JPH1184659A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable development with an alkaline aq. soln., to ensure high sensitivity and high resolution and to easily form a patterned thin film excellent in insulating property, flatness, etc., by using a specified fluorine-contg. copolymer, an acid generating compd. and an org. solvent. SOLUTION: The radiation sensitive resin compsn. consists of a fluorine-contg. copolymer of hexafluoropropylene, a compd. having an ethylenically unsatd. bond and an acid-decomposable group represented by the formula, an unsatd. carboxylic acid and/or its anhydride and an unsatd. compd. copolymerizable with these three components, an acid generating compd., a crosslinking compd. and an org. solvent which dissolves these components. In the formula, M is C, Si, etc., R<1> -R<3> are individually H, 1-10C linear alkyl, etc., and two of R<1> -R<3> may bond to each other to form a 4- to 7-membered ring in combination with M to which they are bonded.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a radiation-sensitive resin composition. More specifically, it is suitable as a positive resist for forming a mask for manufacturing a circuit such as a semiconductor integrated circuit and a thin film transistor (hereinafter, referred to as “TFT”) circuit for a liquid crystal display (hereinafter, “LCD”). The present invention relates to a radiation-sensitive resin composition suitable as a material for forming a permanent film such as an interlayer insulating film and a protective film for a color filter.

[0002]

2. Description of the Related Art Generally, liquid crystal display devices, integrated circuit devices,
2. Description of the Related Art An electronic component such as a solid-state imaging device is provided with a protective film for preventing its deterioration and damage, a flattening film for flattening the element surface, an insulating film for maintaining electrical insulation, and the like. In a TFT type liquid crystal display element and an integrated circuit element, an interlayer insulating film is provided to insulate between wirings arranged in layers.

However, when a conventionally known material for forming a thermosetting insulating film for an electronic component is used to form an interlayer insulating film, for example, an interlayer insulating film having a required pattern is obtained. Therefore, there is a problem that the number of steps is large and an interlayer insulating film having a sufficient flatness cannot be obtained. Therefore, a photosensitive insulating film forming material that can be patterned has been required. In recent years, as the density of wirings and devices has increased, low dielectric properties have been demanded for these materials.

However, it is difficult to lower the dielectric constant of the obtained film while maintaining good photosensitivity, developability with an aqueous alkaline solution after exposure, and good heat resistance, solvent resistance and transparency of the obtained film. there were. That is, many photosensitizers for imparting photosensitivity that can be developed with an alkaline aqueous solution and cross-linking agents for expressing heat resistance and solvent resistance act to increase the dielectric constant of the resulting film. Therefore, it has been difficult to simultaneously realize these characteristics and reduce the dielectric constant.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to develop an alkaline aqueous solution, which has high sensitivity and radiation sensitivity excellent in resolution.
An object of the present invention is to provide a radiation-sensitive resin composition which not only has excellent properties such as heat resistance, solvent resistance and transparency, but also can easily form a patterned thin film having a low dielectric constant.

Another object of the present invention is to provide a TF for IC and LCD.
It is used for manufacturing circuits such as T circuits and for forming permanent films exemplified by interlayer insulating films for LCDs, color filter protective films, circuit protective films, and the like. An object of the present invention is to provide a radiation-sensitive resin composition capable of providing a permanent film having excellent transparency, chemical resistance, insulation properties, and the like in an optical region. Still other objects and advantages of the present invention will become apparent from the following description.

[0007]

According to the present invention, the above objects and advantages of the present invention are as follows: (A), (a-1) hexafluoropropylene, (a-2) an ethylenically unsaturated bond, and 1)

[0008]

Embedded image

Here, M represents a carbon atom, a silicon atom or a germanium atom, and R ¹ , R ² and R ³ independently of one another are a hydrogen atom, a chain alkyl group having 1 to 10 carbon atoms, 1 to 10 carbon atoms. A halogenated alkyl group having 3 to 10 carbon atoms
A cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, or the above formula (2) -OR ⁴ (2) wherein R ⁴ is a chain having 1 to 10 carbon atoms. An alkyl group, a halogenated alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 11 carbon atoms, or R ¹ , any ^two of R ² and R ³ may be bonded to each other to form a 4- to 7-membered ring together with M to which they are bonded; Compound, (a-3) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, and (a-4) component (a-1), component (a-2) and component (a-3). A fluorine-containing copolymer with a copolymerizable unsaturated compound, (B), irradiation of radiation Acid generating compound which generates an acid under, (C),
A radiation-sensitive composition comprising a crosslinkable compound containing at least one crosslinkable group, and an organic solvent in which (D), the components (A), (B) and (C) are dissolved. This is achieved by a resin composition.

Hereinafter, the radiation-sensitive resin composition of the present invention will be specifically described.

<Component (A)> The component (A) is (a-1)
Hexafluoropropylene, (a-2) a compound having an ethylenically unsaturated bond and an acid-decomposable group represented by the formula (1), (a-3) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride And (a-4) the above (a-
It is a fluorinated copolymer of the component (1), the component (a-2), and the component (a-3) with a copolymerizable unsaturated compound (hereinafter, referred to as a specific polymer).

Hereinafter, the constitution of the specific polymer of the present invention will be described in detail. The specific polymer used in the present invention includes hexafluoropropylene, a polymerized unit of a compound having an ethylenically unsaturated bond and a structure represented by the formula (1) (hereinafter, referred to as “polymerized unit (1)”), It is a copolymer containing, as essential components, a polymer unit of an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride and a polymer unit of a copolymerizable unsaturated compound. In the formula (1) in the compound (a-2) having an acid-decomposable group, M represents a carbon atom, a silicon atom or a germanium atom, and R ¹ , R ² and R ³ independently represent a hydrogen atom, a carbon number A chain alkyl group having 1 to 10, a halogenated alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms or the above formula Or (2), or any ^{two of} R ¹ , R ² and R ³ may be bonded to each other to form a 4- to 7-membered ring together with M to which they are bonded. In the formula (2), R ⁴ is a chain alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or It represents an aralkyl group having 7 to 11 carbon atoms.

R ¹ , R ² , R ³ and R ⁴ have 1 to 10 carbon atoms.
May be linear or branched, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, s
ec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group And the like.

Examples of the halogenated alkyl group having 1 to 10 carbon atoms include a trifluoroethyl group, a hexafluoropropyl group and a heptadecafluorodecyl group.

Examples of the cyclic alkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group and an isobornyl group.

The aryl group having 6 to 10 carbon atoms includes, for example, a phenyl group, a tolyl group, a xylyl group, a cumenyl group,
Examples thereof include a 1-naphthyl group and the like.

The aralkyl group having 7 to 11 carbon atoms includes
For example, benzyl, α-methylbenzyl, phenethyl, naphthylmethyl and the like can be mentioned.

Further, R ¹ , R ² and R ³ can be bonded to each other to form a 4- to 7-membered ring together with M to which they are bonded. When R ¹ and R ² , R ¹ and R ^3, or R ² and R ³ are bonded, examples of the 4- to 7-membered ring include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group and a tetrahydropyranyl group. Can be mentioned.

The group represented by the formula (2) is a group called an acetal group or a ketal group. Here, as the acetal group, for example, a 1-methoxyethoxy group,
Ethoxyethoxy group, 1-n-propoxyethoxy group,
1-i-propoxyethoxy group, 1-n-butoxyethoxy group, 1-i-butoxyethoxy group, 1-sec-butoxyethoxy group, 1-t-butoxyethoxy group, 1-
Cyclopentyloxyethoxy group, 1-cyclohexyloxyethoxy group, 1-norbornyloxyethoxy group, 1-bornyloxyethoxy group, 1-phenyloxyethoxy group, 1- (1-naphthyloxy) ethoxy group, 1-benzyl An oxyethoxy group, a 1-phenethyloxyethoxy group, a (cyclohexyl) (methoxy) methoxy group, a (cyclohexyl) (ethoxy) methoxy group,
A (cyclohexyl) (n-propoxy) methoxy group,
A (cyclohexyl) (i-propoxy) methoxy group,
(Cyclohexyl) (cyclohexyloxy) methoxy group, (cyclohexyl) (phenoxy) methoxy group,
(Cyclohexyl) (benzyloxy) methoxy group,
(Phenyl) (methoxy) methoxy group, (phenyl)
(Ethoxy) methoxy group, (phenyl) (n-propoxy) methoxy group, (phenyl) (i-propoxy) methoxy group, (phenyl) (cyclohexyloxy) methoxy group, (phenyl) (phenoxy) methoxy group, (phenyl) (Benzyloxy) methoxy group, (benzyl)
(Methoxy) methoxy group, (benzyl) (ethoxy) methoxy group, (benzyl) (n-propoxy) methoxy group, (benzyl) (i-propoxy) methoxy group, (benzyl) (cyclohexyloxy) methoxy group, (benzyl) Examples thereof include a (phenoxy) methoxy group, a (benzyl) (benzyloxy) methoxy group, a 2-tetrahydrofuranyloxy group, and a 2-tetrahydropyranyloxy group.

Next, examples of the ketal group include 1-methyl-1-methoxyethoxy group, 1-methyl-1-ethoxyethoxy group, 1-methyl-1-n-propoxyethoxy group and 1-methyl-1- i-propoxyethoxy group,
1-methyl-1-n-butoxyethoxy group, 1-methyl-1-i-butoxyethoxy group, 1-methyl-1-se
c-butoxyethoxy group, 1-methyl-1-t-butoxyethoxy group, 1-methyl-1-cyclopentyloxyethoxy group, 1-methyl-1-cyclohexyloxyethoxy group, 1-methyl-1-norbornyloxy Ethoxy group, 1-methyl-1-bornyloxyethoxy group, 1
-Methyl-1-phenyloxyethoxy group, 1-methyl-1- (1-naphthyloxy) ethoxy group, 1-methyl-1-benzyloxyoxyethoxy group, 1-methyl-1-
Phenethyloxyethoxy group, 1-cyclohexyl-1
-Methoxyethoxy group, 1-cyclohexyl-1-ethoxyethoxy group, 1-cyclohexyl-1-n-propoxyethoxy group, 1-cyclohexyl-1-i-propoxyethoxy group, 1-cyclohexyl-1-cyclohexyloxyethoxy group, 1-cyclohexyl-1-phenoxyethoxy group, 1-cyclohexyl-1-benzyloxyethoxy group, 1-phenyl-1-methoxyethoxy group, 1-phenyl-1-ethoxyethoxy group, 1-phenyl-1-n-propoxy Ethoxy group, 1-phenyl-1-i-propoxyethoxy group, 1-phenyl-1-
Cyclohexyloxyethoxy group, 1-phenyl-1-
Phenyloxyethoxy group, 1-phenyl-1-benzyloxyethoxy group, 1-benzyl-1-methoxyethoxy group, 1-benzyl-1-ethoxyethoxy group, 1-
Benzyl-1-n-propoxyethoxy group, 1-benzyl-1-i-propoxyethoxy group, 1-benzyl-1
-Cyclohexyloxyethoxy group, 1-benzyl-1
-Phenyloxyethoxy group, 1-benzyl-1-benzyloxyethoxy group, 2- (2-methyl-tetrahydrofuranyl) oxy group, 2- (2-methyl-tetrahydropyranyl) oxy group, 1-methoxy-cyclopentyloxy And a 1-methoxy-cyclohexyloxy group.

The ethylenically unsaturated bond and the above formula (1)
Preferred examples of the compound having the structure represented by the following include corresponding esters of unsaturated carboxylic acids described below.

In the specific polymer, the polymerized unit (1) is
They can be present alone or in combination.

The fluorine-containing copolymer (a-
2) Compounds having an ethylenically unsaturated bond include crotonic acid, maleic acid, 3-butenoic acid, 4-pentenoic acid, itaconic acid, citraconic acid, muconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, methyl -5-norbornene 2,3-dicarboxylic acid, 5-norbornene-2,
Unsaturated carboxylic acids or unsaturated dicarboxylic acids such as 3-dicarboxylic acid, 3,4,5,6-tetrahydrophthalic acid, cis-1,2,3,6-tetrahydrophthalic acid and dimethyltetrahydrophthalic anhydride; ) (Meth) acrylates of hydroxy fatty acids such as acryloyloxyacetic acid, 3- (meth) acryloyloxypropionic acid, 2- (meth) acryloyloxypropionic acid and 4- (meth) acryloyloxybutanoic acid; 4- (meth) Acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 2- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxyphthalic acid, 3- (meth) acryloyloxyphthalic acid, 4-
(Meth) acrylates of aromatic hydroxycarboxylic acids such as (meth) acryloyloxyisophthalic acid, 5- (meth) acryloyloxyisophthalic acid and 2- (meth) acryloyloxyterephthalic acid; mono (2- (meth) succinate Acryloyloxy) ethyl, mono (2- (meth) acryloyloxy) ethyl phthalate, mono (2- (meth) acryloyloxy) ethyl isophthalate, mono (2- (meth) acryloyloxy) ethyl terephthalate, tetrahydrophthalic acid Mono (2- (meta)
Mono (meth) acryloyloxyethyl esters of dicarboxylic acids such as acryloyloxy) ethyl, mono (2- (meth) acryloyloxy) ethyl tetrahydroisophthalate, mono (2- (meth) acryloyloxy) ethyl tetrahydroterephthalate; itacone Acid monomethyl, monoethyl, monopropyl, mono-i-propyl, monobutyl, mono-sec-butyl, mono-ter
Monoalkyl esters of unsaturated carboxylic acids having a carboxyl group such as t-butyl; maleic anhydride, itaconic anhydride, citraconic anhydride, muconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, methyl -5-norbornene 2,3-dicarboxylic anhydride, 5
-Norbornene-2,3-dicarboxylic anhydride, 3,4,
5,6-tetrahydrophthalic anhydride, cis-1,2,
Unsaturated acid anhydrides such as 3,6-tetrahydrophthalic anhydride and dimethyltetrahydrophthalic anhydride; and the like. These carboxyl group-containing monomers may be used alone or in combination of two or more.

Among these components (a-2), preferred are trimethylsilyl crotonate, triethylsilyl crotonate, t-butyldimethylsilyl crotonate, trimethylgermyl crotonate, triethyl gel crotonate Mill ester, t-butyl dimethyl crotonate, crotonic acid t-butyl ester, crotonic acid benzyl ester, crotonic acid tetrahydrofuranyl ester, crotonic acid tetrahydropyranyl ester, crotonic acid cyclobutyl ester, crotonic acid cyclopentyl ester, Crotonic acid cyclohexyl ester, crotonic acid cycloheptyl ester, crotonic acid-1-methoxyethoxy ester, crotonic acid-1-t-butoxyethoxy ester, Tonsan -1-benzyloxy-ethoxy esters, crotonic acid (cyclohexyl) (ethoxy) methoxy ester, crotonic acid-1-methyl-1-
Methoxyethoxyester, 1-methyl crotonic acid
1-i-butoxyethoxy ester, (benzyl) (ethoxy) methoxy ester crotonate, trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, t-butyldimethylsilyl (meth) acrylate, ( (Meth) acrylic acid trimethylgermyl ester, (meth) acrylic acid triethylgermyl ester, (meth) acrylic acid-t-butyldimethylgermyl ester, (meth) acrylic acid-t-
Butyl ester, benzyl (meth) acrylate, tetrahydrofuranyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, (meth) acryl Acid cyclohexyl ester, (meth) acrylic acid cycloheptyl ester, (meth) acrylic acid-1-methoxyethoxy ester, (meth) acrylic acid-1-t-
Butoxyethoxy ester, (meth) acrylic acid-1-
Benzyloxyethoxy ester, (meth) acrylic acid (cyclohexyl) (ethoxy) methoxy ester,
(Meth) acrylic acid-1-methyl-1-methoxyethoxy ester, (meth) acrylic acid-1-methyl-1-i
-Butoxyethoxy ester, (benzyl) (ethoxy) methoxy (meth) acrylate, trimethylsilyl 5-norbornene-2,3-dicarboxylate, triethylsilyl 5-norbornene-2,3-dicarboxylate, 5-norbornene- 2,3-dicarboxylic acid-t-butyldimethylsilyl ester, 5-norbornene-2,3-dicarboxylic acid trimethylgermyl ester, 5-norbornene-2,3-dicarboxylic acid triethylgermyl ester, 5-norbornene-2, 3-
Dicarboxylic acid-t-butyldimethylgermyl ester,
5-norbornene-2,3-dicarboxylic acid-t-butyl ester, 5-norbornene-2,3-dicarboxylic acid benzyl ester, 5-norbornene-2,3-dicarboxylic acid tetrahydrofuranyl ester, 5-norbornene-2,3 Dicarboxylic acid tetrahydropyranyl ester, 5-norbornene-2,3-dicarboxylic acid cyclobutyl ester, 5-norbornene-2,3-dicarboxylic acid cyclopentyl ester, 5-norbornene-2,3
-Cyclohexyl dicarboxylate, cycloheptyl 5-norbornene-2,3-dicarboxylate,
5-norbornene-2,3-dicarboxylic acid-1-methoxyethoxy ester, 5-norbornene-2,3-dicarboxylic acid-1-tert-butoxyethoxy ester, 5-norbornene-2,3-dicarboxylic acid-1-benzyl Oxyethoxy ester, 5-norbornene-2,3-dicarboxylic acid (cyclohexyl) (ethoxy) methoxy ester, 5-norbornene-2,3-dicarboxylic acid-1-
Methyl-1-methoxyethoxy ester, 5-norbornene-2,3-dicarboxylic acid-1-methyl-1-i-butoxyethoxy ester, 5-norbornene-2,3-
And dicarboxylic acid (benzyl) (ethoxy) methoxy ester.

Examples of the unsaturated carboxylic acid and its anhydride (a-3) constituting the specific polymer include unsaturated carboxylic acids such as crotonic acid, maleic acid, 3-butenoic acid, 4-pentenoic acid and itaconic acid. Or unsaturated dicarboxylic acids; (meth) of hydroxy fatty acids such as (meth) acryloyloxyacetic acid, 3- (meth) acryloyloxypropionic acid, 2- (meth) acryloyloxypropionic acid, and 4- (meth) acryloyloxybutanoic acid
Acrylates; 4- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 2-
(Meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxyphthalic acid, 3- (meth) acryloyloxyphthalic acid, 4- (meth) acryloyloxyisophthalic acid, 5- (meth) acryloyloxyisophthalic acid, 2- (Meth) acrylates of aromatic hydroxycarboxylic acids such as (meth) acryloyloxyterephthalic acid; mono (2- (meth) acryloyloxy) succinate
Ethyl, mono (2- (meth) acryloyloxy) ethyl phthalate, mono (2- (meth) acryloyloxy) ethyl isophthalate, mono (2- (meth) terephthalate
Acryloyloxy) ethyl, mono (2- (meth) acryloyloxy) ethyl tetrahydrophthalate, mono (2- (meth) acryloyloxy) ethyl tetrahydroisophthalate, mono (2-tetrahydroterephthalate)
Mono (meth) acryloyloxyethyl esters of dicarboxylic acids such as (meth) acryloyloxy) ethyl; monomethyl, monoethyl, monopropyl, mono-i-propyl, monobutyl, mono-sec-itaconic acid
Monoalkyl esters of unsaturated carboxylic acids having a carboxyl group such as butyl and mono-tert-butyl;
Maleic anhydride, itaconic anhydride, citraconic anhydride,
Muconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, methyl-5-norbornene 2,3-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 3,4,5 Unsaturated acid anhydrides such as 1,6-tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride and dimethyltetrahydrophthalic anhydride; and the like. These monomers may be used alone or in combination of two or more.

The ethylenically unsaturated bond and the above formula (1)
As a compound having a structure represented by the following,
Esters of the carboxyl group-containing monomer are preferred.

Further, as a monomer (a-4) copolymerizable with hexafluoropropylene, the carboxyl group-containing monomer and the compound having an ethylenically unsaturated bond and an acid-decomposable group of the formula (1) Is, for example, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether,
-Hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, hydroxyl group-containing vinyl ethers such as 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether,
Hydroxyl-containing allyl ethers such as glycerol monoallyl ether, allyl alcohol,

Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-
Alkyl vinyl ethers or cycloalkyl vinyl ethers such as pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether;

Perfluoro (methyl vinyl ether),
Perfluoro (alkyl vinyl ether) such as perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether) and perfluoro (propoxypropyl vinyl ether)
Or perfluoro (alkoxyalkyl vinyl ether) s, or the general formula CH ₂ CH—O—Rf
(Rf represents an alkyl group or an alkoxyalkyl group containing a fluorine atom) (fluoroalkyl)
Vinyl ether or (fluoroalkoxyalkyl) vinyl ethers,

Fluoroolefins such as vinylidene fluoride, chlorotrifluoroethylene, 3,3,3-trifluoropropylene and tetrafluoroethylene;

Vinyl carboxylate esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl versatate and vinyl stearate;

Α-olefins such as ethylene, propylene and isobutene;

2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, Fluorine-containing (meth) acrylates such as (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, and 2- (perfluorodecyl) ethyl (meth) acrylate;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate,
(Meth) acrylic acid esters such as isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and 2- (n-propoxy) ethyl (meth) acrylate;

Glycidyl (meth) acrylate, α-ethyl glycidyl (meth) acrylate, α-n-propyl glycidyl (meth) acrylate, α-n-butyl glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate Epoxy group-containing (meth) acrylates such as 3,4-epoxyheptyl (meth) acrylate and α-ethyl-6,7-epoxyheptyl (meth) acrylate; allyl glycidyl ether;
Epoxy group-containing unsaturated aliphatic compounds such as vinylcyclohexene oxide, 3-vinylcyclohexene oxide and 4-vinylcyclohexene oxide; vinyl glycidyl ether, 2-vinylbenzyl glycidyl ether, 3-vinylbenzyl glycidyl ether, 4-vinylbenzyl glycidyl Ether, α-methyl-2-vinylbenzyl glycidyl ether, α-methyl-3-vinylbenzyl glycidyl ether, α-methyl-4-vinylbenzyl glycidyl ether, 2,3-diglycidyloxymethyl styrene, 2,4-di Glycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene,
2,3,4-triglycidyloxymethylstyrene,
3,5-triglycidyloxymethylstyrene, 2,3,
6-triglycidyloxymethylstyrene, 3,4,5-
Glycidyl ethers such as triglycidyloxymethylstyrene and 2,4,6-triglycidyloxymethylstyrene are exemplified. These monomers may be used alone or in combination of two or more.

Among the copolymerizable monomers, from the viewpoint of increasing the yield of the fluorine-containing copolymer of the present invention, the monomers containing no fluorine atom include alkyl vinyl ethers,
Cycloalkyl vinyl ethers and carboxylic acid vinyl esters are preferably used. Among them, in terms of increasing the fluorine content of the fluorine-containing copolymer, for example, low molecular weight monomers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl pivalate Is preferred. Further, it is also preferable to use hexafluoropropylene in combination with perfluoroalkyl perfluorovinyl ether and perfluoroalkoxyalkyl perfluorovinyl ether. In order to increase the hardness of the fluorine-containing copolymer, it is effective to use a branched monomer such as isopropyl vinyl ether, tert-butyl vinyl ether and vinyl pivalate.

The ratio of the polymerized unit based on each monomer constituting the fluoropolymer of the present invention is 20 to 70% by weight, preferably 25% by weight, of the polymerized unit of hexafluoropropylene.
-60% by weight, polymerized unit (1) 5-50% by weight, preferably 10-40% by weight, polymerized unit based on carboxyl group-containing monomer 0-40% by weight, preferably 5-25% by weight and other Polymerized units 10 based on copolymerizable monomers
７０70% by weight. However, when hexafluoropropylene is less than 53% by weight, for example, perfluoro (alkyl vinyl ether)
Alternatively, it is desirable to copolymerize a fluorine-containing monomer such as perfluoro (alkoxyalkyl vinyl ether). The fluorine content is at least 40% by weight, preferably at least 45% by weight. If the content of the polymerized unit (1) is less than 5% by weight, the resolution as a resist tends to decrease, while if it exceeds 50% by weight, the sensitivity tends to decrease. When the carboxyl group-containing structure content is low, the alkali solubility tends to decrease, and when it exceeds 40% by weight or more, the resolution as a resist tends to decrease.

The specific polymer has other structural units together with the specific carboxyl group-containing structural unit for the purpose of adjusting transparency, alkali solubility, heat resistance, water resistance, solvent resistance, adhesion and the like. You may. Other structural units include:
A copolymerizable monomer copolymerizable with a specific monomer (hereinafter, simply referred to as a “copolymerizable monomer”), such as an unsaturated acid anhydride, an epoxy group-containing unsaturated compound, or other radical polymerization And a structural unit in which the polymerizable double bond of the hydrophilic compound is cleaved.

<Component A> Hexafluoropropylene of the present invention, a compound having an ethylenically unsaturated bond and an acid-decomposable group represented by the formula (1), an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride, Examples of the fluorine-containing copolymer with a copolymerizable unsaturated compound include hexafluoropropylene / trimethylsilyl crotonic acid ester / crotonic acid / ethyl vinyl ether copolymer and hexafluoropropylene / t-butyldimethylsilyl crotonic acid / Crotonic acid / ethyl vinyl ether copolymer, hexafluoropropylene / trimethylgermyl crotonic acid ester / crotonic acid / ethylvinyl ether copolymer, hexafluoropropylene / t-butyldimethylgermyl ester crotonic acid / crotonic acid / ethylvinyl ether Ter copolymer, hexafluoropropylene / crotonic acid-t-butyl ester / crotonic acid / ethyl vinyl ether copolymer, hexafluoropropylene / crotonic acid tetrahydropyranyl ester / crotonic acid / ethyl vinyl ether copolymer, hexafluoropropylene / croton Acid-1-methoxyethoxy ester / crotonic acid / ethyl vinyl ether copolymer,
Hexafluoropropylene / (meth) acrylic acid trimethylsilyl ester / (meth) acrylic acid / ethyl vinyl ether copolymer, hexafluoropropylene / (meth) acrylic acid-t-butyldimethylsilyl ester /
(Meth) acrylic acid / ethyl vinyl ether copolymer,
Hexafluoropropylene / (meth) acrylic acid trimethylgermyl ester / (meth) acrylic acid / ethyl vinyl ether copolymer, hexafluoropropylene /
(Meth) acrylic acid-t-butyldimethylgermyl ester / (meth) acrylic acid / ethyl vinyl ether copolymer, hexafluoropropylene / (meth) acrylic acid-t-butyl ester / (meth) acrylic acid / ethyl vinyl ether Polymer, hexafluoropropylene /
(Meth) acrylic acid tetrahydropyranyl ester /
(Meth) acrylic acid / ethyl vinyl ether copolymer,
Hexafluoropropylene / (meth) acrylic acid-1-
Methoxyethoxy ester / (meth) acrylic acid / ethyl vinyl ether copolymer, hexafluoropropylene / 5-norbornene-2,3-dicarboxylic acid trimethylsilyl ester / 5-norbornene-2,3-dicarboxylic acid / ethyl vinyl ether copolymer, Hexafluoropropylene / 5-norbornene-2,3-dicarboxylic acid-t-butyldimethylsilyl ester / 5-norbornene-2,3-dicarboxylic acid / ethyl vinyl ether copolymer, hexafluoropropylene / 5-norbornene-
2,3-dicarboxylic acid trimethyl gel miel ester /
5-norbornene-2,3-dicarboxylic acid / ethyl vinyl ether copolymer, hexafluoropropylene / 5-
Norbornene-2,3-dicarboxylic acid-t-butyldimethylgermyl ester / 5-norbornene-2,3-dicarboxylic acid / ethyl vinyl ether copolymer, hexafluoropropylene / 5-norbornene-2,3-dicarboxylic acid-t -Butyl ester / 5-norbornene-2,
3-dicarboxylic acid / ethyl vinyl ether copolymer, hexafluoropropylene / 5-norbornene-2,3-
Dicarboxylic acid tetrahydropyranyl ester / 5-norbornene-2,3-dicarboxylic acid / ethyl vinyl ether copolymer, hexafluoropropylene / 5-norbornene-2,3-dicarboxylic acid-1-methoxyethoxy ester / 5-norbornene-2, 3-dicarboxylic acid / ethyl vinyl ether copolymer, hexafluoropropylene / trimethylsilyl crotonic acid / crotonic acid / 5-norbornene-2,3-dicarboxylic anhydride / ethyl vinyl ether copolymer, hexafluoropropylene / crotonic acid-t -Butyldimethylsilyl ester /
Crotonic acid / 5-norbornene-2,3-dicarboxylic anhydride / ethyl vinyl ether copolymer, hexafluoropropylene / crotonic acid trimethylgermyl ester / crotonic acid / 5-norbornene-2,3-dicarboxylic anhydride / ethyl Vinyl ether copolymer, hexafluoropropylene / t-butyldimethylgermyl crotonate / crotonic acid / 5-norbornene-2,3
-Dicarboxylic anhydride / ethyl vinyl ether copolymer, hexafluoropropylene / t-butyl crotonic acid / crotonic acid / 5-norbornene-2,3-
Dicarboxylic anhydride / ethyl vinyl ether copolymer,
Hexafluoropropylene / crotonic acid tetrahydropyranyl ester / crotonic acid / 5-norbornene-2,
3-dicarboxylic anhydride / ethyl vinyl ether copolymer, hexafluoropropylene / crotonic acid-1-methoxyethoxy ester / crotonic acid / 5-norbornene-2,3-dicarboxylic anhydride / ethyl vinyl ether copolymer, hexafluoro Propylene / crotonic acid trimethylsilyl ester / crotonic acid / ethyl vinyl ether / 4-hydroxybutyl vinyl ether copolymer,
Hexafluoropropylene / trimethylsilyl crotonic acid ester / crotonic acid / ethyl vinyl ether / perfluoro (propyl vinyl ether) copolymer, hexafluoropropylene / trimethylsilyl crotonic acid ester / crotonic acid / ethyl vinyl ether / chlorotrifluoroethylene copolymer, hexafluoro Propylene / trimethylsilyl crotonic acid ester / crotonic acid /
Ethyl vinyl ether / vinyl acetate copolymer, hexafluoropropylene / trimethylsilyl crotonic acid ester / crotonic acid / ethyl vinyl ether / vinyl glycidyl ether copolymer, hexafluoropropylene /
(Meth) acrylic acid tetrahydropyranyl ester / crotonic acid / ethyl vinyl ether / 4-hydroxybutyl vinyl ether copolymer, hexafluoropropylene / (meth) acrylic acid tetrahydropyranyl ester /
Crotonic acid / ethyl vinyl ether / perfluoro (propyl vinyl ether) copolymer, hexafluoropropylene / (meth) acrylic acid tetrahydropyranyl ester / crotonic acid / ethyl vinyl ether / chlorotrifluoroethylene copolymer, hexafluoropropylene / (meth) Acrylic acid tetrahydropyranyl ester /
Crotonic acid / ethyl vinyl ether / vinyl acetate copolymer, hexafluoropropylene / tetrahydropyranyl (meth) acrylate / crotonic acid / ethyl vinyl ether / vinyl glycidyl ether copolymer, hexafluoropropylene / trimethylsilyl crotonate / (meth) Acrylic acid tetrahydropyranyl ester / crotonic acid / ethyl vinyl ether / 4-hydroxybutyl vinyl ether copolymer, hexafluoropropylene / trimethylsilyl crotonate / tetrahydropyranyl (meth) acrylate / crotonic acid / ethyl vinyl ether / perfluoro (propyl vinyl ether) ) Copolymer, hexafluoropropylene / trimethylsilyl crotonic acid ester / (meth) acrylic acid tetrahydride Pyranyl ester / crotonic acid / vinyl ether / chlorotrifluoroethylene copolymer, hexafluoropropylene / crotonic acid trimethylsilyl ester / (meth) acrylic acid tetrahydropyranyl ester / crotonic acid / ethyl vinyl ether /
Vinyl acetate copolymer, hexafluoropropylene / trimethylsilyl crotonate / tetrahydropyranyl (meth) acrylate / crotonic acid / ethyl vinyl ether / vinyl glycidyl ether copolymer, hexafluoropropylene / trimethylsilyl crotonate / crotonic acid / ethyl Vinyl ether / 4-hydroxybutyl vinyl ether / perfluoro (propyl vinyl ether) copolymer, hexafluoropropylene / trimethylsilyl crotonate / crotonic acid / ethyl vinyl ether / chlorotrifluoroethylene / perfluoro (propyl vinyl ether) copolymer,
Hexafluoropropylene / trimethylsilyl crotonic acid ester / crotonic acid / ethyl vinyl ether / vinyl acetate / perfluoro (propyl vinyl ether) copolymer, hexafluoropropylene / trimethylsilyl crotonate / crotonic acid / ethyl vinyl ether / vinyl glycidyl ether / perfluoro ( Propyl vinyl ether) copolymer.

The specific polymer is usually produced by radical polymerization of a specific monomer or a specific monomer and a copolymerizable monomer in a polymerization solvent. If necessary, the specific monomer and the copolymerizable monomer may be polymerized in a state where the functional groups are protected, and then deprotection treatment may be performed.

The above specific polymer can also be produced, for example, by the following method. (A) a copolymer derived from an unsaturated carboxylic acid (hereinafter referred to as a “carboxyl group-containing polymer”), for example,
A copolymer of hexafluoropropylene and crotonic acid and the like are prepared, and a part of the carboxyl group is reacted with a compound such as, for example, isobutene, trimethylsilyl chloride, or trimethylgermyl chloride to esterify the compound. A method for producing a polymer containing a polymerized unit. (B) a sodium carboxylate derivatives of the carboxyl group-containing polymer, wherein ^{Cl-M (R 1) (} R 2) (R 3) ( ^{however, M, R 1, R 2} , R 3 are each formula (1) A compound represented by the definition of M, R ¹ , R ² , and R ³ in the above) is subjected to a sodium chloride dechlorination reaction to esterify the compound. (C) A method of directly copolymerizing the unsaturated carboxylic acid compound corresponding to the formula (1).

Examples of the polymerization solvent used for producing the specific polymer include alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol and butyl alcohol; cyclic ethers such as tetrahydrofuran and dioxane; benzene, toluene, xylene and the like. Aromatic hydrocarbons; amide-based protic polar solvents such as N, N-dimethylformamide, N-methyl-2-pyrrolidone;
Esters such as ethyl acetate, butyl acetate, isoamyl acetate and ethyl lactate; methyl 3-methoxypropionate, 2
Alkoxy esters such as methyl-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, and ethyl 2-ethoxypropionate; ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether; (Di) glycol dialkyl esters such as diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether and dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether;
(Di) glycol monoalkyl ethers such as propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether; glycol monoalkyl ether esters such as propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate ; Cyclohexanone, methyl ethyl ketone,
Examples thereof include ketones such as methyl isobutyl ketone and 2-heptanone. These polymerization solvents can be used alone or in combination of two or more.

The ratio of the polymerization solvent to the reaction raw material is not particularly limited, but is usually 20 to 1000 parts by weight of the polymerization solvent with respect to 100 parts by weight of the reaction raw material.

As the polymerization initiator for radical polymerization, for example, 2,2′-azobisisobutyronitrile,
2'-azobis- (2,4-methylvaleronitrile),
Azo compounds such as 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, tert-butylperoxypivalate, 1,1-bis- (tert-butyl) Organic peroxides such as peroxy) cyclohexane or hydrogen peroxide can be mentioned. When a peroxide is used as a polymerization initiator, the peroxide may be used in combination with a reducing agent as a redox polymerization initiator.

The specific polymer has a number average molecular weight in terms of polystyrene of usually from 1,000 to 200,000, preferably from 2,000 to 70,000. When a specific polymer having a number average molecular weight of less than 1000 in terms of polystyrene is used, the shape of the obtained pattern becomes poor, the residual film ratio of the pattern decreases, or the heat resistance of the pattern decreases. There are cases. On the other hand, when a specific polymer having a weight average molecular weight in terms of polystyrene of more than 200,000 is used, the applicability of the radiation-sensitive resin composition becomes poor, or the developability decreases,
The shape of the obtained pattern may be defective.

<Component (B)> Examples of the acid-generating compound which generates an acid upon receiving radiation as the component (B) include:
For example, trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts,
Quaternary ammonium salts, sulfonic esters and the like can be used.

Examples of the above trichloromethyl-s-triazines include tris (2,4,6-trichloromethyl) -s-triazine and 2-phenyl-bis (4,6-
Trichloromethyl) -s-triazine, 2- (4-chlorophenyl) -bis (4,6-trichloromethyl) -s
-Triazine, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2-
(2-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methoxyphenyl) ) -Bis (4,6-
Trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -bis (4,6-trichloromethyl)-
s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine,
-(3-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methylthiophenyl) -bis (4,6-trichloromethyl) -s-
Triazine, 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2-
(3-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy -Β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2-
(3-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxy-β-styryl) -bis (4,6-trichloromethyl)
-S-triazine, 2- (3,4,5-trimethoxy-β
-Styryl) -bis (4,6-trichloromethyl) -s
-Triazine, 2- (4-methylthio-β-styryl)
-Bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2-
(3-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2-piperonyl-
Bis (4,6-trichloromethyl) -s-triazine,
2- [2- (furan-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2-
[2- (5-methylfuran-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2
-[2- (4-diethylamino-2-methylphenyl)
Ethenyl] -bis (4,6-trichloromethyl) -s-
Triazine and the like.

Examples of the above diaryliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate. Nate, diphenyliodonium butyl tris (2,6-
Difluorophenyl) borate, diphenyliodonium hexyltris (p-chlorophenyl) borate, diphenyliodonium hexyltris (3-trifluoromethylphenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate,
4-methoxyphenylphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium-p-toluenesulfonate, 4-methoxyphenylphenyliodonium butyl tris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium hexyl tris ( p-chlorophenyl)
Borate, 4-methoxyphenylphenyliodonium hexyl tris (3-trifluoromethylphenyl) borate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (4-tert-
Butylphenyl) iodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-te
rt-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate, bis (4-ter
t-butylphenyl) iodonium butyl tris (2,
6-difluorophenyl) borate, bis (4-ter
t-butylphenyl) iodonium hexitolis (p
-Chlorophenyl) borate, bis (4-tert-butylphenyl) iodoniumhexyltris (3-trifluoromethylphenyl) borate and the like.

The above triarylsulfonium salts include, for example, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, Phenylsulfonium-p-toluenesulfonate, triphenylsulfoniumbutyltris (2,6-difluorophenyl) borate, triphenylsulfoniumhexyltris (p-chlorophenyl) borate, triphenylsulfoniumhexyltris (3-trifluoromethylphenyl) borate , 4-
Methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfoniumbutyl tris (2,6-difluorophenyl) borate, 4-methoxyphenyldiphenylsulfoniumhexyltris (p-chlorophenyl) borate, 4-
Methoxyphenyldiphenylsulfoniumhexyltris (3-trifluoromethylphenyl) borate, 4-
Phenylthiophenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroarsenate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenyl Sulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenylsulfonium butyl tris (2,
6-difluorophenyl) borate, 4-phenylthiophenyldiphenylsulfoniumhexyl tris (p-
Chlorophenyl) borate, 4-phenylthiophenyldiphenylsulfoniumhexyl tris (3-trifluoromethylphenyl) borate, 4-hydroxy-1-
Naphthalenyl) dimethylsulfonium tetrafluoroborate, 4-hydroxy-1-naphthalenyl) dimethylsulfonium hexafluorophosphonate, 4-hydroxy-1-naphthalenyl) dimethylsulfonium hexafluoroarsenate, 4-hydroxy-1-naphthalenyl) dimethylsulfonium trifluoromethanesulfonate Nato, 4-hydroxy-1-naphthalenyl) dimethylsulfonium trifluoroacetate, 4-hydroxy-1-naphthalenyl) dimethylsulfonium-p-toluenesulfonate, 4-hydroxy-1-naphthalenyl) dimethylsulfoniumbutyltris (2,6- Difluorophenyl) borate, 4-hydroxy-1-naphthalenyl) dimethylsulfoniumhexyltris (p-
Chlorophenyl) borate, 4-hydroxy-1-naphthalenyl) dimethylsulfoniumhexyltris (3-
Trifluoromethylphenyl) borate and the like.

The quaternary ammonium salts include, for example, tetramethylammonium tetrafluoroborate,
Tetramethylammonium hexafluorophosphonate, tetramethylammonium hexafluoroarsenate, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium trifluoroacetate, tetramethylammonium-p-toluenesulfonate, tetramethylammonium butyl tris (2,6- Difluorophenyl) borate, tetramethylammonium hexitolis (p-chlorophenyl)
Borate, tetramethylammonium hexitolis (3-trifluoromethylphenyl) borate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphonate, tetrabutylammonium hexafluoroarsenate, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium Trifluoroacetate, tetrabutylammonium-p-toluenesulfonate, tetrabutylammoniumbutyltris (2,6
-Difluorophenyl) borate, tetrabutylammonium hexitolis (p-chlorophenyl) borate, tetrabutylammonium hexitolis (3-trifluoromethylphenyl) borate, benzyltrimethylammonium tetrafluoroborate, benzyltrimethylammonium hexafluorophosphonate, benzyltrimethylammonium Hexafluoroarsenate, benzyltrimethylammonium trifluoromethanesulfonate, benzyltrimethylammonium trifluoroacetate, benzyltrimethylammonium-p-toluenesulfonate, benzyltrimethylammonium butyl tris (2,6-difluorophenyl) borate, benzyltrimethylammonium hexitolis (P-chlorofu Enyl) borate, benzyltrimethylammonium hexitolis (3-trifluoromethylphenyl) borate, benzyldimethylphenylammonium tetrafluoroborate, benzyldimethylphenylammonium hexafluorophosphonate, benzyldimethylphenylammonium hexafluoroarsenate, benzyldimethylphenylammonium trifluoromethane Sulfonate, benzyldimethylphenylammonium trifluoroacetate, benzyldimethylphenylammonium-p-toluenesulfonate, benzyldimethylphenylammonium butyl tris (2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexitolis (p-chlorophenyl) borate , Benzyldime Tylphenylammonium hexyl tris (3-trifluoromethylphenyl) borate, N-cinnamylideneethylphenylammonium tetrafluoroborate, N-cinnamylideneethylphenylammonium hexafluorophosphonate, N-cinnamylideneethylphenylammonium hexafluoroarcete N-cinnamylideneethylphenylammonium trifluoromethanesulfonate, N-cinnamylideneethylphenylammonium trifluoroacetate, N-cinnamylideneethylphenylammonium-p-toluenesulfonate, N-cinnamylideneethylphenylphenylammonium Butyl tris (2,6-difluorophenyl) borate,
N-cinnamylideneethyl phenyl ammonium hexyl tris (p-chlorophenyl) borate, N-cinnamylidene ethyl phenyl ammonium hexyl tris (3-trifluoromethyl phenyl) borate and the like can be mentioned.

Examples of the above sulfonic acid esters include α-hydroxymethylbenzoin-p-toluenesulfonic acid ester, α-hydroxymethylbenzoin-trifluoromethanesulfonic acid ester, α-hydroxymethylbenzoin-methanesulfonic acid ester, and pyrogallol- Tri (p-toluenesulfonic acid) ester, pyrogallol-tri (trifluoromethanesulfonic acid) ester, pyrogallol-trimethanesulfonic acid ester, 2,4-dinitrobenzyl-p-toluenesulfonic acid ester, 2,4-dinitrobenzyl- Trifluoromethanesulfonic acid ester, 2,4-dinitrobenzyl-methanesulfonic acid ester, 2,4-dinitrobenzyl-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,6-dinitroben Lep-toluenesulfonic acid ester, 2,6-dinitrobenzyl-trifluoromethanesulfonic acid ester, 2,6-dinitrobenzyl-methanesulfonic acid ester, 2,6-dinitrobenzyl-1,2-naphthoquinonediazide-5 Sulfonic acid ester, 2-nitrobenzyl-p-toluenesulfonic acid ester, 2-nitrobenzyl-trifluoromethanesulfonic acid ester, 2-nitrobenzyl-methanesulfonic acid ester, 2-nitrobenzyl-1,2-naphthoquinonediazide-5 -Sulfonic acid ester, 4-nitrobenzyl-p-toluenesulfonic acid ester, 4-nitrobenzyl-trifluoromethanesulfonic acid ester, 4-nitrobenzyl-methanesulfonic acid ester,
4-nitrobenzyl-1,2-naphthoquinonediazide-
5-sulfonic acid ester, N-hydroxynaphthalimide-p-toluenesulfonic acid ester, N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester, N-hydroxynaphthalimide-methanesulfonic acid ester, N-hydroxy-5-norbornene- A few
-Dicarboxyimide-p-toluenesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboximide-trifluoromethanesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboximide- Methanesulfonic acid ester, 2,4,
6,3 ′, 4 ′, 5 ′,-Hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide -4-sulfonic acid ester and the like.

Of these compounds, trichloromethyl-s-triazines include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine and 2- (4-methoxyphenyl)- Screw (4,6-
Trichloromethyl) -s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl)
-S-triazine, 2- (4-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2-piperonyl-bis (4,6-trichloromethyl) -s-triazine, -[2- (furan-2-yl) ethenyl] -bis (4,6-trichloromethyl)-
s-Triazine, 2- [2- (5-methylfuran-2-
Yl) ethenyl] -bis (4,6-trichloromethyl)
-S-triazine, 2- [2- (4-diethylamino-
2-methylphenyl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine or 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl)-
s-triazine; diaryliodonium salts such as diphenyliodonium trifluoroacetate;
Diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate or 4-methoxyphenylphenyliodonium trifluoroacetate; as triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate; quaternary ammonium salts , Tetrame Le ammonium butyl tris (2,
6-difluorophenyl) borate, tetramethylammoniumhexyltris (p-chlorophenyl) borate, tetramethylammoniumhexyltris (3-trifluoromethylphenyl) borate, benzyldimethylphenylammoniumbutyltris (2,6-difluorophenyl) borate, Benzyl dimethyl phenyl ammonium hexyl tris (p-chlorophenyl) borate, benzyl dimethyl phenyl ammonium hexyl tris (3-trifluoromethyl phenyl) borate;
As the sulfonic acid esters, 2,6-dinitrobenzyl-p-toluenesulfonic acid ester, 2,6-dinitrobenzyl-trifluoromethanesulfonic acid ester, N-hydroxynaphthalimide-p-toluenesulfonic acid ester, N-hydroxy Naphthalimide-trifluoromethanesulfonic acid ester can each be mentioned as a preferable one.

The proportion of the component (B) used is (A) 10
0.001 to 30 parts by weight, in particular, 0.
It is preferably from 0.01 to 10 parts by weight. Component (B) is used in an amount of 0.001 to 100 parts by weight of component (A).
When the amount is less than parts by weight, the amount of the acid generated upon irradiation with radiation is small, so that the crosslinking of the component (A) molecules does not proceed sufficiently, the residual film ratio after the development processing, and the heat resistance of the obtained pattern. Properties, chemical resistance, adhesion to a substrate, etc. may be reduced. On the other hand, the use ratio of the component (B) is
When the amount exceeds 30 parts by weight with respect to 0 parts by weight, the composition tends to have low sensitivity.

<Component (C)> Specific examples of the crosslinkable compound having at least one crosslinkable group as the component (C) include epoxy, oxetane, alkoxymethylated melamine, alkoxymethylated glycoluril, and alkoxymethylated. Benzoguanamine, alkoxymethylated urea,
Examples include isocyanate, cyanate, oxazoline, oxazine and the like.

As a commercially available epoxy resin, as the bisphenol A type epoxy resin, Epicoat 1001, 1002, 1003, 1004, 1007, 1
009, 1010, and 828 (both manufactured by Yuka Shell Epoxy Co., Ltd.) and the like. As bisphenol F type epoxy resin, Epicoat 807 (manufactured by Yuka Shell Epoxy Co., Ltd.) and the like, phenol novolak epoxy resin As Epicoat 152 and Epicoat 154 (all manufactured by Yuka Shell Epoxy Co., Ltd.), EPPN201 and EP202
(Nippon Kayaku Co., Ltd.) and the like, as cresol novolak type epoxy resins, EOCN-102, EOC
N-103S, EOCN-104S, EOCN-102
0, EOCN-1025, EOCN-1027 (the above,
Nippon Kayaku Co., Ltd.), Epikote 180S75 (Yukaka Epoxy Co., Ltd.), etc., and CY175, CY177, CY179 (all CIBA-GEIGY AG) as cyclic aliphatic epoxy resins, ERL-42
34, ERL-4299, ERL-4221, ERL-
4206 (all manufactured by UCC), Shodyne 509
(Manufactured by Showa Denko KK), Araldite CY-182, CY-192 and CY-184 (all CIBA-GE
IGY AG), Epicron 200, 400 (all manufactured by Dainippon Ink Industries, Ltd.), Epicoat 871,
872 (both manufactured by Yuka Shell Epoxy Co., Ltd.), ED
-5661 and ED-5662 (all manufactured by Celanese Coatings Co., Ltd.) and the like as aliphatic polyglycidyl ethers; ) And the like.

Among these, preferred are bisphenol A type epoxy resin, phenol novolak type epoxy resin and cresol novolak type epoxy resin.

Although most of the compounds exemplified above are high molecular weight compounds, the molecular weight of this compound is not particularly limited. You can also. The proportion of the compound containing two or more epoxy groups in the molecule is usually 100 parts by weight or less, preferably 5 parts by weight, per 100 parts by weight of the component (A).
0 parts by weight or less.

As the oxetane, for example, bis [(3-ethyl-3-oxetanylmethoxy) methyl]
Benzene (trade name “XDO” manufactured by Toagosei Co., Ltd.), bis [(3-ethyl-3-oxetanylmethoxy) methyl-
Phenyl] methane, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl-
Phenyl] propane, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] sulfone, bis [(3-ethyl-3-oxetanylmethoxy) methyl-
Phenyl] ketone, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] hexafluoropropane, tri [(3-ethyl-3-oxetanylmethoxy)
Methyl] benzene, tetra [(3-ethyl-3-oxetanylmethoxy) methyl] benzene and the like.

The above-mentioned alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril and alkoxymethylated urea are the same as methylolated melamine, methylolated benzoguanamine, methylolated glycoluril and methylolated urea, respectively. Can be obtained by converting The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. Among these crosslinkable compounds, alkoxymethylated melamine and alkoxymethylated benzoguanamine are preferred crosslinkable compounds. Examples of such crosslinkable compounds include Cymel 300, 301, 303, and 37.
0, 325, 327, 701, 266, 26
7, 238, 1141, 272, 202, 1
156, 1158, 1123, 1170, 11
74, UFR65, 300 (all manufactured by Mitsui Cyanamid Co., Ltd.), Nicaraq Mx-750, Mx-0
32, Mx-706, Mx-708, Mx-4
0, Mx-31, Ms-11 and Mw-30 (all manufactured by Sanwa Chemical Co., Ltd.) can be preferably used. These crosslinkable compounds can be used alone or in combination of two or more.

Examples of the isocyanate include phenylene-1,3-diisocyanate and phenylene-1,4
-Diisocyanate, 1-methoxyphenylene-2,4
-Diisocyanate, 1-methylphenylene-2,4-
Diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, biphenylene-4,4′-diisocyanate,
3,3'-dimethoxybiphenylene-4,4'-diisocyanate, 3,3'-dimethylbiphenylene-4,4'-
Diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4,
4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, naphthylene-
1,5-diisocyanate, cyclobutylene-1,3-diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate,
-Methylcyclohexylene-2,4-diisocyanate, 1-methylcyclohexylene-2,6-diisocyanate, 1-isocyanate-3,3,5-trimethyl-
5-isocyanatomethylcyclohexane, cyclohexane-1,3-bis (methylisocyanate), cyclohexane-1,4-bis (methylisocyanate), isophorone diisocyanate, dicyclohexylmethane
2,4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, ethylene diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, dodecamethylene-1,12-diisocyanate, lysine diisocyanatemethyl Examples of the ester include isocyanate prepolymers obtained by reacting an ester or a stoichiometric excess of these organic diisocyanates with a bifunctional active hydrogen-containing compound. These organic diisocyanates can be used alone or in combination of two or more. Other organic polyisocyanates which may be used together with these organic diisocyanates, for example, include phenyl-1,3,5-
Triisocyanate, diphenylmethane-2,4,4'-
Triisocyanate, diphenylmethane-2,5,4'-
Triisocyanate, triphenylmethane-2,4 ',
4 "-triisocyanate, triphenylmethane-4,
4 ', 4 "-triisocyanate, diphenylmethane-
2,4,2 ', 4'-tetraisocyanate, diphenylmethane-2,5,2', 5'-tetraisocyanate, cyclohexane-1,3,5-triisocyanate, cyclohexane-1,3,5-tris (methyl Isocyanate), 3,5-dimethylcyclohexane-1,3,5-tris (methylisocyanate), 1,3,5-trimethylcyclohexane-1,3,5-tris (methylisocyanate), dicyclohexylmethane-2,4, 2'-triisocyanate, dicyclohexylmethane-2,4,4'-
Tri- or higher functional organic polyisocyanate such as triisocyanate or a terminal isocyanate prepolymer obtained by reacting a stoichiometric excess of these tri- or higher functional organic polyisocyanate with a bi- or higher functional polyfunctional active hydrogen-containing compound. Polymers and the like can be mentioned.

As the cyanate, for example, 1,3-
Dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-, 1,
4-, 1,6-, 1.8-, 2.6-, or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 2,2'- or 4,4'-di Cyanate biphenyl, bis (4-cyanatophenyl) methane, 2,2-
Bis (4-cyanatophenyl) propane, 2,2'-
Bis (3,5-dichloro-4-cyanatophenyl) propane, 2,2-bis (4-cyanatophenyl) ethane, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, Screw (4-
Cyanatophenyl) sulfone, 1,1,1,3,3,3-
Hexafluoro-2,2-bis (4-cyanatophenyl) propane, tris (4-cyanatophenyl) phosphite, tris (4-cyanatophenyl) phosphate, and a reaction obtained from the reaction of a phenolic resin with a cyanogen halide. Benzene polynuclear polyisocyanate compounds (for example, JP-B Nos. 45-11712 and 55-9)
433) and the like. 2 derived from bisphenols such as 2,2-bis (4-cyanatophenyl) propane, in that they are readily available and give good moldability and good properties to the final cured product.
Valent cyanate compounds are particularly well used. Also useful are polycyanates obtained by reacting a cyanogen halide with an initial condensate of phenol and formaldehyde.

As the oxazoline, for example, 2,
2'-bis (2-oxazoline), 4-furan-2-ylmethylene-2-phenyl-4H-oxazole-5
On, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, 1,3-bis (4,5-dihydro-2-oxazolyl) benzene, 2,3-bis (4-isopropenyl-2) -Oxazolin-2-yl) butane, 2,2 ′
-Bis-4-benzyl-2-oxazoline, 2,6-bis (isopropyl-2-oxazolin-2-yl) pyridine, 2,2'-isopropylidenebis (4-tert
-Butyl-2-oxazoline), 2,2′-isopropylidenebis (4-phenyl-2-oxazoline),
2'-methylenebis (4-tert-butyl-2-oxazoline), 2,2'-methylenebis (4-phenyl-
2-oxazoline) and the like.

As the oxazine, 2,2′-
Bis (2-oxazine), 4-furan-2-ylmethylene-2-phenyl-4H-oxazyl-5-one,
4-bis (4,5-dihydro-2-oxadyl) benzene, 1,3-bis (4,5-dihydro-2-oxadyl)
Benzene, 2,3-bis (4-isopropenyl-2-oxazin-2-yl) butane, 2,2'-bis-4-benzyl-2-oxazine, 2,6-bis (isopropyl-2-oxazine- 2-yl) pyridine, 2,2'-isopropylidenebis (4-tert-butyl-2-oxazine), 2,2'-isopropylidenebis (4-phenyl-2-oxazine), 2,2'-methylenebis (4
-Tert-butyl-2-oxazine), 2,2'-methylenebis (4-phenyl-2-oxazine) and the like.

The proportion of the crosslinkable compound used as the component (C) is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, per 100 parts by weight of the component (A). (C)
When the use ratio of the component is less than 1 part by weight with respect to 100 parts by weight of the component (A), the crosslinking of the system becomes insufficient, so that it may be difficult to form a pattern itself. On the other hand, when the use ratio of the component (C) exceeds 100 parts by weight based on 100 parts by weight of the component (A), the alkali solubility of the entire composition becomes excessive, and the residual film ratio after the development processing is increased. In a direction of decreasing.

<Other Components> The radiation-sensitive resin composition of the present invention may contain a sensitizer. Examples of the sensitizer include coumarins, flavones, dibenzalacetones, dibenzacyclohexanes, chalcones, xanthenes, thioxanthenes having a substituent at the 3- and / or 7-position, Porphyrins, phthalocyanines, acridines, anthracenes and the like can be used. The proportion of the sensitizer used is (A) component 100
30 parts by weight or less, preferably 0.1 to 10 parts by weight,
20 parts by weight or less.

Further, in the radiation-sensitive resin composition of the present invention, a surfactant can be added to improve coating properties (for example, prevention of striation) and development property. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; and polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Nonionic surfactants such as polyethylene glycol dialkyl esters such as ethylene aryl ethers, polyethylene glycol dilaurate, and polyethylene glycol distearate; F-Top EF301 and EF30
3. EF352 (above, manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, F172, F173 (above, manufactured by Dainippon Ink Industries, Ltd.), Florard FC430, FC431 (above, Sumitomo 3M Co., Ltd.) )), Asahi Guard AG710, Surflon S-382, SC-10
1, SC-102, SC-103, SC-104, SC
-Surfactants commercially available under trade names such as -105, SC-106 (all manufactured by Asahi Glass Co., Ltd.); and organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.)
Acrylic or methacrylic acid (co) polymer polyflow Nos. 57 and 95 (Kyoei Yushi Kagaku Kogyo Co., Ltd.)
And other surfactants commercially available under the trade name such as “Production”.

The use ratio of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less based on 100 parts by weight of the solids in the composition.

Further, in the radiation-sensitive resin composition of the present invention, an adhesion aid such as a silane coupling agent can be added in order to improve the adhesion to the substrate. For the purpose, an unsaturated compound such as a polyvalent acrylate may be added. Further, in the radiation-sensitive resin composition of the present invention, if necessary, an antistatic agent, a storage stabilizer, an antihalation agent, an antifoaming agent, a pigment, a thermal acid generator, and the like can be added.

<Formation of Pattern> By using the radiation-sensitive resin composition of the present invention, a pattern can be formed, for example, as follows. First, the radiation-sensitive resin composition is dissolved in a solvent, for example, so that the concentration of the solid content is 5 to 60% by weight.
A composition solution is prepared by filtering through a filter of a degree. Then, this composition solution is applied to the surface of a substrate such as a silicon wafer, and the solvent is removed by performing prebaking to form a coating film of the radiation-sensitive resin composition.
Next, after performing a radiation irradiation process on the formed coating film, a PEB process is performed. After that, a pattern is formed by performing a developing process to remove the non-irradiated portion.

In the above, as the solvent for preparing the composition solution, the same solvents as those exemplified above as the polymerization solvent used for producing the specific polymer can be used. Further, if necessary, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, High boiling solvents such as benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, carbitol acetate and the like can also be added.

As a method for applying the composition solution to the substrate, various methods such as a spin coating method, a flow coating method, and a roll coating method can be adopted. Prebaking conditions are, for example, a heating temperature of 50 to 150 ° C. and a heating time of 30 seconds to
600 seconds. As radiation used for the radiation irradiation treatment, ultraviolet rays such as i-line having a wavelength of 365 nm, g-line having a wavelength of 436 nm, a KrF excimer laser having a wavelength of 248 nm,
Far ultraviolet rays such as an ArF excimer laser having a wavelength of 193 nm; charged particles such as X-rays or electron beams such as synchrotron radiation;

Examples of the developing solution used in the developing treatment include sodium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, and the like. Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-
Undecene, 1,5-diazabicyclo [4.3.0] -5
-An alkaline aqueous solution in which nonane or the like is dissolved can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent, for example, an alcohol such as methanol or ethanol, or a surfactant to this alkaline aqueous solution can also be used. The development processing time is, for example, 10 to 300 seconds, and as a development method, a liquid puddle method, a dipping method, a rocking immersion method, or the like can be used.

After the development treatment, a rinsing treatment is carried out by washing with running water, and air drying is performed with, for example, compressed air or compressed nitrogen. If necessary, for example, the surface of the thin film is irradiated with ultraviolet rays, and then heated with a heating device such as a hot plate or an oven. Perform post bake. Post-baking conditions are usually, for example, 150 to 3
The temperature may be 3 minutes to 2 hours at a temperature of 00C. In this manner, a cured pattern-like thin film is formed on the substrate. The relative permittivity of the patterned thin film thus obtained is 3 or less, preferably 2.8 or less. In addition, the pattern-like thin film has high resolution, low dielectric constant, insulating property, flatness, heat resistance,
Excellent physical properties such as transparency and hardness. Therefore, it is useful for a protective film, a flattening film, an interlayer insulating film, and the like of an electronic component, and particularly useful for an interlayer insulating film of a liquid crystal display device, an integrated circuit device, and a solid-state imaging device.

[0074]

EXAMPLES Examples of the radiation-sensitive resin composition of the present invention will be described below, but the present invention is not limited to these examples. In the following, the weight average molecular weight in terms of polystyrene of the polymer was measured using GPC Chromatograph SYSTEM-21 manufactured by Showa Denko KK.

[Synthesis Example of Specific Polymer] Synthesis Example 1 of Specific Polymer A stainless steel autoclave having an inner volume of 0.5 L with an electromagnetic stirrer was sufficiently replaced with nitrogen gas.
g, ethyl vinyl ether (EVE) 34.2 g, crotonic acid (CA) 27.2 g, and lauroyl peroxide 5.4.
g, and cooled to -50 ° C with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas. Next, 119 g of hexafluoropropylene (HFP) was charged, and the temperature was raised. The temperature in the autoclave is 7
The pressure when the temperature reached 0 ° C. was 7.6 kgf / cm ² . Thereafter, the reaction was continued under stirring at 70 ° C. for 12 hours,
When the pressure dropped to 6.3 kgf / cm ² , the autoclave was cooled with water to stop the reaction. After reaching room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution having a solid content of 19.6% by weight. The obtained polymer solution was poured into water to precipitate a polymer, which was then purified by reprecipitation with n-hexane, and dried at 50 ° C. under vacuum to obtain a polymer.
g of a fluorine-containing copolymer was obtained (hereinafter, this resin is referred to as “resin (1)”). When the obtained resin (1) was measured for number average molecular weight in terms of polystyrene using a GPC chromatograph SYSTEM-21 manufactured by Showa Denko KK, it was found to be 84.
00.

Synthesis Example 2 of Specific Polymer A nitrogen autoclave having an inner volume of 0.5 L and equipped with a magnetic stirrer was sufficiently substituted with nitrogen gas, and then ethyl acetate 270 was added.
g, ethyl vinyl ether (EVE) 28.3 g, crotonic acid (CA) 33.8 g and lauroyl peroxide 5.4.
g, and cooled to -50 ° C with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas. Next, 118 g of hexafluoropropylene (HFP) was charged, and the temperature was raised. The temperature in the autoclave is 7
The pressure when the temperature reached 0 ° C. was 7.8 kgf / cm ² . Thereafter, the reaction was continued under stirring at 70 ° C. for 12 hours,
When the pressure dropped to 6.9 kgf / cm ² , the autoclave was cooled with water to stop the reaction. After reaching room temperature, the unreacted monomer was released and the autoclave was opened to obtain a polymer solution having a solid content of 18.0%. The obtained polymer solution was poured into water to precipitate a polymer, which was then purified by reprecipitation with n-hexane, followed by vacuum drying at 50 ° C. to obtain 80 g of a fluorine-containing copolymer (hereinafter, this resin was used). Is referred to as “resin (2)”). The obtained resin (2) was measured for number average molecular weight in terms of polystyrene using a GPC chromatograph SYSTEM-21 manufactured by Showa Denko KK, and found to be 39.
00.

Synthesis Example 3 of Specific Polymer A nitrogen autoclave having an inner volume of 0.5 L and equipped with a magnetic stirrer was sufficiently replaced with nitrogen gas.
g, ethyl vinyl ether (EVE) 22.5 g, crotonic acid (CA) 40.3 g and lauroyl peroxide 5.4.
g, and cooled to -50 ° C with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas. Next, 117 g of hexafluoropropylene (HFP) was charged, and the temperature was raised. The temperature in the autoclave is 7
The pressure when the temperature reached 0 ° C. was 8.3 kgf / cm ² . Thereafter, the reaction was continued under stirring at 70 ° C. for 12 hours,
When the pressure dropped to 7.5 kgf / cm ² , the autoclave was cooled with water to stop the reaction. After reaching room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution having a solid content of 16.8%. The obtained polymer solution was poured into water to precipitate a polymer, which was then reprecipitated and purified with n-hexane, and dried under vacuum at 50 ° C. to obtain 80 g of a fluorine-containing copolymer (hereinafter, this resin was used). Is referred to as “resin (3)”). The obtained resin (3) was measured for number average molecular weight in terms of polystyrene using a GPC chromatograph SYSTEM-21 manufactured by Showa Denko KK.
00.

Synthesis Example 4 of Specific Polymer A stainless steel autoclave having an inner volume of 0.5 L and equipped with a magnetic stirrer was sufficiently replaced with nitrogen gas.
g, ethyl vinyl ether (EVE) 34.2 g, crotonic acid (CA) 27.2 g, and lauroyl peroxide 1.8.
g, and cooled to -50 ° C with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas. Next, 119 g of hexafluoropropylene (HFP) was charged, and the temperature was raised. The temperature in the autoclave is 6
The pressure when the temperature reached 0 ° C. was 6.5 kgf / cm ² . Thereafter, the reaction was continued under stirring at 70 ° C. for 24 hours,
When the pressure dropped to 5.1 kgf / cm ² , the autoclave was cooled with water to stop the reaction. After reaching room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution having a solid content of 20.3%. The obtained polymer solution was poured into water to precipitate the polymer, which was then reprecipitated and purified with n-hexane and dried at 50 ° C. in vacuo to obtain 86 g of a fluorine-containing copolymer (hereinafter, this resin was used). Is referred to as “resin (4)”). The obtained resin (4) was measured for number average molecular weight in terms of polystyrene using a GPC chromatograph SYSTEM-21 manufactured by Showa Denko KK.
000.

Synthesis Example 5 of Specific Polymer After a stainless steel autoclave having an electromagnetic stirrer having an inner volume of 0.5 L was sufficiently replaced with nitrogen gas, 270 g of diethylene glycol ethyl methyl ether (EDM), 22.3 g of ethyl vinyl ether (EVE), and croton Acid (C
A) 26.6 g, glycidyl vinyl ether (GVE)
15.5 g and 5.4 g of lauroyl peroxide were charged,
After cooling to -50 ° C with dry ice-methanol,
Oxygen in the system was removed again with nitrogen gas. Next, 116 g of hexafluoropropylene (HFP) was charged, and the temperature was raised. The pressure when the temperature in the autoclave reached 60 ° C. was 7.9 kgf / cm ² . afterwards,
The reaction was continued with stirring at 60 ° C. for 24 hours, and the pressure was 7.1.
The autoclave was cooled with water at the time of the decrease to kgf / cm ² to stop the reaction. After reaching room temperature, the unreacted monomer was released, the autoclave was opened, and the solid concentration was 23.7.
% Polymer solution was obtained. The obtained polymer solution was poured into water to precipitate a polymer, which was then purified by reprecipitation with n-hexane, followed by vacuum drying at 50 ° C. to obtain 88 g of a fluorinated copolymer (hereinafter, this resin). Is referred to as “resin (5)”). The obtained resin (5) was used for GPC manufactured by Showa Denko KK
It was 12600 when the number average molecular weight in terms of polystyrene was measured with a chromatogram SYSTEM-21.

Synthesis Example 6 of Specific Polymer After the eggplant flask having an inner volume of 0.5 L was sufficiently replaced with nitrogen gas, 150 g of THF, 100 g of resin (1) and 13.9 g of triethylamine were charged, and -50 g of dry ice-methanol was added. After cooling to ° C., oxygen in the system was removed again with nitrogen gas. Next, 14.9 g of trimethylsilyl chloride dissolved in 50 g of THF was added dropwise under ice cooling. After completion of the dropwise addition, the reaction was started when the temperature of the reactor was returned to room temperature. Thereafter, the reaction was continued for 12 hours with stirring, and then stopped. After the reaction was stopped, the precipitate was removed by filtration and the filtrate was concentrated. The obtained polymer solution was poured into water to precipitate a polymer. Thereafter, the precipitate was purified by reprecipitation with n-hexane and vacuum dried at 50 ° C. to obtain 105 g of a fluorine-containing copolymer (hereinafter, this resin is referred to as “resin (6)”). The infrared absorption of the obtained resin (6) was measured using IR-700 manufactured by JASCO Corporation.
A new absorption derived from vC = O was confirmed at around 30 cm ^-1 . The resin (6) was measured for number average molecular weight in terms of polystyrene using GPC Chromatograph SYSTEM-21 manufactured by Showa Denko KK, and found to be 8,200.

Synthesis Example 7 of Specific Polymer After an eggplant flask having an inner volume of 0.5 L was sufficiently replaced with nitrogen gas, 150 g of THF, 100 g of resin (2) and 17.4 g of triethylamine were charged, and -50 g of dry ice-methanol was added. After cooling to ° C., oxygen in the system was removed again with nitrogen gas. Next, 18.9 g of trimethylsilyl chloride dissolved in 50 g of THF was added dropwise under ice cooling. After completion of the dropwise addition, the reaction was started when the temperature of the reactor was returned to room temperature. Thereafter, the reaction was continued for 12 hours with stirring, and then stopped. After the reaction was stopped, the precipitate was removed by filtration and the filtrate was concentrated. The obtained polymer solution was poured into water to precipitate a polymer. Thereafter, the precipitate was purified by reprecipitation with n-hexane and vacuum dried at 50 ° C. to obtain 107 g of a fluorine-containing copolymer (hereinafter, this resin is referred to as “resin (7)”). The infrared absorption of the obtained resin (7) was measured using IR-700 manufactured by JASCO Corporation.
A new absorption derived from vC = O was confirmed at around 30 cm ^-1 . The resin (7) was measured for number average molecular weight in terms of polystyrene using a GPC chromatograph SYSTEM-21 manufactured by Showa Denko KK to be 3,800.

Synthesis Example 8 of Specific Polymer After a 0.5 L eggplant flask having an inner volume of 0.5 L was sufficiently replaced with nitrogen gas, 150 g of THF, 100 g of resin (3) and 20.6 g of triethylamine were charged, and -50 g of dry ice-methanol was added. After cooling to ° C., oxygen in the system was removed again with nitrogen gas. Next, 22.2 g of trimethylsilyl chloride dissolved in 50 g of THF was added dropwise under ice cooling. After completion of the dropwise addition, the reaction was started when the temperature of the reactor was returned to room temperature. Thereafter, the reaction was continued for 12 hours with stirring, and then stopped. After the reaction was stopped, the precipitate was removed by filtration and the filtrate was concentrated. The obtained polymer solution was poured into water to precipitate a polymer. Thereafter, the precipitate was purified by reprecipitation with n-hexane, and dried under vacuum at 50 ° C. to obtain 112 g of a fluorine-containing copolymer (hereinafter, this resin is referred to as “resin (8)”). The infrared absorption of the obtained resin (8) was measured using IR-700 manufactured by JASCO Corporation.
A new absorption derived from vC = O was confirmed at around 30 cm ^-1 . The resin (8) was measured for number average molecular weight in terms of polystyrene using a GPC chromatograph SYSTEM-21 manufactured by Showa Denko KK to be 2,800.

Synthesis Example 9 of Specific Polymer After a 0.5 L eggplant flask with an inner volume of 0.5 L was sufficiently replaced with nitrogen gas, 150 g of THF, 100 g of resin (4) and 13.9 g of triethylamine were charged, and -50 g of dry ice-methanol was added. After cooling to ° C., oxygen in the system was removed again with nitrogen gas. Next, 14.9 g of trimethylsilyl chloride dissolved in 50 g of THF was added dropwise under ice cooling. After completion of the dropwise addition, the reaction was started when the temperature of the reactor was returned to room temperature. Thereafter, the reaction was continued for 12 hours with stirring, and then stopped. After the reaction was stopped, the precipitate was removed by filtration and the filtrate was concentrated. The obtained polymer solution was poured into water to precipitate a polymer. Thereafter, the precipitate was purified by reprecipitation with n-hexane and vacuum dried at 50 ° C. to obtain 106 g of a fluorine-containing copolymer (hereinafter, this resin is referred to as “resin (9)”). The infrared absorption of the obtained resin (9) was measured using IR-700 manufactured by JASCO Corporation.
A new absorption derived from vC = O was confirmed at around 30 cm ^-1 . The resin (9) was measured for number average molecular weight in terms of polystyrene using a GPC chromatograph SYSTEM-21 manufactured by Showa Denko KK, and found to be 20,900.

Synthesis Example 10 of Specific Polymer After a 0.5-L eggplant-shaped flask having an inner volume of 0.5 L was sufficiently replaced with nitrogen gas, 150 g of THF, 100 g of resin (5), and 13.6 g of triethylamine were charged, and -50 g of dry ice-methanol was added. After cooling to ° C., oxygen in the system was removed again with nitrogen gas. Then, 14.6 g of trimethylsilyl chloride dissolved in 50 g of THF was added dropwise under ice cooling. After completion of the dropwise addition, the reaction was started when the temperature of the reactor was returned to room temperature. Thereafter, the reaction was continued for 12 hours with stirring, and then stopped. After the reaction was stopped, the precipitate was removed by filtration and the filtrate was concentrated. The obtained polymer solution was poured into water to precipitate a polymer. Thereafter, the precipitate was purified by reprecipitation with n-hexane and vacuum dried at 50 ° C. to obtain 106 g of a fluorine-containing copolymer (hereinafter, this resin is referred to as “resin (10)”). The infrared absorption of the obtained resin (10) was measured using IR-700 manufactured by JASCO Corporation.
A new absorption derived from vC = O was confirmed at around 30 cm ^-1 . The resin (9) was measured for number average molecular weight in terms of polystyrene using a GPC chromatograph SYSTEM-21 manufactured by Showa Denko KK, and found to be 11,900.

Synthesis Example 11 of Specific Polymer After a stainless steel autoclave having an inner volume of 0.5 L and equipped with an electromagnetic stirrer was sufficiently replaced with nitrogen gas, dioxane 200
g, 100 g of resin (1) and 5 g of sulfuric acid, and cooled to −50 ° C. with dry ice-methanol, and oxygen in the system was removed again with nitrogen gas. Then 40 g of isobutene
And heating was started. The reaction was started when the temperature in the autoclave reached 40 ° C. After that, the reaction was continued under stirring at 40 ° C. for 24 hours, and then the autoclave was cooled with water to stop the reaction. After the termination of the reaction, the unreacted monomer was released and the autoclave was opened. The obtained polymer solution was poured into water to precipitate a polymer, which was then purified by reprecipitation with n-hexane, and dried at 50 ° C. under vacuum to obtain 115
g of a fluorinated copolymer was obtained (hereinafter, this resin is referred to as “resin (11)”). When the infrared absorption of the obtained resin (6) was measured using IR-700 manufactured by JASCO Corporation, a new absorption derived from vC = O was confirmed around 1730 cm ^-1 . In addition, resin (11) was manufactured by Showa Denko KK
It was 8200 when the number average molecular weight in terms of polystyrene was measured with a PC chromatograph SYSTEM-21.

Synthesis Example 12 of Specific Polymer After the eggplant flask having an inner volume of 0.5 L was sufficiently replaced with nitrogen gas, 150 g of THF, 100 g of resin (1), and 13.9 g of triethylamine were charged, and -50 g of dry ice-methanol was added. After cooling to ° C., oxygen in the system was removed again with nitrogen gas. Next, 21.0 g of trimethyl gel milk chloride dissolved in 50 g of THF was added dropwise under ice cooling. After completion of the dropwise addition, the reaction was started when the temperature of the reactor was returned to room temperature. Thereafter, the reaction was continued for 12 hours with stirring, and then stopped. After the reaction was stopped, the precipitate was removed by filtration and the filtrate was concentrated. The obtained polymer solution was poured into water to precipitate a polymer. Thereafter, the precipitate was purified by reprecipitation with n-hexane and vacuum dried at 50 ° C. to obtain 104 g of a fluorine-containing copolymer (hereinafter, this resin is referred to as “resin (12)”).
). The infrared absorption of the obtained resin (12) was measured using IR-700 manufactured by JASCO Corporation.
A new absorption derived from vC = O was confirmed at around 730 cm ^-1 . The resin (12) was measured for number average molecular weight in terms of polystyrene using a GPC chromatograph SYSTEM-21 manufactured by Showa Denko KK to be 8,300.

Synthesis Example 13 of Specific Polymer A nitrogen autoclave having an inner volume of 0.5 L and equipped with a magnetic stirrer was sufficiently replaced with nitrogen gas.
g, ethyl vinyl ether (EVE) 22.2 g, 2-ethoxyethyl crotonate (EECA) 48.8 g,
13.4 g of crotonic acid (CA) and 5.4 g of lauroyl peroxide were charged, and -50 was added to dry ice-methanol.
After cooling to ° C., oxygen in the system was removed again with nitrogen gas. Then hexafluoropropylene (HFP) 11
6 g was charged, and the temperature was raised. When the temperature inside the autoclave reaches 70 ° C., the pressure is 8.0 kgf / cm ^2.
showed that. Thereafter, the reaction was continued with stirring at 70 ° C. for 10 hours, and when the pressure dropped to 7.0 kgf / cm ² , the autoclave was cooled with water to stop the reaction. After reaching room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution having a solid content of 24.5%. After pouring the obtained polymer solution into water to precipitate a polymer, n-
After reprecipitation purification with hexane, vacuum drying at 50 ° C.
5 g of a fluorine-containing copolymer was obtained (hereinafter, this resin is referred to as “resin (13)”). The obtained resin (13) was used as a GPC chromatograph SYSTEM-2 manufactured by Showa Denko KK
When the number average molecular weight in terms of polystyrene was measured at 1,
4000.

Synthesis Example 14 of Specific Polymer A stainless steel autoclave having an inner volume of 0.5 L and equipped with a magnetic stirrer was sufficiently replaced with nitrogen gas.
g, ethyl vinyl ether (EVE) 21.8 g, tetrahydropyranyl crotonate (TPCA) 51.6 g,
13.0 g of crotonic acid (CA) and 5.4 g of lauroyl peroxide were charged, and dried ice-methanol to -50 g.
After cooling to ° C., oxygen in the system was removed again with nitrogen gas. Then hexafluoropropylene (HFP) 114
g, and the temperature was raised. The pressure when the temperature in the autoclave reached 70 ° C. was 8.1 kgf / cm ² . Thereafter, the reaction was continued under stirring at 70 ° C. for 10 hours, and when the pressure dropped to 7.2 kgf / cm ² , the autoclave was cooled with water to stop the reaction. After reaching room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution having a solid content of 24.0%. After pouring the obtained polymer solution into water to precipitate a polymer, n-
After reprecipitation purification with hexane, vacuum drying at 50 ° C.
3 g of a fluorine-containing copolymer was obtained (hereinafter, this resin is referred to as “resin (14)”). The obtained resin (14) was used as a GPC chromatograph SYSTEM-2 manufactured by Showa Denko KK
When the number average molecular weight in terms of polystyrene was measured at 1,
3900.

Synthesis Example 15 of Specific Polymer A stainless steel autoclave having an inner volume of 0.5 L with a magnetic stirrer was sufficiently substituted with nitrogen gas, and then ethyl acetate 270 was added.
g, ethyl vinyl ether (EVE) 10.8 g, 2-ethoxyethyl crotonate (EECA) 47.8 g,
13.0 g of crotonic acid (CA), 15.2 g of glycidyl vinyl ether (GVE) and 5.4 of lauroyl peroxide
g, and cooled to -50 ° C with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas. Next, 113 g of hexafluoropropylene (HFP) was charged, and the temperature was raised. The temperature in the autoclave is 7
The pressure when the temperature reached 0 ° C. was 8.1 kgf / cm ² . Thereafter, the reaction was continued under stirring at 70 ° C. for 10 hours,
When the pressure dropped to 6.8 kgf / cm ² , the autoclave was cooled with water to stop the reaction. After reaching room temperature, the unreacted monomer was released and the autoclave was opened to obtain a polymer solution having a solid content of 26.1%. The obtained polymer solution was poured into water to precipitate a polymer, which was purified by reprecipitation with n-hexane, and dried at 50 ° C. under vacuum to obtain 102 g.
Was obtained (hereinafter, this resin is referred to as “resin (15)”). The obtained resin (15) was used as a GPC chromatograph SYSTEM-21 manufactured by Showa Denko KK
When the number average molecular weight in terms of polystyrene was measured with
600.

【Example】

Example 1 As the component (A), 100 parts by weight of the resin (6) was used.
1 part by weight of 4-phenylthiophenyldiphenylhexafluorophosphonate as the component (B) and 20 parts by weight of tetramethoxymethylolglycoluril as the component (C) are mixed with diethylene glycol ethyl methyl ether so that the total solid concentration becomes 35%. After dissolving in
The solution was filtered through a membrane filter having a pore size of 0.2 μm to prepare a composition solution of the present invention.

<Formation of Coating Film> The composition solution 1 was applied on a silicon substrate by using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. .

<Radiation Irradiation Treatment and Development Treatment> The obtained coating film was subjected to radiation irradiation treatment at an optimum depth of focus by an NSR1505i6A reduction projection exposure machine (Nikon Corporation, NA = 0.45, λ = 365 nm). went. Then
A pattern was formed by developing with an aqueous solution of 0.2% by weight of tetramethylammonium hydroxide, washing with water and drying.

<Post-baking> The silicon substrate on which the pattern was formed was heated on a hot plate at 220 ° C. for 1 hour to perform post-baking of the pattern.
A silicon substrate on which a patterned thin film was formed was obtained.

<Measurement of Dielectric Constant> Measurement was performed under the conditions of room temperature and 1 MHz. Table 1 shows the results.

<Evaluation of Radiation Sensitivity> PEB treatment and development were performed by changing the irradiation time at the time of UV irradiation, and the results were adjusted to 5.0.
The radiation sensitivity that can be patterned at a resolution of μm × 5.0 μm or less and the sensitivity at that time is 30 mJ / cm ² or less is indicated by ○, and the radiation sensitivity that can be patterned at 50 mJ / cm ² or less is Δ. The radiation sensitivity at which one of the above resolution and sensitivity of 50 mJ / cm ² or less or both did not reach this standard was evaluated as x. Table 1 shows the results.

<Evaluation of Heat-Resistant Dimensional Stability> After the silicon substrate on which the patterned thin film was formed was heated in an oven at 200 ° C. for 1 hour, a change in the thickness of the patterned thin film was measured. The case where the film thickness after heating exceeded 95% of the film thickness before heating was rated as ○, the case where it was in the range of 90 to 95% was rated as Δ, and the case where it was less than 90% was rated as ×. Table 1 shows the results.

<Evaluation of Transparency> A glass substrate "Corning 7059 (manufactured by Corning)" instead of a silicon substrate
A glass substrate on which a patterned thin film was formed was obtained in the same manner as described above except that was used. Next, the transmittance of the obtained glass substrate was measured at a wavelength of 400 to 800 nm using a spectrophotometer “150-20 double beam (manufactured by Hitachi, Ltd.)”. At this time, the case where the minimum transmittance exceeded 95% was rated as ○, the case where it was in the range of 90 to 95% was rated as Δ, and the case where the minimum transmittance was less than 90% was rated as ×. Table 1 shows the results.

<Evaluation of Solvent Resistance> The glass substrate on which the patterned thin film was formed was immersed in dimethyl sulfoxide at 70 ° C., and the change in film thickness was measured. % When the film thickness changed by not less than%, and X when the film was largely swelled and peeled off from the substrate. Table 1 shows the results.

Examples 2 to 10 Evaluations were made in the same manner as in Example 1 except that the resin components (7) to (15) were used. The results are summarized in Table 1.

Example 11 Evaluation was performed in the same manner as in Example 1 except that 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine was used as the component (B). . The results are shown in Table 1.

Example 12 Evaluation was performed in the same manner as in Example 1 except that diphenyliodonium trifluoroacetate was used as the component (B). The results are shown in Table 1. Examples 13 to 19 Evaluations were performed in the same manner as in Example 1 except that the components (C) (2) to (8) described in Table 1 were used. The results are summarized in Table 1.

[0101]

[Table 1] However, the component (C) includes (1) tetramethoxymethyl glycoluril (trade name “CYMEL1170” manufactured by Mitsui Cymec), (2) Epicoat 807 (manufactured by Yuka Shell Epoxy Co., Ltd.), and (3) bis [(3 -Ethyl-3-oxetanylmethoxy) methyl] benzene (trade name “XD
O "manufactured by Toa Gosei Co., Ltd.), (4) phenylene-1,3-diisocyanate, (5) 1,3,5-tricyanatobenzene, (6) 1,3-bis (4,5-dihydro-2-oxazolyl) ), Benzene, (7) 1,3-bis (4,5-dihydro-2-oxazyl) benzene, and hexamethoxymethylolmelamine (trade name “CYMEL300” manufactured by Mitsui Cymec).

[0102]

The radiation-sensitive resin composition of the present invention can be developed with an alkaline aqueous solution, has high resolution and high sensitivity, and has various properties such as insulation, heat resistance, solvent resistance and transparency. It is possible to easily form a patterned thin film having excellent low dielectric properties, which has conventionally been difficult to realize simultaneously with these properties.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Masayuki Endo 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside Nippon Gosei Rubber Co., Ltd.

Claims (1)

[Claims] (A), (a-1) hexafluoropropylene, (a-2) an ethylenically unsaturated bond and the following formula (1): Here, M represents a carbon atom, a silicon atom or a germanium atom, and R ¹ , R ² and R ³ are each independently a hydrogen atom, a chain alkyl group having 1 to 10 carbon atoms, 1 to 10 carbon atoms.
A halogenated alkyl group, a cyclic alkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, or the following formula (2) -OR ⁴ (2) R ⁴ is a chain alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a 7 to 11 carbon atoms. Or an aralkyl group, or any ^{two of} R ¹ , R ² and R ³ are bonded to each other to form a 4- to 7-membered ring together with M to which they are bonded. A compound having an acid-decomposable group represented by the formula (a-3): an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride; and (a-4) the component (a-1), (a-2) ) And an unsaturated compound copolymerizable with the component (a-3). Nitrogen copolymer, (B), an acid generating compound that generates an acid upon irradiation with radiation, (C), a crosslinkable compound containing at least one crosslinkable group, and (D), the (A) A radiation-sensitive resin composition comprising an organic solvent in which the component, the component (B) and the component (C) are dissolved.