KR20100087668A - Resin composition for forming protective film, and protective film of color filter - Google Patents

Abstract

PURPOSE: A resin composition used for forming a protective film is provided to have high planarization performance of a film surface even when a slit coating method is used as a coating method and to form the protective film having excellent performances including transparency and heat resistance. CONSTITUTION: A resin composition used for forming a protective film comprises: a polymer having a repeating unit which is obtained from a polymerizable unsaturated compound with an epoxy group; a compound which is selected from polyfunctional carboxylic acid anhydride or polyfunctional carboxylic acid; a copolymer having a silicon chain and an average molecular weight of 5,000-25,000; a compound having two or more cation-polymerizable groups; and an alkoxysilane compound having the epoxy group.

Description

RESIN COMPOSITION FOR FORMING PROTECTIVE FILM, AND PROTECTIVE FILM OF COLOR FILTER}

The present invention relates to a protective film of the resin composition for forming a protective film and a color filter.

In display elements, such as a liquid crystal display element, the immersion process by a solvent, an acid, or alkaline solution etc. is performed during the manufacturing process, and when forming a wiring electrode layer by sputtering, the surface of an element is locally exposed to high temperature. In order to prevent an element from deteriorating or damaging by such a process, providing the protective film containing the thin film which is resistant to these processes on the surface of an element is performed.

In such a protective film, the adhesion must be high to the substrate or base layer on which the protective film should be formed, the layer formed on the protective film, the film itself must be smooth and strong, have transparency, and heat resistance. And high light resistance, and should not cause deterioration such as coloring, yellowing or whitening over a long period of time, and excellent water resistance, solvent resistance, acid resistance and alkali resistance. As a material for forming the protective film which satisfy | fills these various characteristics, the resin composition for protective film formation containing the polymer which has glycidyl group, for example is known (refer patent document 1 and patent document 2). In such a resin composition for protective film formation, after apply | coating this resin composition for protective film formation to the surface of the base which should form a protective film, a protective film can be formed by heat-processing and hardening this coating film.

However, in the color liquid crystal display device of the super twisted nematic (STN) system, the uniformity of cell spacing is very important as compared to the liquid crystal display device of the twisted nematic (TN) system. Therefore, as a board | substrate used for the STN type color liquid crystal display element, it is calculated | required that the surface flatness is high. It is because display nonuniformity will arise in the liquid crystal display element obtained when a board | substrate with low surface flatness is used. For example, in the board | substrate with which the color filter was formed (substrate with a color filter), the unevenness | corrugation by a color filter is formed in the surface. Moreover, when a protective film is formed using the well-known resin composition for protective film formation on this color filter board | substrate, even if the resin composition for protective film formation known to be excellent in planarization performance is used, the unevenness | corrugation by a color filter can fully be eliminated. There was no irregularities on the surface of the protective film. To date, this level of flatness has been allowed. However, with the recent demand for higher image quality and higher precision, the generation of slight color unevenness is not allowed, and further improvement in contrast is required. As a result, a higher level of planarization is required for the substrate used in the liquid crystal display device, and it is evident that the conventionally known resin composition for forming a protective film cannot meet such a requirement.

In addition, in recent years, in accordance with the trend of large-screen televisions and request for reduction in process cost, the size of the substrate glass used for the production of substrates with color filters tends to be increased. Therefore, in the application | coating process of the resin composition for protective film formation performed at the time of forming a protective film on a board | substrate, the use of the spin coating method conventionally performed widely becomes difficult, and a coating method discharges a composition from a slit-shaped nozzle and apply | coats, Changed to the so-called slit coating method. This slit coating method also has the advantage that the amount of the composition required for coating can be reduced as compared with the spin coating method, and is also effective for reducing the manufacturing cost of the liquid crystal display element. However, in such a slit coating method, since a coating film is formed, supporting several points of a board | substrate with a micro pin, the nonuniformity containing the micro unevenness | corrugation resulting from a support pin may arise in a coating film, It is hampering the high degree of flatness.

Japanese Patent Laid-Open No. 5-78453 Japanese Patent Laid-Open No. 2001-91732

The present invention has been made on the basis of the above circumstances, and the object thereof is to provide a substrate having a flat surface, having high surface flatness on the substrate even when the slit coating method is used as a coating method, and a variety of properties such as transparency and heat resistance. It is providing the protective film of the protective film formation resin composition which can form the protective film which is excellent in performance, and the color filter which was excellent in various performances, such as transparency and heat resistance, with high flatness of a surface.

The above objects and advantages of the present invention firstly,

(A) A polymer having a repeating unit derived from a polymerizable unsaturated compound having an epoxy group (hereinafter referred to as "(A) polymer"),

(B) at least one compound selected from the group consisting of polyhydric carboxylic anhydrides and polyvalent carboxylic acids (hereinafter referred to as "(B) compound"),

(C) (c1) 25 to 35 mass% of a compound represented by the following general formula (1) (hereinafter referred to as "(c1) compound"),

(c2) 20 to 30 mass% of a compound represented by the following formula (2) (hereinafter referred to as "(c2) compound"),

(c3) 15-20 mass% of polymerizable unsaturated compounds (henceforth "a compound (c3)") which have a group represented by following formula (3),

(c4) 25 to 35 mass% of a polymerizable unsaturated compound having an alkyl group having 1 to 8 carbon atoms (hereinafter referred to as "(c4) compound"), and

(c5) A copolymer of 1 to 5% by mass of a polymerizable unsaturated compound having two or more unsaturated bonds in one molecule (hereinafter referred to as "(c5) compound"), and having a weight average molecular weight of 5,000 to 25,000. (Hereinafter referred to as "(C) copolymer"),

(D) a compound having two or more cationically polymerizable groups, except those corresponding to the polymers (A); and

(E) Alkoxysilane Compound Having Epoxy Group

It is achieved by the resin composition for protective film formation containing these.

(In Formula 1, R ¹ is a hydrogen atom or a methyl group.)

(In formula 2, R <^2> is a hydrogen atom or a methyl group, R <^3> is a methyl group, an ethyl group, a propyl group, or a butyl group, a is a repeating unit number, and the number average value is 4-12.)

(In Formula 3, R <^4> , R <^5> , R <^6> , R <^7> and R <^8> are respectively independently a C1-C20 alkyl group, a phenyl group, or group represented by following formula (4), b is an integer of 0-3. )

(In Formula 4, R <^9> , R <^10> and R <^11> is respectively independently a C1-C20 alkyl group or a phenyl group, c is an integer of 0-3.)

The above objects and advantages of the present invention are second,

It is achieved by the protective film of the color filter formed from said resin composition for protective film formation.

According to the present invention, even when the slit coating method is used as a coating method, a protective film can be formed on a substrate having an uneven surface, and having a high surface flatness on the substrate and excellent protective film such as transparency and heat resistance. The protective film of the color filter which is high in the composition for surface and surface flatness, and excellent in various performances, such as transparency and heat resistance, is provided.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.

<Resin composition for protective film formation>

The resin composition for protective film formation of this invention contains the said (A) polymer, (B) compound, (C) copolymer, (D) compound, and (E) compound. The resin composition for protective film formation of this invention may further contain (F) hardening accelerator arbitrarily other than each said component.

The resin composition for forming a protective film of the present invention is preferably prepared as a solution composition in which each of the above components is dissolved in a solvent, more preferably (A) polymer, (C) copolymer, (D) compound, (E (2) A two-component type containing a compound, a solvent and, if necessary, a first solution containing a curing accelerator (F) and a second solution containing a compound (B) and a solvent, and a mixture of the two solutions when used. It is used as the resin composition for protective film formation of the.

[(A) Polymer]

The polymer (A) in the present invention is a polymer having a repeating unit derived from a polymerizable unsaturated compound having an epoxy group.

The polymer (A) may be a polymer only of a polymerizable unsaturated compound having an epoxy group, or may be a copolymer of a polymerizable unsaturated compound having an epoxy group with another polymerizable unsaturated compound.

Here, as a polymerizable unsaturated compound which has the said epoxy group, (meth) glycidyl (meth) acrylate, the glycidyl (alpha)-ethyl acrylate, the glycidyl (alpha)-n-propyl acrylate, the glycidyl (alpha)-n-butylacrylate, for example. , 3,4-epoxybutyl (meth) acrylic acid, 3,4-epoxybutyl (alpha) -ethylacrylic acid, 6,7-epoxyheptyl (meth) acrylic acid, 6,7-epoxyheptyl (alpha)-ethylacrylic acid, o-vinylbenzylglycol Cylyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxy Methyl oxetane etc. are mentioned. Among these, preferred are (meth) acrylic acid glycidyl, (meth) acrylic acid 6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether And 3-methyl-3- (meth) acryloyloxymethyloxetane and 3-ethyl-3- (meth) acryloyloxymethyloxetane. These compounds are preferably used because they have high copolymerization reactivity and are effective in increasing the heat resistance and surface hardness of the protective film formed.

The polymerizable unsaturated compound which has these epoxy groups can be used individually or in mixture of 2 or more types.

As said other polymerizable unsaturated compound, ester of (meth) acrylic acid, a vinyl aromatic compound, etc. are mentioned, for example. As ester of the said (meth) acrylic acid, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, and (meth) acrylic acid Cyclohexyl, (meth) acrylic acid [5.2.1.0 ^2,6 ] decane-8-yl, (meth) acrylic acid [5.2.1.0 ^2,6 ] decane-8-yloxyethyl, isobornyl (meth) acrylate, etc. ; As said vinyl aromatic compound, N-phenylmaleimide, N-cyclohexyl maleimide, styrene, p-methoxy styrene, (alpha) -methylstyrene, p-methylstyrene, vinyl naphthalene, etc. are mentioned, for example. Preferred among these are methyl methacrylate, methacrylic acid [5.2.1.0 ^2,6 ] decane-8-yl, N-phenylmaleimide, N-cyclohexylmaleimide, styrene and p-methoxy styrene. have. These other preferable polymerizable unsaturated compounds have high copolymerization reactivity.

These other polymerizable unsaturated compounds can be used individually or in combination of 2 or more types.

(A) The content rate of the repeating unit derived from the polymerizable unsaturated compound which has an epoxy group in a polymer becomes like this. Preferably it is 10-70 mass% with respect to all the repeating units, Especially preferably, it is 20-60 mass%. When this value exceeds 70 mass%, the storage stability of the 1st liquid obtained may be impaired, while when this value is less than 10 mass%, the heat resistance and surface hardness of the protective film formed may be insufficient.

The weight average molecular weight (hereinafter, simply referred to as "weight average molecular weight" or "Mw") in terms of polystyrene measured by gel permeation chromatography (GPC) for the polymer (A) is preferably in the range of 2,000 to 20,000. . Here, when Mw is less than 2,000 (A), the applicability | paintability of the resin composition for protective film formation obtained may be impaired, On the other hand, when Mw of (A) polymer exceeds 20,000, the storage stability of the 1st liquid obtained There is a lack of this. The Mw of the polymer (A) is more preferably 2,000 or more and less than 10,000 from the viewpoint of obtaining a protective film having very high surface flatness.

(A) Molecular weight distribution of polymer (Mw / Mn: However, this Mn is the number average molecular weight of polystyrene conversion measured by GPC, and is the same below), Preferably it is 1-4, More preferably, it is 1-3. to be.

Such a polymer (A) can be produced by polymerizing or copolymerizing a polymerizable unsaturated compound having an epoxy group or a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds in the presence of a polymerization initiator, preferably in a suitable solvent.

As a solvent which can be used here, diethylene glycol, a propylene glycol alkyl acetate, ethylene glycol alkyl ether acetate, diethylene glycol dialkyl ether is preferable, and diethylene glycol ethyl methyl ether, propylene glycol methyl ether acetate, and propylene are preferable, for example. Glycol ethyl ether acetate, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol diethyl ether are preferable.

As a polymerization initiator, what is generally known as a radical polymerization initiator can be used, As an example thereof, an azo compound, an organic peroxide, and hydrogen peroxide are mentioned, As these specific examples, as said azo compound, For example, 2,2'- Azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile) and the like of;

Examples of the organic peroxides include benzoyl peroxide, lauroyl peroxide, tert-butylperoxy pivalate, 1,1'-bis- (tert-butylperoxy) cyclohexane, and the like.

When using an organic peroxide or hydrogen peroxide as a radical polymerization initiator, it can also be used as a redox type polymerization initiator combining these and a reducing agent.

[(B) COMPOUND]

The compound (B) in the present invention is at least one compound selected from the group consisting of polyhydric carboxylic anhydrides and polyvalent carboxylic acids. This compound (B) acts as a curing agent for the polymer (A).

As an example of the said polyhydric carboxylic anhydride, aliphatic dicarboxylic anhydride, alicyclic polyhydric carboxylic dianhydride, aromatic polyhydric carboxylic anhydride, acid anhydride which has ester group, etc. are mentioned, for example. Specific examples of these aliphatic dicarboxylic acid anhydrides include, for example, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanylic anhydride, maleic anhydride, hexahydrophthalic anhydride and methyltetra. Hydrophthalic anhydride, himic acid anhydride and the like;

As said alicyclic polyhydric carboxylic dianhydride, For example, 1,2,3, 4- butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, etc .;

As said aromatic polyhydric carboxylic anhydride, For example, phthalic anhydride, a pyromellitic anhydride, a trimellitic anhydride, a benzophenone tetracarboxylic anhydride etc .;

As an acid anhydride which has the said ester group, ethylene glycol bis anhydride trimellitate, glycerine tris anhydride trimellitate, etc. are mentioned, for example. Among them, aromatic polyhydric carboxylic acid anhydride is particularly preferable from the viewpoint of better heat resistance of the protective film formed among them.

As an example of the said polyhydric carboxylic acid, aliphatic polyhydric carboxylic acid, alicyclic polyhydric carboxylic acid, aromatic polyhydric carboxylic acid, etc. are mentioned, As these specific examples, as said aliphatic polyhydric carboxylic acid, for example, Succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, itaconic acid and the like;

As said alicyclic polyhydric carboxylic acid, For example, hexahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexane tricarboxylic acid, cyclopentane tetracarboxylic acid, etc .;

As said aromatic polyhydric carboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 1,2,5,8-naphthalene tetracarboxylic acid, etc. are mentioned, respectively. In this, an aromatic polyhydric carboxylic acid is preferable from a viewpoint of the reactivity of the resin composition for protective film formation obtained, the heat resistance of the protective film formed, etc.

These polyhydric carboxylic anhydrides or polyhydric carboxylic acids can be used individually or in combination of 2 or more types.

The use ratio of the compound (B) in the protective film-forming resin composition of the present invention is preferably 1 to 100 parts by mass, and more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the polymer (A). When the use ratio of the compound (B) is less than 1 part by mass, the protective film formed may not have sufficient crosslinking density, and the protective film may lack various resistances. On the other hand, when the use ratio of the compound (B) exceeds 100 parts by mass, a large amount of unreacted compound (B) remains in the protective film formed, and as a result, the properties of the protective film become unstable or the protective film for the substrate. Adhesiveness may fall.

[(C) Copolymer]

(C) copolymer in this invention is a copolymer of said (c1) compound, (c2) compound, (c3) compound, (c4) compound, and (c5) compound, In the resin composition for protective film formation of this invention The surface flatness of the protective film formed can also be remarkably improved even if it functions as a surfactant with a high performance of lowering the surface tension and uses this in a small proportion.

As said (c1) compound, the compound etc. which are respectively represented by following General formula c1-1 and c1-2 are mentioned, for example.

[Formula c1-1]

CH ₂ = CHCOOCH ₂ CH ₂ (CF ₂ ) ₇ CF ₃

[Formula c1-2]

CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ (CF ₂ ) ₇ CF ₃

The compound (c2) is used as a mixture of compounds having different values of a in the formula (2), and the number average value of a is 4 to 12. The value of this a can be calculated and calculated | required from the number average molecular weight of polystyrene conversion measured by the gel permeation chromatography with respect to (c2) compound.

As such a (c2) compound, a commercial item can be used preferably, For example, NK-ester M-40G, M-90G, AM-90G by Shin-Nakamura Chemical Co., Ltd. make; Nichiyu Corporation Blamer PME-200, PME-400, PME-550, etc. are mentioned.

When a plurality of R ⁵ and R ⁶ are present in Formula 3, each R ⁵ may be the same or different, and each R ⁶ may be the same or different. In addition, when a plurality of R ¹⁰ and R ¹¹ are each present in Formula 4, each R ¹⁰ may be the same or different, and each R ¹¹ may be the same or different.

As the compound (c3), in the general formula (3), R ⁴ , R ⁵ and R ⁶ are each an alkyl group having 1 to 20 carbon atoms or a phenyl group, and each of R ⁷ and R ⁸ has a polymer represented by the above general formula (4). It is preferable that it is an unsaturated compound.

As the compound (c3), it is preferably a compound represented by the following formula (c3-1). As a specific example of a compound (c3), the compound represented by each of following General formula c3-1-1 to c3-1-3 is mentioned.

[Formula c3-1]

(In formula c3-1, R ^Si is a group represented by the formula (3), R ¹² is a hydrogen atom or a methyl group, d is an integer of 1 to 3)

[Formula c3-1-1]

[Formula c3-1-2]

[Formula c3-1-3]

(In the above formula, Me is a methyl group, Ph is a phenyl group, and r, s and t are each an integer of 0 to 3).

As said (c4) compound, the alkyl (meth) acrylate etc. which have a C1-C8 alkyl group are mentioned, for example, specifically, methyl methacrylate, 2-ethylhexyl acrylate, etc. are mentioned, for example. Can be mentioned.

As a specific example of the said (c5) compound, the compound which methacrylated the both ends of tetramethylene glycol, the polyethyleneglycol of the polymerization degree 1-20, the polypropylene glycol of the polymerization degree 1-20, etc. are mentioned, for example. As said (c5) compound, a commercial item can be used preferably, As a specific example, NK ester 1G, copper 2G, copper 3G, copper 4G, copper 9G, copper by Shin-Nakamura Chemical Industries, Ltd., for example. 14G, copper 3G, etc. are mentioned.

The ratio of the repeating unit derived from each of the (c1) compound, the (c2) compound, the (c3) compound, the (c4) compound, and the (c5) compound in the (C) copolymer is (c1) to the total of all the repeating units. ) 25 to 35% by weight relative to the compound, (c2) 20 to 30% by weight relative to the compound, (c3) 15 to 20% by weight relative to the compound, (c4) 25 to 35% by weight relative to the compound, (c5) It is 1 to 5% by weight based on the compound.

Although the weight average molecular weight (Mw) of (C) copolymer is 5,000-25,000, it is preferable that it is 10,000-25,000, and it is especially preferable that it is 15,000-25,000. The molecular weight distribution (Mw / Mn) of the (C) copolymer is preferably 1 to 10, more preferably 2 to 4.

There is no restriction | limiting in particular about the manufacturing method of such (C) copolymer, Based on well-known methods, for example, polymerization mechanisms, such as a radical polymerization method, a cation polymerization method, and an anion polymerization method, solution polymerization method, block polymerization method, and emulsion Although it can manufacture by a polymerization method etc., since it is simple by the radical polymerization method in a solution, it is industrially preferable.

As a polymerization initiator used when manufacturing a copolymer (C), For example, Peroxides, such as benzoyl peroxide and diacyl peroxide; Azo compounds, such as azobisisobutyronitrile and phenyl azo triphenylmethane, etc. are mentioned.

Although manufacture of a copolymer (C) can be performed in presence of a solvent or in absence, it is preferable to carry out in presence of a solvent from a viewpoint of workability. Examples of the solvent include alcohols, ketones, esters, alkyl esters of monocarboxylic acids, polar solvents, ethers, propylene glycol and esters thereof, halogenated hydrocarbons, aromatic hydrocarbons, fluorinated inert liquids, and the like. As said alcohol, For example, ethanol, isopropyl alcohol, n-butanol, iso-butanol, tert-butanol, etc .;

As said ketone, For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amino ketone, etc .;

As said ester, For example, methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate etc .;

Examples of the alkyl ester of the monocarboxylic acid include methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate and ethyl 2-methoxypropionate. Propyl 2-methoxypropionate, butyl 2-methoxypropionate and the like;

As said polar solvent, For example, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc .;

As said ether, For example, methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, ethyl cellosolve acetate, tetrahydrofuran, dioxane, etc .; As said propylene glycol and its ester, For example, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, a propylene glycol monobutyl ether acetate, etc .;

Examples of the halogenated hydrocarbons include 1,1,1-trichloroethane, chloroform and the like;

As said aromatic hydrocarbon, For example, benzene, toluene, xylene, etc .; Examples of the fluorinated inert liquid include perfluorooctane, perfluorotri-n-butylamine, and the like, and all of them can be used.

In the production of the copolymer (C), further, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, ethyl thioglycolic acid and octyl thioglycolic acid may be used, if necessary.

The use ratio of the (C) copolymer in the resin composition for protective film formation of this invention becomes like this. Preferably it is 0.01-3 mass parts with respect to 100 weight part of (A) polymers, More preferably, it is 0.05-2 mass parts.

Here, when the use ratio of (C) copolymer exceeds 3 mass parts, the film roughness of a coating film may become easy to generate | occur | produce, and the surface flatness of the protective film formed may be impaired.

[(D) COMPOUND]

The compound (D) in the present invention is a compound having two or more cationically polymerizable groups (except those corresponding to the polymer (A)). Here, as a cationically polymerizable group, an epoxy group etc. are mentioned, for example.

As such (D) compound, the diglycidyl ether of a dialcohol, the polyglycidyl ether of a polyhydric alcohol, the polyglycidyl ether of a polyether polyol, the bisphenol-A epoxy resin, the bisphenol F-type epoxy resin, phenol novolak Type epoxy resin, cresol novolac type epoxy resin, polyphenol type epoxy resin, cyclic aliphatic epoxy resin, aliphatic polyglycidyl ether, diglycidyl ester of aliphatic long-chain dibasic acid, glycidyl ester of higher fatty acid, natural oil Epoxide can be mentioned. As diglycidyl ether of the said dialcohol, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenation Bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, etc .;

As a polyglycidyl ether of the said polyhydric alcohol, it is 1, 4- butanediol diglycidyl ether, 1, 6- hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether, for example. And polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and the like.

The polyether polyol in the polyglycidyl ether of the polyether polyol can be obtained, for example, by adding one or two or more alkylene oxides to an aliphatic polyhydric alcohol such as ethylene glycol, propylene glycol, glycerin, or the like. .

As an epoxidized product of the said natural oil, epoxidized soybean oil, epoxidized linseed oil, etc. are mentioned, for example.

As a commercial item which can be used as such (D) compound, it is a bisphenol-A epoxy resin, for example, Epicoat 1001, copper 1002, copper 1003, copper 1004, copper 1007, copper 1009, copper 1010, copper 828 (above, Japan) Epoxy resins);

As a bisphenol F-type epoxy resin, Epicoat 807 (made by Japan Epoxy Resin Co., Ltd.) etc. is mentioned, for example;

As a phenol novolak-type epoxy resin, For example, Epicoat 152, Copper 154, Copper 157S65 (above, Japan Epoxy Resin Co., Ltd. product), EPPN201, Copper 202 (above, Nippon Kayaku Co., Ltd. product) etc .;

As a cresol novolak-type epoxy resin, EOCN102, copper 103S, copper 104S, 1020, 1025, 1027 (above, Nippon Kayaku Co., Ltd. make), Epicoat 180S75 (made by Japan Epoxy Resin Co., Ltd.), etc. are mentioned, for example. ; As a polyphenol type epoxy resin, Epicoat 1032H60, copper XY-4000 (above, Japan Epoxy Resin Co., Ltd. product) etc. are mentioned, for example;

As the cyclic aliphatic epoxy resin, for example, CY-175, copper 177, copper 179, araldite CY-182, copper 192, 184 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), ERL-4234, 4299, 4221, 4206 (above, UCC company), Shodine 509 (Showa Denko Co., Ltd.), Epiclone 200, copper 400 (above, DIC Corporation), Epicoat 871, copper 872 (more, Japan epoxy resin Co., Ltd.), ED-5661, 5662 (above, Celanese Coating Co., Ltd. product), etc .;

As aliphatic polyglycidyl ether, epolite 100MF (made by Kyoesha Chemical Co., Ltd.), Epiol TMP (made by Nichi-Yu Oil Co., Ltd.), etc. are mentioned, for example.

The use ratio of the compound (D) in the resin composition for forming a protective film of the present invention is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass, and particularly preferably 100 parts by mass of the polymer (A). It is preferable that it is 10-50 mass parts. When the use ratio of (D) compound exceeds 200 mass parts, the applicability | paintability of the resin composition for protective film formation may be impaired, and when it is less than 3 mass parts, the hardness of the protective film formed may be insufficient.

[(E) COMPOUND]

The compound (E) in the present invention is an alkoxysilane compound having an epoxy group. Specific examples thereof include γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxypropyldiethoxysilane. These compounds can be used individually or in combination of 2 or more types.

The use ratio of the compound (E) in the resin composition for forming a protective film of the present invention is preferably 0.1 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the polymer (A).

When the use ratio of the compound (E) is less than 0.1 part by mass, the effect of imparting adhesion to the substrate of the protective film to be formed may not be sufficiently obtained. On the other hand, when the use ratio of the compound (E) exceeds 200 parts by mass , The alkali resistance and solvent resistance of the protective film formed may be insufficient.

[(F) Curing Accelerator]

In the present invention, (F) a curing accelerator may optionally be further used to promote the reaction of the (A) polymer with the (B) compound. As such (F) hardening accelerator, the compound which has a heterocyclic structure containing a secondary nitrogen atom or a tertiary nitrogen atom can be used preferably.

Specific examples of such compounds include pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, indole, indazole, benzimidazole, isocyanuric acid or derivatives thereof. Among these, an imidazole derivative is mentioned as a preferable thing. Examples of the imidazole derivatives include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, 4-methyl-2-phenylimidazole, and 1-benzyl-2-methyl. Midazole, 2-ethyl-4-methyl-1- (2'-cyanoethyl) imidazole, 2-ethyl-4-methyl-1- [2 '-(3 ", 5" -diaminotriazinyl) Ethyl] imidazole, benzimidazole and the like, most preferably from 2-ethyl-4-methylimidazole, 4-methyl-2-phenylimidazole and 1-benzyl-2-methylimidazole. The compound selected is used. These compounds can be used individually or in combination of 2 or more types.

The use ratio of the (F) hardening accelerator in the resin composition for protective film formation of this invention becomes like this. Preferably it is 30 mass parts or less with respect to 100 mass parts of (A) polymers, It is especially used at the ratio of 0.1-10 mass parts. Do. Here, when the use ratio of the (F) hardening accelerator exceeds 30 mass parts, the storage stability of the 1st liquid obtained may be impaired.

[menstruum]

The solvent which can be used by the resin composition for protective film formation of this invention can melt | dissolve or disperse each said component, and is selected from what does not react with each component.

As such a solvent, ether, ethylene glycol alkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, ketone, etc. are mentioned, for example.

As an example of these solvent, As ether, For example, tetrahydrofuran etc .;

As ethylene glycol alkyl ether acetate, For example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, etc .;

As diethylene glycol dialkyl ether, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As propylene glycol alkyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc .;

As propylene glycol alkyl ether propionate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .;

Examples of the ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, and the like.

Of these, diethylene glycol, propylene glycol alkyl acetate and diethylene glycol dialkyl ether are preferable, and diethylene glycol ethyl methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, diethylene glycol dimethyl ether and diethylene glycol mono Ethyl ether acetate and diethylene glycol diethyl ether are more preferable, and diethylene glycol ethyl methyl ether and diethylene glycol dimethyl ether are particularly preferable.

[Resin composition for protective film formation]

The resin composition for protective film formation of this invention is 1st containing (A) polymer, (C) copolymer, (D) compound, (E) compound, a solvent, and (F) hardening accelerator as needed. It is preferable to divide | segment and store into the 2nd liquid containing a liquid, (B) compound, and a solvent, and to use as a resin composition for protective film formation of the two-liquid system which mixes and uses two liquids at the time of use.

Solid content concentration of the 1st liquid (the ratio which the synthetic weight of all components other than the solvent in a 1st liquid occupies for the total weight of a 1st liquid) becomes like this. Preferably it is 3-40 mass%, More preferably, it is 5-30 mass% to be.

The solid content concentration (the ratio of the weight of the compound (B) in the second liquid to the total weight of the second liquid) of the second liquid is preferably 10 to 40% by mass, more preferably 15 to 30% by mass.

<Formation of protective film>

Using the resin composition for protective film formation of this invention, a protective film can be formed as follows, for example.

The resin composition for protective film formation of this invention becomes like this. Preferably it is a two-component resin composition for protective film formation, and mixes and uses a 1st liquid and a 2nd liquid at the time of use. Here, it mixes so that the ratio with respect to the polymer (A) in a 1st liquid of the quantity of the (B) compound in a 2nd liquid may be said preferable use ratio. The resin composition for protective film formation of this invention is used after mixing of a 1st liquid and a 2nd liquid, Preferably it is within 24 hours, More preferably, it is used within 18 hours.

In order to form a protective film, the resin composition for protective film formation after mixing is first apply | coated to the surface of the base which should form a protective film. Subsequently, the preliminary baking is preferably performed to remove the solvent to form a coating film. The post-baking is then performed to cure the coating film to form a protective film.

As a kind of board | substrate used for formation of a protective film, glass substrate, a silicon wafer, and the board | substrate with which various metals, for example, ITO (indium tin oxide) etc., were formed in these surfaces are mentioned, for example.

It does not specifically limit as a coating method of a resin composition solution, For example, the appropriate method, such as spraying method, the roll coating method, the spin coating method (spin coating method), the slit coating method, the bar coating method, the inkjet method, can be used, and spin The coating method and the slit coating method are preferable. In particular, the slit coating method is preferable because the advantageous effects of the present invention can be exhibited to the maximum.

The conditions of pre-baking and post-baking should be appropriately set according to the kind of each component, the use ratio, etc., respectively. Preliminary baking can be performed, for example at 70-90 degreeC on conditions for about 1 to 15 minutes. Post-baking can be performed by appropriate heating apparatuses, such as a hotplate and a clean oven. As a temperature of post-baking, 150-250 degreeC is preferable. As a time of post-baking, it is preferable to carry out for 5 to 30 minutes, when using a hot plate as a heating apparatus, and for 30 to 90 minutes, respectively, when using a clean oven as a heating apparatus.

The film thickness of the protective film thus formed is preferably 0.1 to 8 µm, more preferably 0.1 to 6 µm, still more preferably 0.1 to 4 µm. In addition, when a protective film is formed on the gas which has a level | step difference, said film thickness means the thickness from the top of a level | step difference.

Since the protective film formed by the resin composition for protective film formation of this invention is high on the surface planarization performance and excellent in various physical properties, even when formed on the board | substrate with a step, as apparent from the following example, for example, It is very preferable as a protective film for optical devices, such as a color filter.

[Example]

Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured by the gel permeation chromatography (GPC) by the following conditions below.

Measuring device: manufactured by Tosoh Corporation, "HLC8220 System"

Separation column: Tosoh Co., Ltd. product, TSKgelGMH _HR- N is connected in series used

Column temperature: 40 ℃

Elution solvent: Tetrahydrofuran (made by Wako Junyaku Kogyo Co., Ltd.)

Flow rate: 1.0 mL / min

Sample concentration: 1.0 mass%

Sample injection volume: 100 μm

Detector: parallax refractometer

Standard material: monodisperse polystyrene

In addition, the solution viscosity of the resin composition for protective film formation was measured at 30 degreeC using the Tokyo Keiki Co., Ltd. type E viscometer.

<Production of (A) Polymer>

Synthesis Example 1

5 parts by mass of 2,2'-azobis-isobutyronitrile and 200 parts by mass of diethylene glycol methylethyl ether were charged into a flask equipped with a cooling tube and a stirrer. Subsequently, 70 mass parts of glycidyl methacrylate and 30 mass parts of styrene were thrown in, and it substituted nitrogen, and stirring was started slowly. The solution temperature was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing copolymer (A-1). Solid content concentration (The ratio which the weight of the polymer in a polymer solution occupies for the total weight of a solution, and is the same below) of the obtained polymer solution was 33.1 mass%. The weight average molecular weight Mw of the obtained polymer was 10,000, and molecular weight distribution (Mw / Mn) was 2.

Synthesis Example 2

5 parts by mass of 2,2'-azobis-isobutyronitrile and 200 parts by mass of diethylene glycol methylethyl ether were charged into a flask equipped with a cooling tube and a stirrer. Subsequently, 50 mass parts of glycidyl methacrylate and 50 mass parts of styrene were thrown in, and nitrogen-substituted, and stirring was started slowly. The solution temperature was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing the copolymer (A-2). Solid content concentration of the obtained polymer solution was 32.6 mass%. The weight average molecular weight Mw of the obtained polymer was 11,000, and molecular weight distribution (Mw / Mn) was 2.

<Production of (C) Copolymer>

Synthesis Example 3

28.4 parts by mass of the compound represented by the above formula (c1-1) as a compound (c1) in a glass flask equipped with a stirring device, a condenser, and a thermometer, and NK-ester M-90G (trade name, Shinnakamura Chemical Co., Ltd.) ) Production) 20.7 parts by mass, (c3) 18.1 parts by mass of the compound represented by the formula c3-1-1-1 as a compound, (c4) 5.9 parts by mass of methyl methacrylate and 23.5 parts by mass of 2-ethylhexyl acrylate (C5) 3.4 mass parts of the compound which methacrylated both ends of tetramethylene glycol as (c5) compound, 414 mass parts of isopropyl alcohol as a solvent, and 2,2'- azo as a polymerization initiator under reflux in nitrogen gas stream. 0.7 mass part of bisisobutyronitrile and 4 mass parts of lauryl mercaptans were added as a chain transfer agent, and it copolymerized by refluxing at 75 degreeC for 8 hours, and obtained the solution containing copolymer (C-1). Thereafter, the solvent was removed under a heating condition of 70 ° C. or lower using an evaporator to isolate the copolymer (C-1). The number average molecular weight Mn of the obtained copolymer (C-1) was 2,800, the weight average molecular weight Mw was 5,300, and the molecular weight distribution (Mw / Mn) was 1.9.

[Formula c3-1-1-1]

(Wherein Me is a methyl group)

Synthesis Example 4

A copolymer (C-2) was obtained in the same manner as in Synthesis Example 3 except that the addition amount of lauryl mercaptan as the chain transfer agent in Synthesis Example 3 was 1 mass part.

 The number average molecular weight Mn of the obtained copolymer (C-2) was 4,700, the weight average molecular weight Mw was 11,000, and the molecular weight distribution (Mw / Mn) was 2.3.

Synthesis Example 5

A copolymer (C-3) was obtained in the same manner as in Synthesis Example 3 except that lauryl mercaptan as the chain transfer agent was not used in Synthesis Example 3 and the copolymerization temperature and time were set to 73 ° C and 10 hours, respectively.

The number average molecular weight Mn of the obtained copolymer (C-3) was 5,600, the weight average molecular weight Mw was 21,000, and the molecular weight distribution (Mw / Mn) was 3.8.

Example 1

<Production of Resin Composition for Protective Film Formation>

Preparation of First Liquid

(A) The said synthesis | combination as (C) copolymer in the solution (Amount equivalent to 100 mass parts in conversion into copolymer (A-1)) containing the copolymer (A-1) obtained by the said synthesis example 1 as a polymer. 0.5 part by weight of the copolymer (C-1) obtained in Example 3 was added thereto, and 40.0 parts by mass of a novolak-type epoxy resin (trade name "Epicoat 152", manufactured by Japan Epoxy Resin Co., Ltd.) as the (D) compound, and ( E) 20.0 mass parts of (gamma)-glycidoxy propyl trimethoxysilane were added as a compound, and diethylene glycol methyl ethyl ether was further added as a solvent, and it filtered by the Millipore filter of 0.5 micrometer of pore diameters, and solid content concentration 18 mass% A first solution of was prepared.

Preparation of Second Liquid

As the compound (B), 40 parts by weight of trimellitic anhydride was dissolved in diethylene glycol methylethyl ether as a solvent to prepare a second liquid having a solid content concentration of 25% by mass.

[Manufacture of Resin Composition for Protective Film Formation]

The resin composition for protective film formation was manufactured by adding and mixing the whole quantity of the said 2nd liquid with respect to the whole quantity of the 1st liquid manufactured above. The solution viscosity of this resin composition for protective film formation was 4.5 cP.

It evaluated as follows using this resin composition for protective film formation.

The evaluation results are shown in Table 1.

<Evaluation of Resin Composition for Protective Film Formation>

(1) Appearance Evaluation of Coating Film

The resin composition for protective film formation manufactured above was apply | coated using slit die coater (Tokyo Kogyo Co., Ltd. make, model "TR632105-CL") on 550x650 mm chromium film-forming glass, and the arrival pressure was 100 Pa. The solvent was removed by vacuum drying and prebaked at 80 ° C. for 2 minutes to form a coating film having a film thickness of 1.0 μm.

The appearance of the coating film was visually observed under a sodium lamp. The occurrence state of these nonuniformity was evaluated as the fog nonuniformity which generate | occur | produced as a whole and the nonuniformity originating from the proxy pin by prebaking as a pin nonuniformity. The case where almost no irregularity was observed was made into the appearance "goodness" for the external appearance "good" for the coating film external appearance "good", and the case where an irregularity was observed for a while and the case where the nonuniformity was clearly observed.

(2) evaluation of transparency

The resin composition for protective film formation prepared above was apply | coated using a slit die coater "TR632105-CL" on an alkali free glass substrate of 550x650 mm, the reaching pressure was set to 100 Pa, and the solvent was removed by vacuum drying. Then, prebaking was performed at 80 degreeC for 2 minutes, and after-baking at 230 degreeC for 60 minutes in oven, the cured film (protective film) of 1.0 micrometer in thickness was formed.

For a substrate having the protective film, a spectrophotometer (manufactured by Hitachi Seisakusho Co., Ltd., model "150-20 type double beam") was used as a reference side, using the alkali free glass substrate which does not have a protective film as a reference side from 400 to 400 wavelength range. The transmittance of 800 nm was measured. The minimum value of the transmittance | permeability in this wavelength range is shown in Table 1 as a value of transparency. When this value is 95% or more, it can be said that transparency of a protective film is favorable.

(3) Evaluation of heat discoloration resistance

About the board | substrate with a protective film formed by said "(2) transparency evaluation", after heating at 250 degreeC in oven for 1 hour, transparency was measured similarly to said (2) again. At this time, the heat discoloration resistance calculated according to the following equation (1) is shown in Table 1. When this value is 5% or less, it can be said that heat discoloration resistance is favorable.

&Quot; (1) &quot;

Heat discoloration resistance (%) = transparency (%) before heating-transparency (%) after heating

(4) evaluation of planarization performance

Pigment-based color resists (trade names "JCR RED 689", "JCR GREEN 706" and "CR 8200B", above, manufactured by JSR Co., Ltd.) on a SiO ₂ immersed glass substrate were used. A stripe color filter was formed. That is, one of the color resists is applied by a spinner, prebaked at 90 ° C. for 150 seconds on a hot plate to form a coating film, and then using an exposure machine Canon PLA501F (manufactured by Canon Co., Ltd.) through a predetermined pattern mask. Ghi line (intensity ratio of wavelength 436 nm, 405 nm, 365 nm = 2.7: 2.5: 4.8) was irradiated at an exposure dose of 2,000 J / m 2 in terms of i-line, and then developed using 0.05 mass% potassium hydroxide aqueous solution. After rinsing with ultrapure water for 60 seconds, heat treatment was performed at 230 ° C. for 30 minutes in an oven to form a monochromatic stripe color filter. By repeating this operation for three colors, a stripe-like color filter (stripe width of 200 mu m) of three colors of red, green, and blue was formed.

It was 1.0 micrometer when the unevenness | corrugation of the surface of the board | substrate with which this color filter was formed was measured with the surface roughness meter "(alpha) -step" (brand name: KLA Tenco Co., Ltd. product). However, it measured by 2,000 micrometers in measurement length, 2,000 micrometers in each side of a measurement range, and measuring number n = 5. That is, the measurement direction is set to two directions of the stripe line short axis direction in the red, green, and blue directions and the stripe line major axis direction of the same color of red, red, green, green, blue, and blue, and n = 5 for each direction. It measured (the n-number of the sum is 10).

After applying the composition for forming a protective film with a spinner thereon, the film is prebaked at a temperature of 90 ° C. for 5 minutes on a hot plate to form a coating film, followed by post-baking at 230 ° C. for 60 minutes in an oven. A protective film having a film thickness of 2.0 mu m was formed.

The surface unevenness | corrugation of a protective film was measured with the contact type film thickness measuring apparatus "(alpha) -step" about the board | substrate which has a protective film on the color filter formed as mentioned above. That is, it measured by the measurement length 2,000 micrometers, the measurement range each side 2,000 micrometers, and the measurement number n = 5. That is, the measurement direction is set to two directions of the stripe line short axis direction in the red, green, and blue directions and the stripe line major axis direction of the same color of red, red, green, green, blue, and blue, and n = 5 for each direction. It measured (the n-number of the sum is 10). Table 10 shows the average values of ten times of the difference between the highest and lowest portions (nm) for each measurement. When this value is 300 nm or less, it can be said that planarization performance is favorable.

(5) Evaluation of film thickness uniformity of coating film

In the same manner as in the above "(2) transparency evaluation", a protective film was formed on the alkali free glass substrate. About the protective film on this board | substrate, 20 coating film thicknesses in the same board | substrate were measured and the film thickness uniformity of the coating film was computed by following formula (2).

<Equation 2>

Film thickness uniformity (%) of coating film = [(maximum value-minimum value of film thickness) ÷ {(average value of film thickness of 20 points) x 2}] x 100

In addition, the said 20 measuring point was determined as follows. That is, the inside area (450x550mm) except the range of 5 cm from each end of the long side and the short side of the board | substrate (550x650 mm) is made into a measurement area, and the long side direction and the short side direction in the said area | region Each 10 points (total 20 points) were determined at 4 cm intervals on a straight line, respectively, and these were taken as measuring points.

When the film thickness uniformity of the coating film computed in this way is 1% or less, it can be said that the film thickness uniformity of a coating film is favorable.

Examples 2 to 7 and Comparative Examples 1 to 3

Except having performed the kind and usage-amount of each component as Table 1, respectively, it produced and evaluated the resin composition for protective film formation similarly to Example 1.

The evaluation results are shown in Table 1.

In Examples 5 to 7, in addition to the components (A) to (E), 1.0 parts by mass of 1-benzyl-2-methylimidazole were each used as the (F) curing accelerator. In Examples 6 and 7, 2 types of (C) copolymers were used, respectively. In Comparative Examples 1 and 2, a commercially available surfactant was used instead of the (C) copolymer, and in Comparative Example 3, neither the (C) copolymer nor the commercially available surfactant was used.

"-" In Table 1 shows that the component corresponding to the said column was not used.

The abbreviation of each component shown in Table 1 shows the following, respectively.

<(A) Polymer>

A-1: copolymer (A-1) prepared in Synthesis Example 1

A-2: copolymer (A-2) prepared in Synthesis Example 2

In addition, the (A) polymer was used for manufacture of a 1st liquid as a solution containing this, respectively. The usage-amount of the (A) polymer in Table 1 is the value converted into the quantity of each (A) polymer contained in the used polymer solution.

<(C) Copolymer>

C-1: copolymer (C-1) prepared in Synthesis Example 3

C-2: copolymer (C-2) prepared in Synthesis Example 4

C-3: copolymer (C-3) prepared in Synthesis Example 5

<Surfactant>

c-1: Silicone type surfactant (Toray Dow Corning Co., Ltd. brand name: SH-193)

c-2: Fluorine-type surfactant (Neos Co., Ltd. brand name: Pgentgent 222F)

<(E) Compound>

E-1: γ-glycidoxypropyltrimethoxysilane

<(F) Curing accelerator>

F-1: 1-benzyl-2-methylimidazole

Claims (4)

(A) a polymer having a repeating unit derived from a polymerizable unsaturated compound having an epoxy group,
(B) at least one compound selected from the group consisting of polyhydric carboxylic anhydrides and polyhydric carboxylic acids,
(C) 25 to 35 mass% of the compound represented by following formula (c1),
(c2) 20 to 30 mass% of a compound represented by the following formula (2),
(c3) 15 to 20 mass% of a polymerizable unsaturated compound having a group represented by the following formula (3),
(c4) 25 to 35 mass% of a polymerizable unsaturated compound having an alkyl group having 1 to 8 carbon atoms, and
(c5) a copolymer of 1 to 5% by mass of a polymerizable unsaturated compound having two or more unsaturated bonds in one molecule, and having a weight average molecular weight of 5,000 to 25,000,
(D) a compound having two or more cationically polymerizable groups, except those corresponding to the polymers (A); and
(E) Alkoxysilane Compound Having Epoxy Group
It contains, The resin composition for protective film formation characterized by the above-mentioned.
<Formula 1>
CH ₂ = CR ¹ COOCH ₂ CH ₂ C ₈ F ₁₇
(In Formula 1, R ¹ is a hydrogen atom or a methyl group.)
<Formula 2>
CH ₂ = CR ² COO (C ₂ H ₄ O) _a R ³
(In formula 2, R <^2> is a hydrogen atom or a methyl group, R <^3> is a methyl group, an ethyl group, a propyl group, or a butyl group, a is a repeating unit number, and the number average value is 4-12.)
<Formula 3>

(In Formula 3, R <^4> , R <^5> , R <^6> , R <^7> and R <^8> are respectively independently a C1-C20 alkyl group, a phenyl group, or group represented by following formula (4), b is an integer of 0-3. )
<Formula 4>

(In Formula 4, R <^9> , R <^10> and R <^11> is respectively independently a C1-C20 alkyl group or a phenyl group, c is an integer of 0-3.) The resin composition for protective film formation of Claim 1 which further contains (F) hardening accelerator. The resin composition for protective film formation of Claim 1 or 2 used for the slit coating method. It is formed from the resin composition for protective film formation of any one of Claims 1-3, The protective film of the color filter characterized by the above-mentioned.