JPH0554515B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a thermosetting resin composition for forming a color filter protective film. [Prior Art] In recent years, various liquid crystal display elements and solid-state image sensors equipped with color filters have been announced. It is formed through several steps. That is, polyvinyl alcohol,
Grieux, gelatin, etc. are imparted with photosensitivity and coated uniformly onto a substrate, and only the first color pattern is photocured and developed using a mask exposure method, and the other portions are removed. This pattern portion is dyed with a dye having predetermined spectral characteristics. A transparent anti-dye protection layer is then applied. The pattern portion of the second color is also dyed using the same process and coated with an anti-dye protection layer. The pattern portion of the third color is also dyed using the same process, and finally a surface protective layer is formed. In addition to adhesion, smoothness, toughness, heat resistance, light resistance, water resistance, and solvent resistance, this anti-dye protection layer and surface protection layer have properties such as transparency and stain resistance so that they are not dyed by dyes. Performance is required. Furthermore, the materials forming these layers are applied as a solution in order to form a dye-resistant protective layer and a surface protective layer.
In order to form a uniform coating film, a spin coating method using spin coating is sometimes used, and the coating method is also required to be suitable for this coating method. In addition, as a material for forming a protective layer in the production of color filters, in particular, a combination of cyclized rubber and a sensitizer and polymethyl methacrylate have been proposed (Japanese Unexamined Patent Publication No. 59-49507). However, even if a protective layer is formed using these materials, it is not possible to obtain a protective layer that has the above-mentioned properties required for a protective layer in a well-balanced manner. has a problem that it is not possible to obtain a satisfactory color filter because polymethyl methacrylate has poor transparency, heat resistance, etc., and polymethyl methacrylate has poor weldability with the dyed substrate layer and heat resistance. [Problems to be Solved by the Invention] As described above, it is not possible to obtain a coating film that satisfies the above-mentioned required properties in a well-balanced manner using conventional coating film forming materials. ,
It was difficult to balance solvent resistance and dye resistance, and many of them were not suitable for spin coating. The purpose of the present invention is to solve the above-mentioned problems of the prior art, and to provide smoothness, toughness, high heat resistance and light resistance, as well as adhesion to substrates, transparency, water resistance, solvent resistance and stain resistance. To provide a thermosetting resin composition that can form a coating film that is excellent in all of the following points, has high hardness, and is suitable as a material for forming a protective layer of a color filter and is suitable for spin coating. It is. [Means for Solving the Problems] The present invention provides, as a means for solving the above problems, (A) general formula (): [In the formula, R ¹ is a hydrogen atom or a lower alkyl group, and n is an integer of 1 to 5] A monomer unit derived from a monomer compound represented by the general formula (): [In the formula, R ² is a hydrogen atom or a lower alkyl group, R ³ is a lower alkyl group, and n is an integer of 1 to 5.] and (B) at least one selected from aromatic polycarboxylic acids and anhydrides of aromatic polycarboxylic acids. This is what we provide. The polymer that is component (A) of the composition of the present invention includes a copolymer of a compound of general formula () and a compound of general formula (), and a copolymer of a compound of general formula () and a compound of general formula (). and other polymerizable monomers. Specific examples of compounds of general formula () include glycidyl acrylate, glycidyl methacrylate, α
- Glycidyl ethyl acrylate, glycidyl α-n-propylacrylate, glycidyl α-n-butylacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 4,5-methacrylate -epoxypentyl,
Examples include 4,5-epoxypentyl acrylate, 6,7-epoxyheptyl methacrylate, and 6,7-epoxyheptyl α-ethyl acrylate. Among these compounds, R in the general formula () is preferably a hydrogen atom, a methyl group or an ethyl group, and n is preferably 1 or 2. Specific examples of compounds of general formula () include 2-
acryloyloxyethyltrimethoxysilane,
2-acryloyloxytriethoxysilane, 2
-methacryloyloxytrimethoxysilane, 2
-methacryloyloxytriethoxysilane, 3
-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltripropoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-(α- Examples include ethyl acryloyloxy)propyltrimethoxysilane, 4-methacryloyloxybutyltrimethoxysilane, and 4-methacryloyloxybutyltripropoxysilane.
Among these compounds, preferred compounds are 2
-methacryloyloxyethyltrimethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltritoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane It is ethoxysilane. In the copolymer of component (A), the monomer unit derived from the compound of general formula () is 60% by weight or more;
The monomer unit derived from the compound of general formula () is preferably 0.1% by weight or more. 60 monomer units derived from the compound of general formula ()
If the amount is less than 0.1% by weight, it will be difficult to obtain a coating film with excellent heat resistance, and if the amount of monomer units derived from the compound of general formula () is less than 0.1% by weight, the adhesion to the substrate will be insufficient. . Other polymerizable monomer compounds other than the monomer compounds of general formulas () and () used in the production of the copolymer of component (A) include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, Esters of acrylic acid or methacrylic acid such as ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl methacrylate, phenyl acrylate, phenyl methacrylate; styrene, α-methylstyrene, p-methylstyrene, vinylnaphthalene Examples include vinyl aromatic compounds such as. Among these polymerizable monomers, it is particularly preferable to use esters of acrylic acid or methacrylic acid in terms of forming a tougher and more transparent coating film. However, monomer units derived from these other polymerizable monomer compounds are not included in the copolymer of component (A).
It is desirable that the amount does not exceed 30% by weight.
If their content exceeds 30% by weight, not only will the adhesion to the substrate deteriorate, but it will also be difficult to form a uniform and smooth coating film by spin coating. In addition, the polymerizable monomers include acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate,
Functional acrylic compounds such as 2-hydroxybutyl methacrylate; diene compounds such as butadiene, isoprene, piperylene, dimethylbutadiene, etc. can also be used, but the content of monomer units derived from these is component (A). 5% by weight of the polymer of
It is desirable that the range does not exceed . If their content exceeds 5% by weight, the adhesive strength to the substrate will decrease. The copolymerization form of the copolymer of component (A) is not particularly limited, and may be either a random copolymer or a block copolymer by addition polymerization, and the copolymerization method may also be a solution polymerization method, an emulsion polymerization method, etc. Either is fine. The molecular weight of the copolymer of component (A) is not particularly limited as long as the composition of the present invention can be applied to a substrate as a uniform film, but it usually has a polystyrene equivalent weight average molecular weight of 5,000 to 500,000, and the coating to be formed is It can be appropriately selected depending on the purpose and conditions of coating film formation, such as film thickness and coating method. The composition of the present invention contains at least one selected from aromatic polycarboxylic acids and aromatic polycarboxylic acid anhydrides as the component (B). Specific examples of the polyhydric carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, 1,2,3-tricarboxylbenzene, 1,2,3-tricarboxyl-4-methylbenzene, 1,2,3- Tricarboxyl-5-methylbenzene, 1,2,3-tricarboxyl-4-phenylbenzene, 1,2,
3-tricarboxyl-5-phenylbenzene,
1,2,4-tricarboxylbenzene (i.e. trimellitic acid), 1,2,4-tricarboxyl-3-methylbenzene, 1,2,4-tricarboxyl-3-phenylbenzene, 1,2,
4-tricarboxyl-5-methylbenzene,
1,2,4-tricarboxyl-5-phenylbenzene, 1,2,4-tricarboxyl-6-methylbenzene, 1,2,4-tricarboxyl-
6-phenylbenzene, 1,2,3,4-tetracarboxybenzene, 1,2,3,4-tetracarboxyl-5-methylbenzene, 1,2,3,
4-tetracarboxyl-5-phenylbenzene, 1,2,3,5-tetracarboxylbenzene, 1,2,3,5-tetracarboxyl-4-
Methylbenzene, 1,2,3,5-tetracarboxyl-4-phenylbenzene, 1,2,4,5
- benzene derivatives such as tetracarboxylbenzene (i.e. pyromellitic acid); 1,2,3-tricarboxylnaphthalene,
1,2,4-tricarboxylnaphthalene, 1,
2,5-tricarboxylnaphthalene, 1,2,
6-tricarboxylnaphthalene, 1,2,7-
Tricarboxylnaphthalene, 1,2,8-tricarboxylnaphthalene, 1,2,3,4-tetracarboxylnaphthalene, 1,2,3,5-tetracarboxylnaphthalene, 1,2,3,6-
Tetracarboxylnaphthalene, 1,2,3,7
-tetracarboxylnaphthalene, 1,3,5,
6-tetracarboxylnaphthalene, 1,3,
5,7-tetracarboxylnaphthalene, 1,
4,5,6-tetracarboxylnaphthalene,
Naphthalene derivatives such as 1,4,5,7-tetracarboxylnaphthalene, 1,4,5,8-tetracarboxylnaphthalene; 2,2,3-tricarboxylbenzophenone, 2,3,3-tricarboxylbenzo Phenone, 2,3,4-tricarboxylbenzophenone, 2,3,4-tricarboxylbenzophenone, 3,3,4-tricarboxylbenzophenone, 3,4,4-tricarboxylbenzophenone , 2,3,4-tricarboxylbenzophenone, 2,3,6-tricarboxylbenzophenone, 2,3,4,5-tetracarboxylbenzophenone, 2,3,5,6-tetracarboxylbenzophenone Phenone, 2,2',3,3'-tetracarboxylbenzophenone, 2,3,3',5-tetracarboxylbenzophenone, 3,3',4,4'-
Tetracarboxylbenzophenone, 3,3′,
Examples of the polyvalent carboxylic acid include aromatic polycarboxylic acids such as benzophenone derivatives such as 4,5'-tetracarboxylbenzophenone, and examples of the polycarboxylic acid anhydrides include the anhydrides of the above-mentioned exemplified compounds. The above-mentioned aromatic polycarboxylic acids and aromatic polycarboxylic acid anhydrides can be used alone or in combination of two or more. The amount of component (B) in the composition of the present invention is (A)
The amount ranges from 0.01 to 50 parts by weight, preferably from 1 to 50 parts by weight, per 100 parts by weight of the component polymer.
If the amount of component (B) is less than 0.01 part by weight, the curing will be insufficient and a strong coating film cannot be formed, and if it exceeds 50 parts by weight, the adhesion of the coating film to the substrate will deteriorate. In addition, it is difficult to form a uniform and smooth coating film by spin coating. Components other than the component (A) and component (B) can be added to the composition of the present invention. Examples of such components include (C) a (co)polymer containing, for example, 60% by weight or more of monomer units derived from the monomer compound of the general formula (). When component (C) is a copolymer, the monomer compound copolymerized with the monomer compound of general formula () is used in the production of the copolymer of component (A). Similar general formulas () and ()
Polymerizable monomer compounds other than the compounds mentioned above can be mentioned. The copolymerization form of the copolymer of the above polymerizable monomer compound and the compound of general formula () is also not particularly limited,
It may be a random copolymer or a block copolymer formed by addition polymerization, and the copolymerization method may be a solution polymerization method, an emulsion polymerization method, or the like. The molecular weight of the (co)polymer of component (C) is not particularly limited, but it usually has a polystyrene equivalent weight average molecular weight of 5,000 to 300,000. It can be selected as appropriate depending on the conditions. The amount of the (co)polymer (C) added is usually about 50 parts by weight or less per 100 parts by weight of the copolymer (A). In addition to the above-mentioned components (A) to (C), the composition of the present invention may optionally contain stabilizers such as anti-aging agents and ultraviolet absorbers to an extent that does not impair transparency. can do. The composition of the present invention can be obtained by uniformly mixing the above components. As a method for mixing these components, a solution mixing method is usually preferred, in which these components are mixed by dissolving them in a suitable solvent. The solvent used for solution 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. Specific examples include:
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, di-n - Ketone solvents such as propyl ketone, diisobutyl ketone, cyclohexanone, and holone; ethyl ether, isopropyl ether, n-
Ether solvents such as butyl ether, diisoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane, tetrahydrofuran, etc.
Ethyl formate, propyl formate, n-butyl formate,
Ethyl acetate, n-propyl acetate, isopropyl acetate, n-methyl acetate, n-amyl acetate, ethylene glycol, dimethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc. The following ester solvents can be mentioned. When preparing the composition of the present invention by solution mixing, the mixing order is not particularly limited. For example, a solution of the composition of the present invention may be prepared by dissolving all components in a solvent at the same time, or as necessary. Accordingly, each component may be dissolved separately in the same or different solvents to form two or more solutions, and these solutions may be mixed to prepare a solution of the composition of the present invention. For example, by preparing a solution of component (B) and a solution of the remaining other components and mixing them in the desired ratio immediately before use, the long-term storage stability of each component can be improved. By simply changing the mixing ratio of the two types of solutions, it becomes possible to easily change the coating film performance depending on the purpose. The concentration of the composition solution is not particularly limited and can be appropriately selected depending on the purpose of use, but it is generally used at about 5 to 50% by weight. A desired coating film can be obtained by applying the solution of the composition of the present invention prepared as described above onto the surface of a substrate and curing it by heating. The method of applying the solution of the composition of the present invention to the substrate surface is not particularly limited, and various methods such as a spray method, roll coating method, and spin coating method can be used. One of the features of the present invention is that it is suitable for The heat curing conditions for the composition of the present invention are appropriately selected depending on the specific types and proportions of each component of the composition, but are usually at 80 to 250°C for about 15 minutes to 10 hours. [Examples] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 10.2 g of a copolymer of 75 parts by weight of glycidyl methacrylate and 25 parts by weight of 3-methacryloyloxypropyltrimethoxysilane (weight average molecular weight in terms of polystyrene of about 45,000) was dissolved in 95 g of ethyl cellosolve acetate. 0.5 g of trimellitic acid was added to the solution thus obtained and stirred until uniformly mixed. The solution thus obtained was filtered through a filter with a pore size of 0.2 μm, and then spin-coated onto a glass plate at a rotation speed of 3000 rpm using a spin coater. After coating, the glass plate was heat treated in a clean oven at 150°C for 30 minutes to cure the coating film. The surface of the resulting coating film was extremely smooth, and no film roughness was observed at all. The film thickness measured with a stylus-type film thickness meter (Talystep (manufactured by Hobson Taylor)) was 0.35 μm. The following tests were conducted on the coating film prepared as described above. First, the absorption spectrum of a glass plate coated with the above coating was measured using the same glass plate as a control. 350nm~800nm
The light transmittance was 95% or more in all regions. Next, in order to examine the adhesion of the coating film applied and cured to the glass plate, a cross-cut test (JIS K-5400) by tape peeling was conducted. As a result, no peeling was observed at all. Furthermore, after placing this glass plate in boiling water and leaving it for 5 hours, a similar cross-cut test was performed, but no peeling was observed in this case as well. Further, the glass plate with the above-mentioned coating film was placed in toluene, heated under reflux for 5 hours, and then subjected to a cross-cut test, but no peeling was observed in this case as well. Furthermore, when a glass plate with a coating film prepared in the same manner as above was heat-treated in a gear oven at 200°C for 200 hours, no cracks appeared in the coating film, and no change in the absorption spectrum was observed. Furthermore, a glass plate with a coating film prepared in the same manner as above was placed in a dyeing bath with the following composition and heated at 100℃.
After leaving it for 30 minutes, the glass plate was taken out, thoroughly washed with water, dried, and then the condition of the paint film was visually inspected. No abnormalities such as cracks or roughness were observed, and the paint film remained colorless and transparent. It was not stained at all. Dyeing bath acidic dye (Kayanor Milling Red RS-125
[Nippon Kayaku]) ...2g Acetic acid ...2g Distilled water 100g From the above results, the coating film of the composition of the present invention is smooth, has good transparency, adhesion, water resistance, solvent resistance, heat resistance and resistance. It is clear that the dyeing property is extremely good. Example 2 4.8 g of a copolymer of 75 parts by weight of glycidyl methacrylate and 25 parts by weight of 3-methacryloyloxypropyltrimethoxysilane (weight average molecular weight in terms of polystyrene of about 45,000) and polyglycidyl methacrylate (weight average molecular weight in terms of polystyrene of about 80,000) 6g
and dissolved in 95g of ethyl cellosolve acetate,
Furthermore, 0.5 g of trimellitic acid was added, and a composition solution was prepared in the same manner as in Example 1. Then, in the same manner as in Example 1, a film was formed on a glass plate.
A coating film of 0.35 μm was formed. The obtained coating film was subjected to the same test as in Example 1, and the results were as shown in Table 1. Example 3 Glycidyl methacrylate in Example 2 and 3
-Methacrylic acid-3 in place of 4.8g of copolymer of methacryloyloxypropyltrimethoxysilane,
Copolymer of 80 parts by weight of 4-epoxybutyl and 20 parts by weight of 2-methacryloyloxyethyltrimethoxysilane (weight average molecular weight in terms of polystyrene: approx.
A composition solution was prepared in the same manner as in Example 1 except for using 5.0 g of 50000). Then, in the same manner as in Example 1, a coating film having a thickness of 0.42 μm was formed on a glass plate.
The obtained coating film was subjected to the same test as in Example 1, and the results were as shown in Table 1. Example 4 Glycidyl methacrylate in Example 2 and 3
- Copolymer of 70 parts by weight of glycidyl methacrylate, 27 parts by weight of tert-butyl methacrylate, and 3 parts by weight of 3-methacryloyloxypropyltrimethoxysilane in place of 4.8 g of copolymer of methacryloyloxypropyltrimethoxysilane. A composition solution was prepared in the same manner as in Example 1 except that 5.0 g (weight average molecular weight in terms of polystyrene of about 50,000) was used. Then, in the same manner as in Example 1, a film with a thickness of 0.40 μm was formed on a glass plate.
A coating film was formed. The surface of the coating film was very smooth. The obtained coating film was subjected to the same test as in Example 1, and the results were as shown in Table 1. Example 5 A composition solution was prepared in the same manner as in Example 2 except that 0.5 g of trimellitic acid in Example 2 was replaced with 0.3 g of pyromellitic acid. Then, in the same manner as in Example 1, a coating film of 0.32 μm was formed on a glass substrate. The obtained coating film was subjected to the same test as in Example 1, and the results were as shown in Table 1. Example 6 In place of the polyglycidyl methacrylate in Example 2, 6.0 g of a copolymer of 62 parts by weight of glycidyl methacrylate and 38 parts by weight of tert-butyl methacrylate (weight average molecular weight in terms of polystyrene 150,000) was used, and the other examples were as follows. A composition solution was prepared in the same manner as in Example 1, and a coating film with a thickness of 0.40 μm was formed on a glass substrate. The obtained coating film was subjected to the same test as in Example 1, and the results were as shown in Table 1. Comparative Example 1 Glycidyl methacrylate in Example 2 and 3
- Instead of 4.8 g of copolymer of methacryloyloxypropyltrimethoxysilane, a copolymer of 75 parts by weight of glycidyl methacrylate and 25 parts by weight of methyl methacrylate (weight average molecular weight in terms of polystyrene)
A coating film having a thickness of 0.38 μm was formed on a glass substrate in the same manner as in Example 1 except that 5.0 g of 50000) was used. The obtained coating film was subjected to the same test as in Example 1, and the results were as shown in Table 1.

[Table] Comparative Example 2 Same as Example 1 except that 0.5 g of hexahydrophthalic anhydride (manufactured by Shin Nihon Rika Co., Ltd.), which is an alicyclic acid anhydride, was used instead of 0.5 g of trimellitic acid in Example 1. The thickness of the film is increased on the glass substrate.
A coating film of 0.42 μm was formed. The obtained coating film was subjected to the same test as in Example 1, and the results were as shown in Table 2. Comparative Example 3 Glass was prepared in the same manner as in Example 1, except that 0.5 g of tetrahydrophthalic anhydride (manufactured by Shin Nippon Chemical Co., Ltd.), which is an alicyclic acid anhydride, was used instead of 0.5 g of trimellitic acid in Example 1. film thickness on the substrate
A coating film of 0.39 μm was formed. The obtained coating film was subjected to the same test as in Example 1, and the results were as shown in Table 2.

〔Effect of the invention〕

Since the composition for forming a color filter protective film of the present invention has excellent stability at room temperature, it is advantageous for preparing it as a one-component thermosetting resin composition. The coating film for the protective film of a color filter obtained by curing the composition of the present invention has high light transmittance in a wide range of wavelengths from ultraviolet to visible regions, and has excellent transparency. ,
Shows excellent adhesion to substrates made of various materials such as metals and plastics. In addition, this coating has high smoothness, high hardness, and toughness, so it has high scratch resistance, and has excellent light and heat resistance, so it will not change in quality such as discoloration even after long-term use. Furthermore, it has excellent water resistance, solvent resistance, and stain resistance, and has high hardness.
Due to these characteristics, the coating film formed by the composition of the present invention can be used as an anti-dye protective layer of a color separation filter,
It is extremely suitable as a surface protective layer, etc., and a highly reliable color separation filter with excellent color clarity and brightness can be obtained. A major feature of the coating film obtained using the composition of the present invention is that, as described above, the required properties are well-balanced and all of them are good.

Claims (1)

[Claims] 1 (A) General formula (): [In the formula, R ¹ is a hydrogen atom or a lower alkyl group, R ³ is a lower alkyl group, and n is an integer of 1 to 5] A monomer unit derived from a monomer compound represented by and general formula (): [wherein R ² is a hydrogen atom or a lower alkyl group, and n is an integer of 1 to 5] A copolymer containing a monomer unit derived from a monomer compound represented by B) A thermosetting resin composition for forming a color filter protective film, comprising at least one selected from aromatic polycarboxylic acids and aromatic polycarboxylic acid anhydrides.