JPH08183819A - Radiation-sensitive resin composition - Google Patents

Abstract

PURPOSE: To obtain a radiation-sensitive resin composition suitable for use in forming a protective film having a section effective in preventing wiring breakage on an optical device. CONSTITUTION: The composition comprises a copolymer (A) obtained from (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, (a2) an epoxidized unsaturated compound, (a3) a monoolefin compound other than the ingredients (a1) and (a2), and (a4) 1-15wt.% conjugated diene compound; a polymerizable ethylenic compound and a radiation-sensitive polymerization initiator (B).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive resin composition having heat resistance suitable as a protective film forming material for optical devices.

[0002]

2. Description of the Related Art Optical devices such as liquid crystal display devices and solid-state image pickup devices are subjected to a dipping treatment in a manufacturing process such as a solvent, an acid or an alkaline solution, or a surface thereof is sputtered when a wiring electrode layer is formed. May be subjected to severe treatment such as locally heated to high temperature. For this reason, these elements may be provided with a protective film on their surfaces in order to prevent deterioration during manufacturing.

This protective film is required to have various properties that can withstand the above-mentioned treatments. Specifically, it has excellent adhesion to the substrate or the lower layer, is smooth and has a high surface hardness, and is transparent. Excellent heat resistance and light resistance to prevent deterioration such as coloring, yellowing, and whitening over a long period of time, solvent resistance, acid resistance, chemical resistance such as alkali resistance, etc. It is required to have excellent water resistance.

On the other hand, when such a protective film is applied to a color filter of a color liquid crystal display device, it is generally desired that the steps of the color filter, which is a base substrate, can be flattened. In particular, when manufacturing a STN type color liquid crystal display device, it is necessary to perform the bonding of the color filter and the counter substrate with strict accuracy, and it is essential to make the cell gap between the substrates uniform. Has become.

For this reason, conventionally, a polymer solution having a low viscosity and a high concentration is applied to the surface of the color filter to be flattened to some extent in advance, and then a protective film material is applied, and such a flattening operation is required. However, the manufacturing of color liquid crystal display devices is complicated.

In recent years, as a mounting method for a color liquid crystal display element, COG (CHIP ON G) suitable for downsizing is adopted.
The LASS) method is drawing attention, but when manufacturing a color liquid crystal display element by this COG method, it is necessary to prevent the protective film from remaining on a portion other than the color filter.

Conventionally, in order to provide a protective film on a color filter so that the protective film does not remain on a portion other than the color filter, a resist pattern is formed on the formed protective film, and the resist pattern is used as a mask for protection. A method is employed in which the film is dry-etched and the protective film other than the color filter is removed by dry etching. However, in this dry etching method,
Since the used resist pattern must be removed after dry etching, the process is complicated and the dry etching may cause defects in the color liquid crystal display element. For this reason, it is possible to satisfy the above-mentioned characteristics required for the protective film, to flatten the level difference on the surface of the color filter which is the base substrate, and to expose and develop unnecessary portions (for example, other than the color filter). A material that can easily remove the protective film (part) is desired. Radiation-sensitive resin compositions described in JP-A-6-43643 and JP-A-6-192389 are known as materials capable of forming a protective film satisfying such requirements.

In the process of manufacturing a color liquid crystal display device using these radiation-sensitive resin compositions, the surface of the color filter, which is the base substrate, is flattened, and unnecessary portions are removed by radiation and development to form a predetermined pattern. After the protective film of (1) is provided on the color filter, the wiring electrode layer is formed thereon, but in this case, the cross-sectional shape of the protective film poses a problem. That is, when the cross-sectional shape of the protective film is an acute angle or when the corner is sharp, the wiring electrode layer is easily broken. For this reason, there is a demand for a material that forms a smooth cross-sectional shape that is unlikely to cause wire breakage.

[0009]

The object of the present invention is to provide various properties conventionally required as a protective film, specifically, adhesion, surface hardness, transparency, heat resistance, light resistance, chemical resistance, In addition to satisfying water resistance, it is possible to flatten the steps of the color filter that is the base substrate, and also to easily remove unnecessary parts (eg, parts other than the color filter) by irradiation and development. Moreover, it provides a protective film that forms a cross-sectional shape that is hard to break.
It is intended to provide a radiation-sensitive resin composition suitable as a protective film forming material for an optical device.

[0010]

Means for Solving the Problems The above problem is the present invention, [A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (hereinafter, also referred to as "compound (a1)"), (A2) Epoxy group-containing unsaturated compound (hereinafter,
Also referred to as "compound (a2)". ), (A3) above (a
Monoolefin unsaturated compounds other than 1) and (a2) (hereinafter, also referred to as “compound (a3)”) and (a
4) A copolymer of a conjugated diolefin unsaturated compound (hereinafter, also referred to as “compound (a4)”) in which the copolymerization amount of (a4) is 1 to 15% by weight (hereinafter, “copolymer”). Also referred to as a polymer [A].), [B] a polymerizable compound having an ethylenically unsaturated bond (hereinafter, also referred to as "polymerizable compound [B]"), and [C] radiation-sensitive polymerization initiator ( Hereinafter, this is also achieved by a radiation-sensitive resin composition containing a "polymerization initiator [C]").

The radiation-sensitive resin composition of the present invention will be described in detail below. The radiation-sensitive resin composition of the present invention is characterized by comprising a copolymer [A], a polymerizable compound [B] and a polymerization initiator [C].

Copolymer [A] The copolymer [A] comprises the compound (a1), the compound (a2),
The compound (a3) and the compound (a4) can be synthesized by radical polymerization in a solvent in the presence of a polymerization initiator.

Compound (a1) The compound (a1) is necessary for controlling the solubility in an alkaline aqueous solution which is a developing solution and for increasing the surface hardness of the resulting protective film, and is the copolymer [A] used in the present invention. ] Is a structural unit derived from the compound (a1),
Preferably 5 to 40% by weight, particularly preferably 10 to 30
Contains by weight percent. A copolymer having less than 5% by weight of this structural unit is difficult to dissolve in an alkaline aqueous solution, while a copolymer exceeding 40% by weight tends to have too high solubility in an alkaline aqueous solution. Compound (a
Examples of 1) include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; maleic acid, fumaric acid,
Dicarboxylic acids such as citraconic acid, mesaconic acid and itaconic acid; and anhydrides of these dicarboxylic acids. Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from the viewpoint of copolymerization reactivity, solubility in an alkaline aqueous solution and easy availability. These may be used alone or in combination.

Compound (a2) The compound (a2) is necessary for increasing the heat resistance and surface hardness of the resulting protective film, and the copolymer [A] used in the present invention is derived from the compound (a2). The constituent unit is preferably 10 to 70% by weight, particularly preferably 2
It contains 0 to 50% by weight. When the content of this structural unit is less than 10% by weight, the heat resistance of the resulting protective film tends to decrease, while when it exceeds 70% by weight, the storage stability of the copolymer tends to decrease.

Examples of the compound (a2) include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and acrylic acid-3,4. -Epoxybutyl, methacrylic acid-3,4
-Epoxy butyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-
Examples include ethyl acrylate-6,7-epoxyheptyl and the like. Among these, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl and the like are preferably used from the viewpoint of enhancing the copolymerization reactivity and the heat resistance of the resulting protective film. These may be used alone or in combination.

Compound (a3) The compound (a3) is necessary for improving the storage stability of the copolymer [A], and the copolymer [A] used in the present invention is the same as the compound (a3). The derived unit
Preferably 10-70% by weight, particularly preferably 20-5
Contains 0% by weight. When this structural unit is less than 10% by weight, the storage stability of the copolymer [A] tends to be lowered, while when it exceeds 70% by weight, the copolymer [A] is reduced.
Is less likely to dissolve in an alkaline aqueous solution, and the heat resistance of the resulting protective film tends to decrease.

Examples of the compound (a3) include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate; acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; Cyclic alkyl ester of methacrylic acid such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate;
Acrylic acid cyclic alkyl esters such as cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentaoxyethyl acrylate, isobornyl acrylate;
Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and itaconic acid diethyl; 2-hydroxyethyl methacrylate, 2-hydroxy Hydroxyalkyl ester such as propylmethacrylate;
And styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate and the like. Of these, styrene, dicyclopentanyl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate and the like are preferable from the viewpoint of enhancing the copolymerization reactivity and the heat resistance of the resulting protective film. These may be used alone or in combination.

Compound (a4) The compound (a4) is necessary for improving the storage stability of the copolymer [A] and the flatness and cross-sectional shape of the resulting protective film. The combined product [A] contains 1 to 15% by weight of the structural unit derived from the conjugated diolefin unsaturated compound (a4). If this constituent unit is less than 1% by weight, the cross-sectional shape of the resulting protective film will be poor, and if it exceeds 15% by weight, the surface hardness and heat resistance of the protective film will be poor. When the content of the constituent unit is particularly 1 to 10% by weight, a protective film having extremely excellent cross-sectional shape, surface hardness and heat resistance can be obtained.
Examples of the compound (a4) include 1,3-butadiene,
Examples include isoprene and 2,3-dimethyl-1,3-butadiene. These may be used alone or in combination.

As described above, the copolymer [A] used in the present invention has a carboxyl group and / or a carboxylic acid anhydride group and an epoxy group, and has a suitable solubility in an alkaline aqueous solution. Besides, it can be easily cured by heating without using a special curing agent.

The radiation-sensitive resin composition containing the above-mentioned copolymer [A] does not cause development residue during development, and
Further, it is possible to easily form a protective film having a predetermined pattern without film sticking. When the radiation-sensitive resin composition containing such a copolymer [A] is applied on a color filter having a step on the surface, the step can be flattened.

Examples of the solvent used for the synthesis of the copolymer [A] include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether; Examples include cellosolve esters such as methyl cellosolve acetate,
Aromatic hydrocarbons, ketones, esters and the like can also be used.

As the polymerization initiator used for producing the copolymer [A], those generally known as radical polymerization initiators can be used, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-
Azo compounds such as methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, 1,1′-
Organic peroxides such as bis- (t-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox type initiator.

Polymerizable Compound [B] As the polymerizable compound [B] used in the present invention, monofunctional, difunctional or trifunctional or higher functional (meth) acrylates have good polymerizability and the resulting protective film is obtained. From the viewpoint of improving the heat resistance of, it is preferable.

Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate and 2- (meth) acrylate. Acryloyloxyethyl-
2-Hydroxypropyl phthalate and the like may be mentioned, and examples of commercially available products thereof include Aronix M-101, M-111 and M-114 (Toagosei Kagaku Kogyo Co., Ltd.).
Made), KAYARAD TC-110S, TC-12
0S (Nippon Kayaku Co., Ltd.), Viscoat 158, 231
1 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate and the like can be mentioned. Examples of commercially available products thereof include Aronix M-2.
10, M-240, M-6200 (manufactured by Toagosei Chemical Industry Co., Ltd.), KAYARAD HDDA, HX-22.
0, the same R-604 (manufactured by Nippon Kayaku Co., Ltd.), Viscoat 26
0, 312, 335 HP (Osaka Organic Chemical Industry Co., Ltd.)
Manufactured) and the like.

Examples of the trifunctional or higher functional (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, and pentaerythritol tetra (meth) acrylate. (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, and examples of commercially available products thereof include Aronix M-309, M-400, and M-40.
5, the same M-450, the same M-7100, the same M-8030,
Same M-8060 (Toagosei Chemical Industry Co., Ltd.), KAYA
RAD TMPTA, DPHA, DPCA-20,
Same DPCA-30, same DPCA-60, same DPCA-1
20 (manufactured by Nippon Kayaku Co., Ltd.), Viscoat 295, and 30
0, the same 360, the same GPT, the same 3PA, the same 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like. These monofunctional, difunctional or trifunctional or higher functional (meth) acrylates may be used alone or in combination.

Polymerization Initiator [C] As the polymerization initiator [C] used in the present invention, a radiation sensitive radical polymerization initiator, a radiation sensitive cationic polymerization initiator or the like can be used.

When using these polymerization initiators, it is necessary to consider whether the radiation irradiation conditions are an oxygen atmosphere or an oxygen-free atmosphere. When the irradiation is carried out in an oxygen-free atmosphere, all general types of radiation-sensitive radical polymerization initiators and radiation-sensitive cationic polymerization initiators can be used. On the other hand, when irradiation is performed in an oxygen atmosphere, depending on the type of the radiation-sensitive radical polymerization initiator, radicals are inactivated by oxygen, which causes a decrease in sensitivity. In some cases, sufficient hardness cannot be obtained, and it is necessary to select and use a radiation-sensitive radical polymerization initiator. However, the radiation-sensitive cationic polymerization initiator hardly deactivates active species due to oxygen, and can be freely used in an oxygen atmosphere or an oxygen-free atmosphere.

Examples of the radiation-sensitive radical polymerization initiator used in an oxygen-free atmosphere include α-diketones such as benzyl and diacetyl; acyloins such as benzoin; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and the like. Acyloin ethers; benzophenones such as thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone; Acetophenone, p-dimethylaminoacetophenone, α, α′-dimethoxyacetoxybenzophenone, 2,2′-dimethoxy-2-
Phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-
Acetophenones such as morpholino-1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; quinones such as anthraquinone and 1,4-naphthoquinone; phenacyl chloride Halogen compounds such as tribromomethylphenyl sulfone and tris (trichloromethyl) -S-triazine; and peroxides such as di-t-butyl peroxide. Commercially available products of this radiation-sensitive radical polymerization initiator include Irgacure 184 and Irgacure 184.
9, ibid 500, ibid 651, ibid 907, Darocure
1116, 1173, 1664, 2956, 4
043 (manufactured by Ciba Geigy) and the like.

As the radiation-sensitive radical polymerization initiator used in an oxygen atmosphere, for example, 2-methyl- [4
-(Methylthio) phenyl] -2-morpholino-1-
Propanone, 2-benzyl-2-dimethylamino-1-
Acetophenones such as (4-morpholinophenyl) -butan-1-one; and halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone, tris (trichloromethyl) -S-triazine.

Further, as the radiation-sensitive cationic polymerization initiator, for example, phenyldiazonium tetrafluoroborate, phenyldiazonium hexafluorophosphonate, phenyldiazonium hexafluoroarsenate, phenyldiazonium trifluoromethanesulfonate, phenyldiazonium trifluoroacetate,
Phenyldiazonium-p-toluenesulfonate, 4
-Methoxyphenyldiazonium tetrafluoroborate, 4-methoxyphenyldiazonium hexafluorophosphonate, 4-methoxyphenyldiazonium hexafluoroarsenate, 4-methoxyphenyldiazonium trifluoromethanesulfonate, 4-methoxyphenyldiazonium trifluoroacetate, 4-methoxyphenyl Diazonium-p-toluenesulfonate, 4-ter-butylphenyldiazonium tetrafluoroborate, 4-ter-butylphenyldiazonium hexafluorophosphonate, 4-ter-butylphenyldiazonium hexafluoroarsenate, 4
Diazonium salts such as -ter-butylphenyldiazonium trifluoromethanesulfonate, 4-ter-butylphenyldiazonium trifluoroacetate, 4-ter-butylphenyldiazonium-p-toluenesulfonate; diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoro Phosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenyl Cycloalkenyl iodonium hexafluoroarsenate, 4-methoxyphenyl phenyl iodonium trifluoromethanesulfonate, 4-methoxyphenyl phenyl iodonium trifluoroacetate, 4
-Methoxyphenylphenyl iodonium-p-toluene sulfonate, bis (4-ter-butylphenyl)
Iodonium tetrafluoroborate, bis (4-te
r-Butylphenyl) iodonium hexafluorophosphonate, bis (4-ter-butylphenyl) iodonium hexafluoroarsenate, bis (4-ter
-Butylphenyl) iodonium trifluoromethanesulfonate, bis (4-ter-butylphenyl) iodonium trifluoroacetate, bis (4-ter-
Iodonium salts such as butylphenyl) iodonium-p-toluenesulfonate; triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoro Acetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoro Rmethanesulfonate, -Methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoro Arsenate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, 4-phenylthiophenyldiphenyl-p
-Sulfonium salts such as toluene sulfonate; and metallocene compounds such as (1-6- [eta] -cumene) ([eta] -cyclopentadienyl) iron (1+) hexafluorophosphate (1-). Examples of commercially available products of this radiation-sensitive cationic polymerization initiator include ADEKA ULTRASET PP-33 (manufactured by Asahi Denka Kogyo Co., Ltd.), which is a diazonium salt, OPTOMER SP-150 and -170 (Asahi Denka Kogyo, which are sulfonium salts). (Manufactured by Ciba Geigy) and a metallocene compound, Irgacure261.
And the like.

Further, by using these radiation-sensitive radical polymerization initiators or radiation-sensitive cationic polymerization initiators in combination with radiation-sensitive sensitizers, it is possible to obtain a highly sensitive radiation-sensitive resin composition with little inactivation by oxygen. Is also possible.

Radiation-sensitive resin composition In the radiation-sensitive resin composition of the present invention, the above-mentioned copolymer [A], polymerizable compound [B] and polymerization initiator [C] are uniformly mixed. It is prepared by Usually, the radiation-sensitive resin composition of the present invention is dissolved in an appropriate solvent and used in a solution state. For example, by mixing the copolymer [A], the polymerizable compound [B], the polymerization initiator [C] and other compounding agents in a predetermined ratio,
A radiation sensitive resin composition in a solution state can be prepared.

The radiation-sensitive resin composition of the present invention contains the polymerizable compound [B] based on 100 parts by weight of the copolymer [A].
Is preferably 40 to 200 parts by weight, more preferably 8
0 to 150 parts by weight and the polymerization initiator [C] are contained in a proportion of preferably 1 to 50 parts by weight, particularly preferably 5 to 30 parts by weight. When the amount of the polymerizable compound [B] is less than 40 parts by weight, the resulting protective film is liable to have film roughness or film slippage. Further, when the amount of the polymerization initiator [C] is less than 1 part by weight, the resulting protective film is liable to have film roughness or film slippage, and when it exceeds 50 parts by weight, the transparency of the resulting protective film is likely to be lowered.

As the solvent used for preparing the radiation-sensitive resin composition of the present invention, the components of the copolymer [A], the polymerizable compound [B] and the polymerization initiator [C] are uniformly dissolved, Those that do not react with each component are used. Specifically, for example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate. Kind;
Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether; propylene glycol methyl ether acetate, propylene Propylene glycol alkyl ether acetates such as glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate; propylene glycol methyl ether propionate, propylene glycol ethyl ether ether Propylene glycol alkyl ether acetates such as pionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2- Ketones such as pentanone; and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, hydroxyacetic acid Methyl, ethyl hydroxyacetate,
Butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, protyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3- Methyl methyl butanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, propoxyacetic acid Butyl, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropyl Propyl pionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxypropione Ethyl acid, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate,
Propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3
-Ethyl ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-
Methyl propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate,
Butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3
-Esters such as propyl butoxypropionate, butyl 3-butoxypropionate, and the like.

Among these solvents, glycol ethers, ethylene glycol alkyl ether acetates, esters, and diethylene glycols are preferably used because of their solubility, reactivity with each component, and ease of forming a coating film. .

Further, a high boiling point solvent may be used in combination with the above solvent. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethylether. , Dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol,
1-nonanol, benzyl alcohol, benzyl acetate,
Examples thereof include ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate and phenyl cellosolve acetate.

The radiation-sensitive resin composition of the present invention may contain other components other than the above, if necessary, within the range not impairing the object of the present invention.

Here, as the other component, a surfactant for improving coating property and flattening property can be mentioned. A fluorine-based surfactant can be preferably used as this surfactant, and examples of commercially available products thereof include BM-1.
000, BM-1100 (manufactured by BM CHEMIE),
MegaFac F142D, F172, F173, F183 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-135, FC-170C, FC-430, FC-431 (manufactured by Sumitomo 3M Limited). ), Surflon S
-112, S-113, S-131, S-14
1, the same S-145 (manufactured by Asahi Glass Co., Ltd.), SH-28PA,
SH-190, SH-193, SZ-6032, SF-
8428 (manufactured by Toray Dow Corning Silicone Co., Ltd.)
And the like.

These surfactants are used in the copolymer [A] 1.
It is used in an amount of preferably 5 parts by weight or less, more preferably 0.01 to 2 parts by weight, based on 00 parts by weight. When the amount of the surfactant is more than 5 parts by weight, the resulting protective film tends to be rough.

Further, an adhesion aid can be used to improve the adhesion to the substrate. As such an adhesion aid, a functional silane coupling agent is preferably used, and examples thereof include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. Include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

Such an adhesion aid is used as a copolymer [A] 1.
It is used in an amount of preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 00 parts by weight. When the amount of the adhesion aid exceeds 20 parts by weight, the undeveloped portion is likely to occur.

The composition solution prepared as described above can be used after being filtered using a Millipore filter having a pore size of about 0.2 μm.

Formation of Protective Film The radiation-sensitive resin composition of the present invention is applied on the surface of a base substrate such as a color filter manufactured by a printing method, a pigment dispersion method, an electrodeposition method, a dyeing method or the like, and prebaked. The solvent can be removed by means of to obtain a coating film.
As a coating method, for example, a spray method, a roll coating method,
Various methods such as spin coating can be adopted.
The pre-baking condition is usually 70 to 90 ° C. for 5 to 15 minutes, although it varies depending on the type of each component, the mixing ratio, and the like. Next, the prebaked coating film is irradiated with radiation such as ultraviolet rays through a predetermined pattern mask, and further developed with a developing solution to remove unnecessary portions to form a predetermined pattern. The developing method may be any of a puddle method and a dipping method, and the developing time is usually 30 to 180 seconds.

As the above-mentioned developing solution, an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.
0] -7-undecene, 1,5-diazabicyclo [4.
An aqueous solution such as 3.0] -5-nonene can be used. Further, an aqueous solution prepared by adding an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant to the above alkaline aqueous solution can be used as a developing solution.

After development, washing with running water is carried out for 30 to 90 seconds,
A pattern is formed by removing unnecessary portions and further air drying with compressed air or compressed nitrogen. After that, this pattern is heat-treated by a heating device such as a hot plate or an oven at a predetermined temperature, for example, 150 to 250 ° C. for a predetermined time, for example, 5 to 30 minutes on a hot plate or 30 to 90 minutes in an oven. Thus, the desired protective film can be obtained.

[0047]

EXAMPLES The present invention will be described in more detail below with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. The evaluation of various characteristics was performed by the following methods.

Evaluation of Transparency Spectrophotometer (150-20 type double beam (Hitachi Ltd.
(Manufactured by K.K.) was used to measure the transmittance of 400 to 800 nm. At this time, the case where the minimum transmittance exceeded 95% was marked as [◯], the case of 90 to 95% was marked as [Δ], and the case where it was less than 90% was marked as [x].

Evaluation of heat resistance The heat resistance was evaluated by heating the patterned substrate for 1 hour using a hot plate at 250 ° C. and measuring the film thickness before and after heating. The case where the residual film rate exceeded 95% was [O], the case of 90 to 95% was [A], and the case where it was less than 90% was [X].

Evaluation of heat discoloration resistance The measurement substrate was heated on a hot plate at 250 ° C. for 1 hour,
The heat resistance was evaluated by the change in transmittance before and after heating. If the rate of change at this time is less than 5%, [○], 5 to 10
% Was [Δ] and 10% was [X]. The transmittance was determined in the same manner as the transparency evaluation.

Measurement of Surface Hardness The surface hardness was measured by the 8.4.1 pencil scratch test of JIS K-5400-1990.

Evaluation of Flatness A step difference of the substrate was measured using a stylus type film thickness measuring device.

Cross-sectional shape of protective film The cross-sectional shape of a 20 μm × 20 μm pattern was observed using an optical microscope. As shown in Fig. 1, when the shoulder portion of the cross section has a gentle slope and there is no ridge, [○],
The case where there was no shoulder on the shoulder and the inclination angle was steep was designated as [△]. In addition, when the shoulder part was not smooth and a kerb was observed, the inclination angle was vertical or nearly vertical, there were protrusions (horns), or the film was observed on the inclined part, it was marked as [x]. .

Synthesis Example 1 A flask equipped with a dry ice / methanol reflux was purged with nitrogen, and then 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2'-azobisisobutyronitrile was dissolved was charged. Styrene 2
After charging 2.5 g, 45.0 g of methacrylic acid, 56.25 g of dicyclopentanyl methacrylate, 90.0 g of glycidyl methacrylate and 11.25 g of 1,3-butadiene, gentle stirring was started. The temperature of the solution is 8
After raising the temperature to 0 ℃ and maintaining this temperature for 5 hours,
The polymerization was terminated by heating for 1 hour.

Then, the reaction product was dropped into a large amount of methanol to solidify the product. This coagulated product was washed with water, redissolved in 200 g of tetrahydrofuran, and coagulated again with a large amount of methanol. This redissolving-coagulation operation was performed three times in total, and the obtained coagulated product was vacuum dried at 60 ° C. for 48 hours to obtain the target copolymer. Then, it was dissolved in diethylene glycol dimethyl ether so that the solid content concentration was 25% by weight to prepare a copolymer solution [A-1]. The copolymerization amount of the compound (a4) in this copolymer was determined from the polymerization conversion rate and the amount of unreacted butadiene,
The copolymerization amount was 5.0% by weight. (In the following synthesis examples, the copolymerization amount of 1,3-butadiene in the copolymer was similarly obtained.)

Synthesis Example 2 A flask equipped with a dry ice / methanol reflux was purged with nitrogen, and then 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved. I prepared it. Styrene 11.25 g, methacrylic acid 36.0
g, dicyclopentanyl methacrylate 76.5 g, glycidyl methacrylate 90.0 g, and 1,3-butadiene 11.25 g were charged, and then gentle stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 5 hours, and then heated at 90 ° C. for 1 hour to terminate the polymerization. Then, in the same manner as in Synthesis Example 1, the copolymer solution [A-
2] was prepared. The copolymerization amount of 1,3-butadiene in this copolymer was 5.0% by weight.

Synthesis Example 3 A flask equipped with a dry ice / methanol reflux was replaced with nitrogen, and then 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved. I prepared it. Subsequently, 18.0 g of styrene, 36.0 g of methacrylic acid,
After charging 76.5 g of dicyclopentanyl methacrylate, 90.0 g of glycidyl methacrylate and 4.5 g of 1,3-butadiene, gentle stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 5 hours, and then heated at 90 ° C. for 1 hour to terminate the polymerization. Then, a copolymer solution [A-3] was prepared in the same manner as in Synthesis Example 1. The copolymerization amount of 1,3-butadiene in this copolymer was 2.0% by weight.

Synthesis Example 4 A flask equipped with a dry ice / methanol reflux was purged with nitrogen, and then 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2'-azobisisobutyronitrile was dissolved was charged. Styrene 1
1.25 g, maleic anhydride 36.0 g, dicyclopentanyl methacrylate 76.5 g, glycidyl methacrylate 90.0 g and 1,3-butadiene 11.25 g.
After charging, the mixture was gently stirred. The temperature of the solution was raised to 80 ° C. and kept at this temperature for 5 hours, then 90
Polymerization was terminated by heating at ℃ for 1 hour. Then, a copolymer solution [A-4] was prepared in the same manner as in Synthesis Example 1. The copolymerization amount of 1,3-butadiene in this copolymer is 5.0.
% By weight.

Synthesis Example 5 A flask equipped with a dry ice / methanol reflux was purged with nitrogen, and then 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2'-azobisisobutyronitrile was dissolved was charged. Subsequently, p-methoxystyrene 11.25 g, methacrylic acid 45.0 g, 2
After charging 67.5 g of -methylcyclohexyl acrylate, 90.0 g of -6,7-epoxyheptyl methacrylate and 11.25 g of 1,3-butadiene, gentle stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 5 hours, and then heated at 90 ° C. for 1 hour to terminate the polymerization. Then, a copolymer solution [A-5] was prepared in the same manner as in Synthesis Example 1. 1,3 in this copolymer
The copolymerization amount of butadiene was 5.0% by weight.

Synthesis Example 6 A flask equipped with a dry ice / methanol reflux was purged with nitrogen, and then 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2'-azobisisobutyronitrile was dissolved was charged. Styrene 2
After charging 2.5 g, 45.0 g of methacrylic acid, 67.5 g of dicyclopentanyl methacrylate and 90.0 g of glycidyl methacrylate, gentle stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 5 hours, and then heated at 90 ° C. for 1 hour to terminate the polymerization. Then, in the same manner as in Synthesis Example 1, the copolymer solution [A-
6] was prepared.

Synthesis Example 7 A flask equipped with a dry ice / methanol reflux was replaced with nitrogen, and then 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved. I prepared it. Styrene 11.25 g, methacrylic acid 36.0
g, dicyclopentanyl methacrylate 65.25 g,
After charging 90.0 g of glycidyl methacrylate and 22.5 g of 1,3-butadiene, gentle stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 5 hours, and then heated at 90 ° C. for 1 hour to terminate the polymerization. Then, in the same manner as in Synthesis Example 1, the copolymer solution [A-
7] was prepared. The copolymerization amount of 1,3-butadiene in this copolymer was 10.0% by weight.

Synthesis Example 8 A flask equipped with a dry ice / methanol reflux was replaced with nitrogen, and then 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved. I prepared it. Styrene 11.25 g, methacrylic acid 36.0
After charging g, 54.0 g of dicyclopentanyl methacrylate, 90.0 g of glycidyl methacrylate and 33.75 g of 1,3-butadiene, gentle stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 5 hours, and then heated at 90 ° C. for 1 hour to terminate the polymerization. Then, in the same manner as in Synthesis Example 1, the copolymer solution [A-
8] was prepared. The copolymerization amount of 1,3-butadiene in this copolymer was 15.1% by weight.

Synthesis Example 9 A flask equipped with a dry ice / methanol reflux was purged with nitrogen, and then 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved. I prepared it. Styrene 11.25 g, methacrylic acid 36.0
g, dicyclopentanyl methacrylate 42.75 g,
After charging 90.0 g of glycidyl methacrylate and 45.0 g of 1,3-butadiene, gentle stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 5 hours, and then heated at 90 ° C. for 1 hour to terminate the polymerization. Then, in the same manner as in Synthesis Example 1, the copolymer solution [A-
9] was prepared. The copolymerization amount of 1,3-butadiene in this copolymer was 20.0% by weight.

Synthesis Example 10 A flask equipped with a dry ice / methanol reflux was purged with nitrogen, and then 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved. I prepared it. Styrene 21.375 g, methacrylic acid 36.0
g, 76.5 g of dicyclopentanyl methacrylate, 90.0 g of glycidyl methacrylate and 1.125 g of 1,3-butadiene were charged, and then gentle stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 5 hours, and then heated at 90 ° C. for 1 hour to terminate the polymerization. Then, in the same manner as in Synthesis Example 1, the copolymer solution [A-
10] was prepared. The copolymerization amount of 1,3-butadiene in this copolymer was 0.5% by weight.

Example 1 Preparation of Composition 100 g of the copolymer solution [A-1] obtained in Synthesis Example 1
(Copolymer amount 25 g) was diluted with 13.64 g of diethylene glycol dimethyl ether, and then 2-benzyl-2-dimethylamino-1- was used as a polymerization initiator [C].
(4-morpholinophenyl) -butan-1-one 7.
5 g, Aronix M-400 which is a polyfunctional acrylate as the polymerizable compound [B] (Toa Gosei Chemical Industry Co., Ltd.)
25.0 g, γ-glycidoxypropyltrimethoxysilane 1.25 g as an adhesion aid, and SH-28PA (manufactured by Toray Silicone Co., Ltd.) 1.0 as a surfactant.
Weight% diethylene glycol dimethyl ether solution 0.
625g was melt | dissolved and it filtered with the Millipore filter with a pore diameter of 0.22 micrometer, and prepared the composition solution (S-1).

(I) Formation of coating film Using a spinner on a SiO ₂ dip glass substrate,
The composition solution (S-1) was applied, and then prebaked at 80 ° C. for 5 minutes on a hot plate to form a coating film having a film thickness of 2.0 μm.

(Ii) Removal of unnecessary portions by exposure and development The coating film obtained in (i) above was irradiated with ultraviolet rays having an intensity of 10 mW / cm ² at 365 nm for 30 seconds using a predetermined pattern mask. . The ultraviolet irradiation at this time was performed in an oxygen atmosphere (in air). Next, after developing with a 0.14 wt% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 1 minute, rinse with pure water for 1 minute. By these operations, unnecessary portions were removed, and a 20 μm × 20 μm pattern (remaining) could be resolved. The cross-sectional shape of the protective film was determined using the coating film having this pattern.
The results are shown in Table 1.

(Iii) Curing of coating film The coating film having the pattern obtained in (ii) above was heated on a hot plate at 200 ° C. for 20 minutes to cure the coating film. The heat resistance was evaluated using the substrate having the cured coating film obtained here. The results are shown in Table 1.

(Iv) Evaluation of transparency, thermal discoloration resistance and surface hardness In the same manner as (i) except that a Corning 7059 (manufactured by Corning) substrate was used in place of the SiO ₂ dip glass substrate in the above (i). To form a coating film of the composition solution. Then, the whole surface was exposed for 30 seconds, developed with a 0.14 wt% tetramethylammonium hydroxide aqueous solution, and rinsed with ultrapure water for 1 minute. It was then heated on a hot plate at 200 ° C. for 20 minutes. The Corning 7059 substrate having the obtained coating film was used to evaluate transparency, heat discoloration resistance and surface hardness. The results are shown in Table 1.

(V) Evaluation of flattening property Instead of the SiO ₂ glass substrate used in (i) above,
A coating film having a cured pattern was formed in the same manner as in (i) to (iii) above, except that a SiO ₂ wafer having a step of 1.0 μm was used. Using this, the step difference of the substrate was measured. The results are shown in Table 1.

Example 2 100 g of the copolymer solution [A-2] (25 g of copolymer) in place of the copolymer solution [A-1] in Example 1
Example 6, except that 6.25 g of Irgacure369 and 20.0 g of Aronix M-400 were used.
A composition solution (S-2) was prepared and evaluated in the same manner as in.
Tetramethylammonium hydroxide 0.14% by weight
A 20 μm × 20 μm pattern could be resolved with the aqueous solution. The results are shown in Table 1.

Example 3 A composition solution (S) was prepared in the same manner as in Example 2 except that the copolymer solution [A-3] was used in place of the copolymer solution [A-2]. -3) was prepared and evaluated. A 20 μm × 20 μm pattern could be resolved with a 0.14% by weight aqueous solution of tetramethylammonium hydroxide. The results are shown in Table 1.

Example 4 In Example 2, the copolymer solution [A-4] was used in place of the copolymer solution [A-2], and a 1.2 wt% tetramethylammonium hydroxide aqueous solution was used as a developing solution. A composition solution (S-4) was used in the same manner as in Example 2 except that it was used.
Was prepared and evaluated, and a pattern of 20 μm × 20 μm could be resolved. The results are shown in Table 1.

Example 5 A composition solution (S) was prepared in the same manner as in Example 2 except that the copolymer solution [A-5] was used instead of the copolymer solution [A-2]. -5) was prepared and evaluated. A 20 μm × 20 μm pattern could be resolved with a 0.14% by weight aqueous solution of tetramethylammonium hydroxide. The results are shown in Table 1.

Example 6 A composition solution (S-6) was prepared and evaluated in the same manner as in Example 1 except that Irgacure907 was used instead of Irgacure369. A 20 μm × 20 μm pattern could be resolved with a 0.14% by weight aqueous solution of tetramethylammonium hydroxide. The results are shown in Table 1.

Example 7 In Example 1, Irgacure369; 7.5 g
Instead of Irgacure369; 3.75g and I
rgacure907; 3.75 g was used in combination, and a composition solution (S-7) was prepared and evaluated in the same manner as in Example 1. Tetramethylammonium hydroxide 0.14
A 20 μm × 20 μm pattern could be resolved with a wt% aqueous solution. The results are shown in Table 1.

Example 8 In the same manner as in Example 1 except that Irgacure261 was used instead of Irgacure369 and a 0.20% by weight aqueous solution of tetramethylammonium hydroxide was used as a developing solution, a composition solution ( S-
When 8) was prepared and evaluated, a pattern of 20 μm × 20 μm could be resolved. The results are shown in Table 1.

Example 9 A composition solution (S-9) was prepared and evaluated in the same manner as in Example 2 except that KAYARAD DPHA was used instead of Aronix M-400. A 20 μm × 20 μm pattern could be resolved with a 0.14% by weight aqueous solution of tetramethylammonium hydroxide. The results are shown in Table 1.

Example 10 In Example 2, Biscoat 295 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used in place of Aronix M-400,
A composition solution (S-10) was prepared and evaluated in the same manner as in Example 1 except that a 0.40 wt% aqueous solution of tetramethylammonium hydroxide was used as a developer.
It was possible to resolve a pattern of 20 μm × 20 μm. The results are shown in Table 1.

Example 11 In Example 2, 100 g of copolymer solution [A-7] (25 g of copolymer) was used instead of the copolymer solution [A-2].
Except that the composition solution (S-
11) was prepared and evaluated. Tetramethylammonium hydroxide 0.14% by weight aqueous solution 20 μm × 20 μm
I was able to resolve the pattern. The results are shown in Table 1.

Example 12 In Example 2, 100 g of copolymer solution [A-8] (25 g of copolymer) was used instead of copolymer solution [A-2].
Except that the composition solution (S-
12) was prepared and evaluated. Tetramethylammonium hydroxide 0.14% by weight aqueous solution 20 μm × 20 μm
I was able to resolve the pattern. The results are shown in Table 1.

Comparative Example 1 100 g of copolymer solution [A-6] (25 g of copolymer) in Example 1 was used instead of the copolymer solution [A-1].
Except that the composition solution (CS
-1) was prepared and evaluated. Tetramethylammonium hydroxide 0.14% by weight aqueous solution 20 μm × 20 μm
I was able to resolve the pattern. The results are shown in Table 1.

Comparative Example 2 100 g of copolymer solution [A-9] (25 g of copolymer) in place of copolymer solution [A-1] in Example 1 was used.
Except that the composition solution (CS
-2) was prepared and evaluated. Tetramethylammonium hydroxide 0.14% by weight aqueous solution 20 μm × 20 μm
I was able to resolve the pattern. The results are shown in Table 1.

Comparative Example 3 In Example 1, 100 g of the copolymer solution [A-10] was used instead of the copolymer solution [A-1] and the amount of the copolymer was 25 g).
Except that the composition solution (CS
-3) was prepared and evaluated. Tetramethylammonium hydroxide 0.14% by weight aqueous solution 20 μm × 20 μm
I was able to resolve the pattern. The results are shown in Table 1.

[0085]

[Table 1]

[0086]

According to the present invention, various properties conventionally required as a protective film, specifically, adhesion, surface hardness, transparency, heat resistance, light resistance, chemical resistance and water resistance are satisfied. At the same time, it is possible to flatten the step of the color filter that is the base substrate, and further, it is possible to easily remove the protective film of an unnecessary portion (for example, a portion other than the color filter) by radiation irradiation and development. Moreover,
It is possible to obtain a radiation-sensitive resin composition suitable as a protective film forming material for an optical device, which gives a protective film having a cross-sectional shape that does not easily break.

Next, preferred embodiments of the present invention will be listed. 1) The radiation-sensitive resin composition, wherein the copolymer [A] has a copolymerization amount of the compound (a1) of 5 to 40% by weight. 2) The radiation-sensitive resin composition, wherein the copolymer [A] has a copolymerization amount of the compound (a2) of 10 to 70% by weight. 3) The radiation-sensitive resin composition, wherein the copolymer [A] has a copolymerization amount of the compound (a3) of 10 to 70% by weight. 4) The radiation-sensitive resin composition, wherein the copolymer [A] has a copolymerization amount of the compound (a4) of 1 to 10% by weight. 5) The radiation-sensitive resin composition, wherein the compound (a1) is at least one compound selected from the group consisting of acrylic acid, methacrylic acid and maleic anhydride. 6) A radiation-sensitive resin composition, wherein the compound (a2) is at least one compound selected from the group of glycidyl methacrylate and -6,7-epoxyheptyl methacrylate. 7) The radiation-sensitive resin composition, wherein the compound (a3) is at least one compound selected from the group consisting of styrene, dicyclopentanyl methacrylate, p-methoxystyrene and 2-methylcyclohexyl acrylate. 8) A radiation-sensitive resin composition, wherein the compound (a4) is at least one compound selected from the group consisting of 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing a cross-sectional shape of a protective film.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuo Bessho 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. An [A] (a1) unsaturated carboxylic acid and / or
Or unsaturated carboxylic acid anhydride, (a2) epoxy group-containing unsaturated compound, (a3) the above (a1) and (a2)
A copolymer of a monoolefinic unsaturated compound other than (a4) and a conjugated diolefinic unsaturated compound, and the copolymerization amount of (a4) is 1 to 15% by weight, [B] ethylene A radiation-sensitive resin composition comprising a polymerizable compound having a polyunsaturated bond and [C] a radiation-sensitive polymerization initiator.