JPH06281801A - Thermosetting composition and surface protective agent for color filter - Google Patents

Abstract

PURPOSE:To improve an adhesion property, light resistance, heat resistance, transparency and surface flatness after coating and curing by constituting the thermosetting compsn. of a specific vinylic polymer, acid anhydride and alicyclic polyepoxide. CONSTITUTION:This thermosetting compsn. consists of (A) a vinylic polymer contg. >=20 to <60wt.% glycidyl group-contg. vinylic monomer units, (B) acid anhydride and (C) alicyclic, polyepoxide. This surface protective agent for color filters consists of such compsn. The vinylic polymer (A) is a copolymer consisting of >=1 kinds of the glycidyl group-contg. vinylic monomers and >=1 kinds of other vinylic monomers. The glycidyl group-contg. vinylic monomers and the other polymerizable monomers may be bonded to blocks or may be randomly bonded. Further, glycidyl methacrylate is more preferable as the glycidyl group-contg. vinylic monomers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting composition and a surface protecting agent for a color filter comprising the composition.

[0002]

2. Description of the Related Art A protective layer such as a coating film layer or a sealant layer is formed on a substrate for the purpose of preventing scratches on the substrate surface, preventing various kinds of deterioration due to light and heat, and sealing various functional elements. It is widely used, and heat resistance, light resistance, and adhesion are required, and various materials are used. In addition, color filters such as liquid crystal display devices and solid-state image pickup devices [charge coupled devices (CCD), etc.] are usually manufactured by a method such as a dyeing method, a printing method, an electrodeposition method, etc. A protective layer is formed on the colored layers such as red, green, and blue for the purpose of protection and anti-staining when manufactured by a dyeing method. Conventionally, as this surface protective material, a thermosetting composition containing a polymer containing 60% by weight or more of glycidyl methacrylate units, a polycarboxylic acid (anhydride), and a silane coupling agent (for example, Kaisho 60
No. 217230) was known.

[0003]

In a liquid crystal display device, a solid-state image pickup device and the like, flattening of the color filter surface is required in order to improve the display quality and resolution. However, the conventional surface protective agent as described above has a problem that it cannot be flattened.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that they are excellent in various properties such as adhesion, light resistance, heat resistance and transparency and can be used as a protective layer. Since it is also excellent in flattening the surface after coating and curing, a thermosetting composition that can be used as a surface protective agent for a color filter has been found, and the present invention has been achieved.
That is, the present invention provides (A) a vinyl polymer containing 20% by weight or more and less than 60% by weight of a glycidyl group-containing vinyl monomer unit, (B) an acid anhydride, and (C) a cycloaliphatic polyepoxide. And a surface protective agent for a color filter comprising the above composition.

In the present invention, the vinyl polymer (A)
Is a copolymer having at least one glycidyl group-containing vinyl monomer as a structural unit and at least one other vinyl monomer as a structural unit. In addition, the glycidyl group-containing vinyl monomer and the other polymerizable monomer may be bonded to the block or may be bonded at random. Examples of the glycidyl group-containing vinyl monomer include glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether. Of these, glycidyl methacrylate is preferred. Further, as the other vinyl-based monomer, ester compounds of (meth) acrylic acid [methyl (meth) acrylate, ethyl (meth) acrylate, (meth))
Acrylic acid-n-propyl, methacrylic acid isopropyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-t-butyl , (Meth) acrylate-n-amyl, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth)
Phenyl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, etc.]; vinyl group-containing aromatic compound (styrene, p-hydroxystyrene, p-acetoxystyrene, α) -Methylstyrene, p-methylstyrene, vinylnaphthalene, etc.) and the like. Among these, preferred are ester compounds of (meth) acrylic acid from the viewpoint of preventing coloring due to heating, and more preferred are alkyl ester compounds of methacrylic acid (alkyl groups) from the viewpoint of water resistance and chemical resistance. Has 1 to 4) carbon atoms.

The content of the glycidyl group-containing vinyl monomer unit in the vinyl polymer (A) is usually 20% by weight or more and less than 60% by weight, preferably 30% by weight or more and 60% by weight or less.
It is less than wt%. If it is less than 20% by weight, the curing strength of the cured product will be insufficient, and if it is 60% by weight or more, the water resistance and the durability to chemicals will decrease.

The weight average molecular weight of the vinyl polymer (A) is usually 5 in terms of polystyrene when measured by GPC.
00-50000, preferably 1000-15000,
In particular, it is 2000 to 7000. Weight average molecular weight is 50
If it is less than 0, the chemical resistance of the cured product will be insufficient and 5
If it exceeds 0000, the flattening property when applied and used becomes insufficient.

As a method for synthesizing the vinyl polymer (A), for example, a glycidyl group-containing vinyl monomer and another vinyl monomer are mixed with an organic peroxide (benzoyl peroxide, t-). Butyl peroxybenzoate, di-t
-Butyl peroxide, lauroyl peroxide,
Dicumyl peroxide), azobisisobutyronitrile and other polymerization initiators for radical polymerization to obtain (A); and butyllithium and diphenylethylene, diphenylhexyllithium, 9-
A method of obtaining (A) by anionic polymerization using an organometallic compound such as anthracenylmethyllithium or α-methylstyryllithium as a polymerization initiator is mentioned.

Specific examples of the acid anhydride (B) in the present invention include aromatic acid anhydrides [phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid, ethylene glycol bis (anhydrotrimellitate). ), Glycerol tris (anhydrotrimellitate), etc.], alicyclic acid anhydrides [methyl nadic acid anhydride,
Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, chlorendic anhydride, 5-
(2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride and the like], aliphatic acid anhydride (dodecyl succinic anhydride and the like) and the like. Among these, preferred are aromatic acid anhydrides. Two or more of these acid anhydrides may be used in combination, and for example, utilization as a eutectic mixture is also useful.

The amount of the acid anhydride (B) in the composition of the present invention is usually 1 to 150 parts by weight, preferably 5 to 120 parts by weight, based on 100 parts by weight of the vinyl polymer (A). . If the amount is less than 1 part by weight, the curing will be insufficient, resulting in 15
If it exceeds 0 parts by weight, it becomes difficult to obtain a uniform cured film.

In the present invention, the cycloaliphatic polyepoxide (C) is not particularly limited, but a specific example thereof is a cycloaliphatic polyepoxide [2- (3,4-epoxy) cyclohexyl having a cyclohexene oxide group. -5,1-Spiro (3,4-epoxy) cyclohexyl-m-dioxane, bis (3,4-epoxy-6-methylcyclohexyl) adipate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate , 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4-vinylcyclohexene dioxide, 1- (1'-methyl-1,2-epoxyethyl)-
3,4-epoxy-3-methylcyclohexane, 2-
(3-glycidyl ether propyl) -5,1-spiro (3,4-epoxy) cyclohexyl-m-dioxane and the like]; and cycloaliphatic polyepoxides having a tricyclodecene oxide group and the like. Of these, preferred are cycloaliphatic polyepoxides having a cyclohexene oxide group. Two or more kinds of these cycloaliphatic polyepoxides (C) may be used in combination.

The amount of the cycloaliphatic polyepoxide (C) in the composition of the present invention is the amount of the vinyl polymer (A) 1
It is usually 1 to 200 parts by weight, preferably 1 to 150 parts by weight with respect to 00 parts by weight. By using (C),
It has an effect of not only improving the flatness of the surface of the protective layer but also improving physical properties such as arc resistance, tracking resistance and light resistance.

In the composition of the present invention, if necessary (A)
In addition to (C) to (C), a silane coupling agent (D) may be further contained. Specific examples of (D) include epoxy group-containing silane coupling agents [eg, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc.], vinyl group-containing silane cups. Ring agent [for example, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, etc.], amino group-containing silane coupling agent (for example, γ-aminopropyltrimethoxysilane, etc.), mercapto group-containing silane coupling agent (for example, γ- Mercaptopropyltrimethoxysilane etc.) and the like. Of these, preferred are epoxy group-containing silane coupling agents. The amount of the silane coupling agent (D) is usually 0 to 60 parts by weight, preferably 0 to 30 parts by weight, based on 100 parts by weight of the vinyl polymer (A). The use of the silane coupling agent (D) is effective in improving the adhesion to the substrate.

In the composition of the present invention, if necessary, a polysiloxane (for example, polyphenylmethylsiloxane, polyether-modified polysiloxane, etc.), an antioxidant [for example, 2,6-di-t-butyl-4-methylphenol] is used. Phenolic antioxidants such as Tris (2,4-di-t-
Butylphenyl) phosphite and other phosphorus-based antioxidants, dilauryl-3,3'-thiodipropionate and other sulfur-based antioxidants, etc.], UV absorbers (eg phenyl salicylate UV absorbers, benzophenone UV absorbers) , Benzotriazole-based UV absorbers, cyanoacrylate-based UV absorbers, benzoate-based UV absorbers, etc.) and the vinyl-based polymer (A).
It can be contained in the range of 0 to 20 parts by weight per 100 parts by weight.

The composition of the present invention comprises (A), (B),
(C), if necessary, a solventless composition in which (D) and optionally the other components exemplified above are uniformly mixed,
Alternatively, it can be used as a solution-like composition in which these components are uniformly mixed in a solvent. As a solvent in the case of a solution composition, these components are dissolved, and
It is not particularly limited as long as it does not react, and specific examples thereof include esters (for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethyl acetate, butyl acetate, isobutyl isobutyrate, diethylene glycol monomethyl ether acetate, diethylene glycol). Monoethyl ether acetate etc.), ethers (eg ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, butyl ether, diisoamyl ether, diethylene glycol, ethylene glycol monomethyl ether etc.), ketones (eg methyl isobutyl ketone,
Cyclohexanone, etc.), halogenated hydrocarbons (eg 1,2-ethylene dichloride, dichlorobenzene, etc.)
And mixed solvents thereof. There is no limitation on the mixing method, and in the case of a solution-like composition, all the constituent components may be mixed in a solvent at one time, and if necessary, each component may be used alone or in combination of two or more. Alternatively, the thermosetting composition of the present invention can be prepared by separately dissolving in different solvents to prepare two or more solutions and then mixing these solutions. The concentration in the case of a solution composition is not particularly limited and may be appropriately selected depending on the purpose of use and the coating method, but normally it is preferably about 10 to 80% by weight for use. Further, in order to obtain a solventless composition, for example, the components of the present invention can be sufficiently mixed in a heated and molten state to give the composition of the present invention having a uniform composition similar to solution mixing.

The surface protective agent for the color filter of the present invention is the name when the composition of the present invention is used as it is for a color filter. Examples of the color filter to which the surface protective agent of the present invention is applied include liquid crystal display devices, color filters usually used for applications such as solid-state imaging devices, and usually, dyeing method, printing method, electrodeposition method, etc. Manufactured by the method.

Exemplifying the method of applying the surface protective agent of the present invention onto a color filter, the surface protective agent of the present invention is
In the form of a solution or a heat-melted product, it is usually applied to a color filter by a method such as spin coating, roll coating, bar coater coating, spray coating, or printing coating so that the coating film thickness is 0.2 to 10 μm. To do.
A flattened cured film can be obtained by applying the above method and then heat-treating it. The heating conditions are
For example, it varies depending on the specific composition of the surface protective agent of the present invention, the desired flatness, the desired physical properties of the cured film, etc., but is usually 60 to 250 ° C., preferably 100 to 250 ° C.
The curing temperature is usually selected from the range of 0.1 minutes to 15 hours. An air circulation furnace, a hot plate, an infrared furnace, a far infrared furnace, or the like can be used for heating.

The cured film thus formed is used as a surface protective film when a color filter is produced by a printing method or an electrodeposition method, and as a surface protective film when a color filter is produced by a dyeing method. It can be used as a dye-proof film of a dyeing layer.

[0019]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Example 1 5 g of a copolymer of glycidyl methacrylate 50 parts by weight and methyl methacrylate 50 parts by weight (polystyrene-equivalent weight average molecular weight about 4000), trimellitic anhydride 2 g, 2-
(3,4-epoxy) cyclohexylmethyl-5,1-
3 g of spiro (3,4-epoxy) cyclohexyl-m-dioxane was mixed with ethyl cellosolve acetate and diethylene glycol dimethyl ether (mixing ratio 7
After dissolving in 18 g (5:25 parts by weight), the mixture was filtered through a 0.2 μm filter to obtain a surface protective agent of the present invention. The above surface protective agent was spin-coated on a glass substrate having a color filter pattern having a thickness of 1.7 μm to obtain a coated substrate having a coating thickness of 2.0 μm. This coated substrate under air 1
A cured film was obtained by heat curing at 80 ° C. for 30 minutes. This film has a visible light (400 to 800 nm) transmittance of 98%.
As described above, good transparency was exhibited, and cracks, wrinkles, and coloring were not generated during heating of ITO deposition, and good heat resistance was exhibited. Table 1 shows the results of the evaluation of flatness and chemical resistance.

Example 2 5 g of a copolymer of 40 parts by weight of glycidyl methacrylate and 60 parts by weight of methyl methacrylate (polystyrene-equivalent weight average molecular weight of about 4000), 2 g of trimellitic anhydride, 3,
After dissolving 3 g of 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate in 18 g of a mixed solvent of ethyl cellosolve acetate and diethylene glycol dimethyl ether (mixing ratio 75:25 parts by weight), the mixture was filtered through a 0.2 μm filter to obtain the present invention. To obtain a surface protective agent. The above surface protective agent was spin-coated on a glass substrate having a color filter pattern having a thickness of 1.7 μm to obtain a coated substrate having a coating thickness of 2.0 μm. Using this coated substrate as a cured film in the same manner as in Example 1, the flatness and chemical resistance were evaluated. The results are shown in Table 1.

Example 3 5 g of a copolymer of glycidyl methacrylate (50 parts by weight) and ethyl methacrylate (50 parts by weight) (polystyrene-equivalent weight average molecular weight about 4000), trimellitic anhydride 2 g, 2-
(3,4-epoxy) cyclohexylmethyl-5,1-
3 g of spiro (3,4-epoxy) cyclohexyl-m-dioxane and 0.5 g of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane were mixed solvent of ethyl cellosolve acetate and diethylene glycol dimethyl ether (mixing ratio 75:25 parts by weight). ) Was dissolved in 18 g and filtered through a 0.2 μm filter to obtain the surface protective agent of the present invention. The above surface protective agent was spin-coated on a glass substrate having a color filter pattern having a thickness of 1.7 μm to obtain a coated substrate having a coating thickness of 2.0 μm. This coated substrate was heated and cured at 200 ° C. for 30 minutes in the air to obtain a cured film. The cured film was evaluated for flatness and chemical resistance in the same manner as in Example 1. The results are shown in Table 1.

Example 4 Copolymer of 50 parts by weight of glycidyl methacrylate with 25 parts by weight of methyl methacrylate and 25 parts by weight of ethyl methacrylate (polystyrene-equivalent weight average molecular weight of about 400)
0) 5 g, trimellitic anhydride 2 g, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 3 g, and γ-glycidoxypropyltrimethoxysilane 0.5 g mixed solvent of ethyl cellosolve acetate and diethylene glycol dimethyl ether. (Mixing ratio 75:25 parts by weight) 0.2 μm after dissolution in 18 g
After filtering with a filter of No. 1, the surface protective agent of the present invention was obtained. The surface protective agent was used as a cured film as in Example 2, and the flatness and chemical resistance were evaluated. The results are shown in Table 1.

Example 5 5 g of a copolymer of glycidyl methacrylate (50 parts by weight) and methyl methacrylate (50 parts by weight) (polystyrene-equivalent weight average molecular weight of about 4000), trimellitic anhydride 2 g, 3,
3 g of 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 0.5 g of γ-glycidoxypropyltrimethoxysilane were added to 18 g of a mixed solvent of ethyl cellosolve acetate and diethylene glycol dimethyl ether (mixing ratio 75:25 parts by weight). After dissolution, the solution was filtered through a 0.2 μm filter to obtain the surface protective agent of the present invention. The surface protective agent was used as a cured film as in Example 2, and the flatness and chemical resistance were evaluated. The results are shown in Table 1.

Example 6 5 g of a copolymer of glycidyl methacrylate (40 parts by weight) and methyl methacrylate (60 parts by weight) (polystyrene-equivalent weight average molecular weight about 4000), 2 g of phthalic anhydride, 2-
(3,4-epoxy) cyclohexylmethyl-5,1-
3 g of spiro (3,4-epoxy) cyclohexyl-m-dioxane and 0.5 g of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane were mixed solvent of ethyl cellosolve acetate and diethylene glycol dimethyl ether (mixing ratio 75:25 parts by weight). ) Was dissolved in 18 g and filtered through a 0.2 μm filter to obtain the surface protective agent of the present invention. The surface protective agent was used as a cured film as in Example 2, and the flatness and chemical resistance were evaluated. The results are shown in Table 1.
Shown in.

Example 7 5 g of a copolymer of glycidyl methacrylate (50 parts by weight) and ethyl methacrylate (50 parts by weight) (polystyrene-equivalent weight average molecular weight about 4000), trimellitic anhydride 2 g, 3,
3 g of 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 0.5 g of γ-glycidoxypropyltrimethoxysilane were added to 18 g of a mixed solvent of ethyl cellosolve acetate and diethylene glycol dimethyl ether (mixing ratio 75:25 parts by weight). After dissolution, the solution was filtered through a 0.2 μm filter to obtain the surface protective agent of the present invention. The surface protective agent was used as a cured film as in Example 2, and the flatness and chemical resistance were evaluated. The results are shown in Table 1.

Comparative Example 1 5 g of polyglycidyl methacrylate (polystyrene-converted weight average molecular weight of about 70,000), trimellitic anhydride 2
g, γ-glycidoxypropyltrimethoxysilane 0.
5 g of a mixed solvent of ethyl cellosolve acetate and diethylene glycol dimethyl ether (mixing ratio 75:25
(Part by weight) 18 g, and filtered with a 0.2 μm filter to obtain a polymer solution. Using this as a cured film in the same manner as in Example 2, the flatness and chemical resistance were evaluated. The results are shown in Table 1.

[0027]

[Table 1]

Note) <Evaluation method> Flatness evaluation method: spin coating on a glass substrate having a color filter pattern having a thickness of 1.7 μm,
A coated substrate having a coating thickness of 2.0 μm was obtained. This coated substrate was cured under the conditions of each Example and Comparative Example to obtain a cured film.
The flatness was evaluated by the residual step corresponding to the unevenness of the color filter on the surface of the coating film. Chemical resistance evaluation method: Alkali resistance: 30% in 10% NaOH aqueous solution (40 ° C)
Tape peeling test after immersion in minutes (JISD-0202) Acid resistance; Tape peeling test after immersion in 35% hydrochloric acid aqueous solution (40 ° C) for 30 minutes (JISD-0202)

Example 8 The surface protective agents prepared in Examples 1 to 7 were spin-coated on a glass substrate to obtain a coated substrate having a coating thickness of 2.0 μm.
After heat-curing this coated substrate under air at 180 ° C. for 30 minutes, it was placed in a dyeing bath composed of 2 g of Suminol Fast Red G [Sumitomo Chemical Co., Ltd.], 3 g of acetic acid and 100 g of water at 100 ° C. for 1 hour. Soaked. No staining was confirmed in the evaluation after washing and drying this substrate.

[0030]

The thermosetting composition of the present invention is excellent in various properties such as adhesion and heat resistance and can be used as a material for forming a protective layer on various substrates. Also, since it has excellent flatness of the surface after coating and curing, when used as a surface protective agent for color filters, it not only has properties such as chemical resistance and heat resistance as a protective agent, but also improves display quality and resolution. , Has practically excellent characteristics. Further, since it has excellent properties as an optical material such as light resistance and transparency, it can be used as a protective layer for various optical materials such as a lens, a light emitting element, a light receiving element, an adhesive layer, a seal layer and the like. .

Claims (3)

[Claims] 1. A vinyl polymer containing (A) a glycidyl group-containing vinyl monomer unit in an amount of 20% by weight or more and less than 60% by weight, (B) an acid anhydride, and (C) a cycloaliphatic polyepoxide. A thermosetting composition comprising: 2. A thermosetting composition which further comprises a silane coupling agent (D) in addition to (A) to (C) of claim 1. 3. A surface protecting agent for a color filter comprising the thermosetting composition according to claim 1.