these, an ethylenically unsaturated monomer having an epoxy group (a
When the ethylenically unsaturated monomer having an alicyclic epoxy group (a12) is used as a part of 1), the other ethylenically unsaturated monomer having an epoxy group is represented by the general formula (1). It is preferable to use the compound (a11) represented in combination.

In the present invention, during the production of the copolymer (A), a thermosetting resin composition and a photocurable resin composition which are less prone to gelation due to a reaction between a carboxyl group and an epoxy group, are easy to produce and have excellent storage stability are provided. Since a protective film material for devices can be obtained, the ethylenically unsaturated monomer (a2) having a blocked carboxyl group is used as the ethylenically unsaturated monomer having a carboxyl group.

The ethylenically unsaturated monomer (a2) having a blocked carboxyl group used in the present invention is not particularly limited, but for example, an ethylenically unsaturated monomer having a carboxysilane group blocked with silanol is used. Even if coating defects or the like occur in the polymer, it is preferable that the polymer can be washed with an alkaline solution before being completely cured.

The ethylenically unsaturated monomer having a carboxysilane group is represented by the following general formula (2)

[Chemical 2] (Wherein R ₁ , R ₂ and R ₃ may be the same or different and each represents an alkyl group having 1 to 18 carbon atoms, a phenyl group, an allyl group or a hydrogen atom). Examples thereof include an ethylenically unsaturated monomer having a group.

Examples of the ethylenically unsaturated monomer having a carboxysilane group include (meth) acrylic acid having a trialkylsilane such as trimethylsilane (meth) acrylic acid; diethylsilane (meth) acrylate and the like. (Meth) acrylic acid having a dialkylsilane; (meth) acrylic acid triphenylsilane, (meth) acrylic acid triallylsilane and the like can be mentioned. Among them, (meth) acrylic acid having a trialkylsilane is preferable,
Trimethylsilane (meth) acrylate is particularly preferred.

When the copolymer (A) used in the present invention is polymerized, the monomer composition contains at least two ethylenically unsaturated monomers (a2) having a blocked carboxyl group. But good.

Other copolymerizable ethylenically unsaturated monomers (a3) used in the present invention include, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, ( Dodecyl (meth) acrylate, tetradecyl (meth) acrylate,
Hexadecyl (meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate, docosyl (meth) acrylate, and the like (meth) acrylate having an alkyl group having 1 to 22 carbon atoms;

Acrylic esters having alicyclic alkyl groups such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate; tetrahydrofurfuryl alcohol and ε-caprolactone addition (Meth) acrylic acid ester of a substance; hydroxyethyl (meth) acrylate,
(Meth) acrylic acid ester having a hydroxyl group at the terminal such as hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, and lactone-modified hydroxyethyl (meth) acrylate;

Benzoyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc. Acrylic ester having an aromatic ring; (meth) acrylic acid ester having a polyalkylene glycol group such as (meth) acrylic acid polyethylene glycol and (meth) acrylic acid polypropylene glycol; dimethyl fumarate, diethyl fumarate, dibutyl fumarate, Dimethyl itaconate, dibutyl itaconate, methyl ethyl fumarate, methyl butyl fumarate,
Unsaturated dicarboxylic acid esters such as methyl ethyl itaconate;

Styrene compounds such as styrene, α-methylstyrene and chlorostyrene; diene compounds such as butadiene, isoprene, piperylene and dimethylbutadiene; halogenated vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene fluoride and the like. Vinyl and vinylidene halides; unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone; vinyl esters such as vinyl acetate and vinyl butyrate; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; cyanides such as acrylonitrile, methacrylonitrile and vinylidene cyanide. Vinyl chloride; acrylamide and alkyd-substituted amides thereof; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;

Β- (meth) acryloxyethyltrimethoxysilane, β- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane (Meth) acryloxyalkyltrialkoxysilanes such as; vinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane;
It has a (per) fluoroalkyl group having 1 to 18 carbon atoms such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, and heptadecafluorodecyl (meth) acrylate. Fluorine-containing (meth) acrylic acid ester represented by per) fluoroalkyl (meth) acrylate; (meth) acrylic acid ester having an amino group such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; 2 Examples thereof include phosphorus-containing (meth) acrylic acid esters represented by-(meth) acryloyloxyethyl acid phosphate, and these may be used alone or in combination of two or more.

Among the above-mentioned other copolymerizable ethylenically unsaturated monomers (a3), a (meth) acrylic acid ester having an alkyl group, a styrene compound, and a (meth) acrylic acid ester having a hydroxyl group at a terminal are included. , A (meth) acrylic acid ester having fluorine is preferable, a (meth) acrylic acid ester having a styrene compound as an essential component and optionally an alkyl group, a (meth) acrylic acid ester having a hydroxyl group at the terminal, and fluorine It is particularly preferable to use a (meth) acrylic acid ester having

The above-mentioned monomers (a1), (a2) and (a) used when polymerizing the copolymer (A) used in the present invention.
As for the usage ratio of 3), the ethylenically unsaturated monomer (a1) having an epoxy group is 45 to 75% by weight, and the ethylenically unsaturated monomer (a2) having a blocked carboxyl group is 10 to 10% by weight. 40% by weight and 5 to 45% by weight of other copolymerizable ethylenically unsaturated monomer (a3) (provided that the total of (a1), (a2) and (a3) is 100% by weight. To do. ] Is essential, and outside this range, unevenness is likely to occur on the coated surface, the heat resistance of the coating film is poor, there is a decrease in coloring and film thickness due to heating, and a cured coating with a good coating surface state. It is not preferable because it is difficult to obtain a film. The proportion of the monomers (a1), (a2) and (a3) used is, among others, that the monomer (a1) is 4
5 to 60% by weight, and 20 to 35% by weight of the monomer (a2)
In addition, when the monomer (a3) is 5 to 35% by weight, there is no unevenness and there is no coloring or reduction in film thickness due to heating.
Since a cured coating film with a particularly good coating surface state can be obtained,
preferable.

The number average molecular weight of the copolymer (A) used in the present invention is preferably 1,500 to 20,000 because it has excellent heat resistance and a smooth coating film can be obtained.
More preferably, it is 2,000 to 10,000.

The copolymerization method of the copolymer (A) of the present invention is not particularly limited and may be any of random copolymerization by addition polymerization, block copolymerization, graft copolymerization and the like, and the copolymerization method is also a solution polymerization method. , Emulsion polymerization method or the like. Among them, random copolymerization by addition polymerization is preferably performed by a solution polymerization method.

A coupling agent may be added to the thermosetting resin composition and the protective film material for an optical device of the present invention for the purpose of enhancing the adhesion to the substrate. Here, the coupling agent is defined as a compound that enhances the function of the composite material by chemically binding the composite materials or by improving the affinity with a chemical reaction. Examples of such coupling agents include silane compounds, titanium compounds, and aluminum compounds.

As the silane coupling agent, for example,
γ-ureidopropyltriethoxysilane, γ- (2-
Aminoethyl) aminopropyltrimethoxysilane, γ
-(2-aminoethyl) aminopropylmethyldimethoxysilane; γ-methacryloxypropyltrimethoxysilane; γ-glycidoxypropyltrimethoxysilane,
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-mercaptopropyltrimethoxysilane; vinyltriacetoxysilane, vinyltrimethoxysilane; trimethoxysilylbenzoic acid; γ-isocyanatopropyltriethoxysilane and the like, Examples thereof include oligomers and polymers including these silane coupling agents.

As the titanium coupling agent, for example,
Tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetrakis (2-ethylhexoxy) titanium,
Tetra stearoxy titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (triethanolaminato) titanium, dihydroxy
Bis (lactato) titanium, tetrakis (2-ethylhexanediolato) titanium, tri-n-butoxytitanium monostearate, isopropyltriisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetra Isopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctyl pyrophosphate) Oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctano titanate,
Isopropyl dimethacryl isostearoyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate,
Isopropyltri (N-aminoethyl / aminoethyl)
Examples thereof include titanate, dicumylphenyloxyacetate titanate, diisostearoyl ethylene titanate and the like.

Examples of the aluminum coupling agent include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), Alkyl acetoacetate aluminum diisopropylate,
Aluminum monoacetylacetate bis (ethylacetoacetate), aluminum tris (acetylacetonate), cyclic aluminum oxide isopropylate and the like can be mentioned.

Among these coupling agents, the silane coupling agent is preferable, and γ-is preferable because it gives particularly excellent adhesion, water resistance and solvent resistance to various substrates.
Silane coupling agent having amino group such as ureidopropyltriethoxysilane, silane coupling agent having epoxy group such as γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Is particularly preferable. These coupling agents may be used either individually or in combination of two or more.

The amount of the coupling agent added is such that the formed coating film has good smoothness, adhesion to a substrate, water resistance and solvent resistance, and improved adhesion to cure the formed coating film. In order to improve the properties, it is in the range of 0.1 to 30 parts by weight, preferably 0.1 to 100 parts by weight of the copolymer (A).
It is 5 to 20 parts by weight, and particularly preferably 1.0 to 10.0 parts by weight.

In the present invention, 1) reduction of unreacted functional groups which adversely affects physical properties such as water resistance, 2)
Introduction of a stronger cross-linked structure by increasing the number of reaction points 3)
An epoxy group activating catalyst may be used for the purpose of reducing the energy required for heat curing. Specific examples of the epoxy group activating catalyst include electrophiles and nucleophiles.

As the epoxy group activating catalyst, for example,
Lewis acids such as carboxylic acid, phenol, boron fluoride, magnesium chloride, etc .; primary amines such as diethylenetriamine, secondary amines such as metaphenylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol, benzyl Amines such as tertiary amines such as dimethylamine and 1,8-diazabicyclo (5,4,0) undecane (DBU); imidazoles such as 2-methyl-4-ethylimidazole; tetramethylphosphonium bromide, triphenyl Phosphines such as phosphine;
Examples include organic selenium such as phenyl selenium. These epoxy group activating catalysts may be used alone or in combination of two or more.

Of these, tertiary amines, imidazoles, and phosphines are preferable because they are catalytically utilized without themselves being incorporated into the composition. Among them, imidazoles and phosphines do not exert a catalytic effect even in a mixed state with a compound having an epoxy group at room temperature, and have a thermal potential of easily exerting a catalytic effect by giving a specific temperature. Therefore, it is more preferable as a one-pack type thermosetting resin composition that requires storage stability. In particular, phosphines are more preferable as a protective film material for color filters among the protective film materials for optical devices because they are less colored by heat and have high thermal latent performance.

The amount of the epoxy activating catalyst blended is sufficient to sufficiently exert the effect as a catalyst and to maintain good coating physical properties such as storage stability and adhesion to a substrate, so that the copolymer (A)
It is in the range of 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, and particularly preferably 0.05 to 3 parts by weight, per 100 parts by weight.

In the thermosetting resin composition and the protective film material for an optical device of the present invention, if necessary, a polyvalent carboxylic acid and its acid anhydride, an epoxy compound; an antioxidant,
A stabilizer such as an ultraviolet absorber; various additives such as a leveling agent can be added within a range that does not impair transparency. When transparency is not required depending on the purpose of the coating film, pigments, dyes, fillers and the like may be added.

The thermosetting resin composition and the protective film material for an optical device of the present invention can be obtained by uniformly mixing the above components. As a method of mixing these components, a solvent mixing method of dissolving and mixing these components in an appropriate organic solvent is usually preferable.

The organic solvent used for solvent mixing is not particularly limited as long as it dissolves the above components and does not react with these components, and various organic solvents can be used. For example, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, methyl-
Ketone solvents such as n-hexyl ketone, diethyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, and holone;

Ethyl ether, isopropyl ether,
ether solvents such as n-butyl ether, diisoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane and tetrahydrofuran;

Ethyl formate, propyl formate, n-butyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate Ester solvents such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate.

When the thermosetting resin composition and the protective film material for an optical device are prepared by solvent mixing, the order of mixing is not particularly limited. For example, all components are dissolved in an organic solvent at the same time for adjustment. Alternatively, if necessary, each component may be separately dissolved in the same or different organic solvent to prepare two or more solutions, and these solutions may be mixed and adjusted.

The concentration of the solution used as the thermosetting resin composition or the protective film material for the optical device is not particularly limited, and can be appropriately selected according to the purpose of use, but in general, It is about 5 to 50% by weight.

A cured product or a protective film can be obtained by applying the thermosetting resin composition prepared as described above or a solution as a protective film material for an optical device to the surface of a substrate and curing it by heating. The coating method is not particularly limited, and various methods such as a spray method, a roll coating method, and a spin coating method using a spin coater can be used. One of the features of the present invention is that it is particularly suitable for the spin coating method. Is one

The thermosetting conditions are appropriately selected depending on the type and mixing ratio of each component of the thermosetting resin composition and the protective film material for optical devices, but usually at 80 to 250 ° C. for about 15 minutes to 10 hours. is there.

A coating film obtained from the thermosetting composition or the protective film material for an optical device has a high light transmittance in a wide range of wavelength range from ultraviolet to visible region and is excellent in transparency. , Shows excellent adhesion to various substrates. Examples of the substrate include glass, metal, plastic and the like.

When the thermosetting resin composition or the protective film material for optical devices of the present invention is used, the coated plate before being cured by heat, for example, treatment under relatively mild conditions such as predrying at 100 ° C. or lower. The coated plate can be easily solubilized and washed with an aqueous alkali solution such as sodium carbonate or sodium hydroxide or an aqueous solution containing an organic alkali such as tetramethylammonium hydroxide.

That is, while the thermosetting resin composition and the protective film material for optical devices are being applied by a spin coater or the like,
Alternatively, if coating defects such as cissing, coating unevenness, and foreign matter occur during setting after coating and during preliminary drying at 100 ° C or less for several minutes, it is expensive to simply solubilize and wash with an alkaline aqueous solution. It is possible to reuse various substrates, etc., and contribute to effective use of resources.
The concentrations of sodium carbonate and sodium hydroxide may be appropriately determined. Usually, those having a concentration of 0.1 to 5% by weight are used, and washing is performed by a showering or dipping method.

Further, since the thermosetting resin composition and the protective film material for optical devices of the present invention are of one-pack type, the mixing and mixing of the main agent and the curing agent as in the two-pack type, and further defoaming, etc. The workability is excellent because the work is omitted, and the long-term storage stability is excellent in the sealed state.

Due to these characteristics, the coating film formed from the thermosetting resin composition of the present invention is useful as a surface protective film for various article substrates.

[0054]

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% are by weight unless otherwise specified.

Examples 1 to 5 and Comparative Examples 1 to 2 Mixtures of the monomer and the polymerization initiator compounded in the compounding formulations shown in Tables 1 and 2 were heated to 60 ° C. to obtain propylene glycol monomethyl ether acetate (hereinafter , P
Abbreviated as GMAc. ) It was added dropwise to 105 parts over 2 hours, and the reaction was continued at the same temperature for 6 hours. As a result, a copolymer solution having a number average molecular weight shown in the same table (resin solid content concentration 50%) was obtained.

Then, with respect to 50 parts of each copolymer solution,
50 parts of PGMAc and 1.5 parts of γ-ureidopropyltriethoxysilane were added and mixed to obtain a protective film material for an optical device composed of a thermosetting resin composition.

[0057]

[Table 1]

[0058]

[Table 2]

Footnotes in Tables 1 and 2 GMA: glycidyl methacrylate ECHMA: 3,4-epoxycyclohexyl methacrylate TMSM: trimethylsilyl methacrylate St: styrene MMA: methyl methacrylate LHEMA: methacrylic acid lactone modified hydroxyethyl ADVN: 2,2'-azobis- (2,4-dimethylvaleronitrile)

Then, using each of the obtained protective film materials for optical devices, a coating method and a curing method described below are used,
A test sample was prepared and an evaluation test was conducted. The result is the third
Shown in the table.

(1) Coating method: Each of the obtained protective film materials for optical devices was filtered through a filter having a pore size of 0.2 μm, and then rotated at 1000 rpm for 7 seconds using a spin coater to obtain 10 cm × 10 cm. A glass plate was applied onto a glass plate to obtain a glass plate coated with each protective film material for optical devices having a coating thickness of 2 μm after curing.

(2) Curing method: The glass plate coated with the protective film material for optical devices in the coating method (1) was heated to 80 ° C.
Pre-dry at room temperature for 2 minutes and then in a constant temperature bath at 230 ° C for 3
The coating film was cured by heat treatment for 0 minutes to obtain a glass plate having a cured coating film of the protective film material for each optical device.

(3) Evaluation test Applicability test: The appearance of the cured coating film of the glass plate having the cured coating film of the protective film material for each optical device obtained by the curing method (2) was visually observed with a sodium lamp. The case where there was no abnormality in appearance was evaluated as ◯, the case where slight unevenness was observed on the coated surface was evaluated as Δ, and the case where a lot of apparent unevenness was observed on the coated surface was evaluated as x.

Alkali solubility test: The glass plate having the cured coating film of the protective film material for each optical device obtained by the coating method (1) was pre-dried at 80 ° C. for 2 minutes, then allowed to stand for 3 hours, then 40 Immerse in 1% sodium carbonate aqueous solution at ℃ for 2 minutes, then wash with running water and observe the peeling / solubility of the coating film. What was not dissolved at all was evaluated as x.

Heat resistance test: A glass plate having a cured coating film of the protective film material for each optical device obtained by the curing method (2) was heated in a constant temperature bath at 230 ° C. for 10 hours to change the color before and after heating (color difference). ΔE) is a color difference meter [ZE2 manufactured by Nippon Denshoku Industries Co., Ltd.
000]. Furthermore, the change in film thickness (residual film rate) was measured by a contact surface roughness meter [Surfcom 550 manufactured by Tokyo Seimitsu Co., Ltd.]. Sputtering resistance test: A glass plate having a cured coating film of the protective film material for each optical device obtained by the curing method (2) was applied to a sputtering film forming apparatus [SH-4 manufactured by Nippon Vacuum Co., Ltd.].
50] was used to form a transparent electrode composed of an oxide of indium and tin (ITO) on the cured coating film, and whitening of the coating film and abnormality of the coating film were observed. ○, the case where a slight whitening of the coating film or abnormal coating film was seen, △,
The case where the whitening of the coating film or the abnormality of the coating film was clearly observed was evaluated as x.

[0066]

[Table 3]

Example 6 Instead of a glass plate of 10 cm × 10 cm, 30 cm ×
A color filter having a protective film with a thickness of 2 μm made of a protective film material for an optical device was obtained in the same manner as in Examples 1 to 5 except that a 40 cm color filter without a surface protective film was used. When the same evaluation tests as in Examples 1 to 5 were performed, the same results as in Examples 1 to 5 were obtained.

[0068]

INDUSTRIAL APPLICABILITY The thermosetting resin composition and the protective film material for an optical device of the present invention are excellent in heat resistance without causing unevenness on the coated surface, excellent in uniformity of the coated surface, and coloring without heating or reduction in film thickness. A cured resin product such as a cured coating film having excellent properties is obtained.
Further, by using these as a protective film material, an optical device such as a color filter having a good surface protective film can be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme coat (reference) G02F 1/1335 505 G02F 1/1335 505 F term (reference) 2H048 BA02 BB02 BB37 BB42 2H091 FA02Y FB03 FC24 GA01 LA15 LA30 4J002 BG043 BG053 BG071 BG072 BQ002 CD191 FD070 4J038 DB221 DB261 GA06 GA15 KA02 KA03 KA06 KA07 MA07 MA09 NA01 NA03 NA04 NA11 NA12 NA14 PA19 PB08 4J100 AL03R AL04R AL08P AL08Q AL10P AL62Q BA54Q BA80Q BA80Q

Claims (11)

[Claims] 1. An ethylenically unsaturated monomer (a1) having an epoxy group, an ethylenically unsaturated monomer (a2) having a blocked carboxyl group, and other copolymerizable ethylenically unsaturated monomers. The monomer (a3) and the ethylenically unsaturated monomer (a1) having an epoxy group are 45 to 7
5% by weight, 10 to 40% by weight of the ethylenically unsaturated monomer (a2) having a blocked carboxyl group,
In addition, other copolymerizable ethylenically unsaturated monomer (a3) is 5 to 45% by weight (provided that (a1) and (a
The total of 2) and (a3) is 100% by weight. ] The thermosetting resin composition characterized by containing the copolymer (A) which is used and polymerized at a ratio of. 2. The ethylenically unsaturated monomer (a1) having an epoxy group is partially or wholly an ethylenically unsaturated monomer (a12) having an alicyclic epoxy group. The thermosetting resin composition. 3. The content of the alicyclic epoxy group-containing ethylenically unsaturated monomer (a12) in the epoxy group-containing ethylenically unsaturated monomer (a1) is 10 to 40.
The thermosetting resin composition according to claim 2, which is a mol%. 4. The copolymer (A) is an ethylenically unsaturated monomer (a1) having an epoxy group, an ethylenically unsaturated monomer having a carboxysilane group, and other copolymerizable ethylene. Of the ethylenically unsaturated monomer (a1) having an epoxy group is 45 to 6
Ratio of 0 wt%, 20-35 wt% of ethylenically unsaturated monomer having carboxysilane group, and 5-35 wt% of other copolymerizable ethylenically unsaturated monomer (a3) The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is a copolymer obtained by polymerizing. 5. The epoxy group-containing ethylenically unsaturated monomer (a1) contains 10 to 40 mol% of an alicyclic epoxy group-containing ethylenically unsaturated monomer (a12). The thermosetting resin composition according to claim 4. 6. The thermosetting resin composition according to claim 1, which is obtained by dissolving the copolymer (A) in an organic solvent. 7. A composition containing a coupling agent,
The thermosetting resin composition according to claim 6. 8. A protective film material for an optical device, comprising the thermosetting resin composition according to claim 1. 9. The protective film material for an optical device according to claim 8, further comprising a leveling agent and an antioxidant. 10. The thermosetting resin composition according to claim 1, which is cured.
Resin cured product. 11. A color filter, comprising a cured film made of the protective film material for an optical device according to claim 8 as a surface protective film.