JP2002082438A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition having high transparency to radiation, excellent in basic physical properties as a resist, e.g. sensitivity, resolution and pattern shape, excellent also in shelf stability as a composition and retaining satisfactory adhesiveness to a substrate. SOLUTION: The radiation sensitive resin composition contains (A) a low molecular compound obtained by preparing a compound having one or more amino groups with at least one hydrogen atom bonding to a nitrogen atom and substituting a t-butoxycarbonyl group for one or more of such hydrogen atoms bonding to a nitrogen atom, (B) a radiation sensitive acid generating agent and (C) an alkali-insoluble or slightly alkali-soluble acid dissociable group- containing resin having an alicyclic structure in the principal chain and/or a side chain and a carboxylic acid anhydride structure in a side chain and convertible to an alkali-soluble resin when the acid dissociable group is dissociated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a radiation-sensitive resin composition useful as a resist suitable for ultrafine processing using various radiations such as ultraviolet rays, far ultraviolet rays, X-rays or charged particle beams.

[0002]

2. Description of the Related Art In the field of microfabrication represented by the manufacture of integrated circuit elements, the processing size in lithography has been reduced in order to obtain a higher degree of integration. There is a need for a technique capable of performing fine processing with good reproducibility, and it is also necessary to accurately form a resist pattern of 0.2 μm or less even in a resist used for fine processing. However, conventional visible light (wavelength 800 to 400n)
m) or a method using near-ultraviolet light (wavelength 400 to 300 nm), it is extremely difficult to form a fine pattern of sub-quarter micron level or less with high precision. The use is being studied diligently. Examples of such short-wavelength radiation include an emission line spectrum of a mercury lamp (wavelength: 254 nm) and a KrF excimer laser (wavelength: 248 nm).
m) or ArF excimer laser (wavelength 193n)
m) and the like, and charged particles such as X-rays such as synchrotron radiation and electron beams, and electron beams. Of these, lithography using an excimer laser is particularly suitable for its high output and high efficiency. For reasons such as characteristics,
Particular attention has been paid. Therefore, the resist used for lithography is also controlled by excimer laser.
It is required that a fine pattern of 2 μm or less can be formed with high sensitivity, high resolution, and good reproducibility. In addition, as a resist suitable for deep ultraviolet rays such as excimer lasers, a chemically amplified resist that uses a radiation-sensitive acid generator that generates an acid upon irradiation with radiation and improves the sensitivity of the resist by the catalytic action of the acid. Has been proposed. Examples of such a chemically amplified resist include, for example,
No. 27660 proposes a resist containing a polymer having a t-butyl ester group of a carboxylic acid or a t-butyl carbonate group of phenol and an acid generator. In this composition, the t-butyl ester group or t-butyl carbonate group present in the polymer is dissociated by the action of an acid generated by irradiation with radiation, and the polymer is dissociated from a carboxyl group or a phenolic hydroxyl group. This method utilizes a phenomenon in which an acidic group has an acidic group, and as a result, a radiation-irradiated region of the resist film becomes easily soluble in an alkali developing solution.

[0003] By the way, most conventional chemically amplified resists are based on phenolic resins.
In the case of such a resin, when far-ultraviolet rays are used as radiation, the far-ultraviolet rays are absorbed due to an aromatic ring in the resin, so that the irradiated far-ultraviolet rays cannot reach the lower layer portion of the resist film sufficiently. There is a drawback, so the radiation dose is large in the upper layer of the resist film and smaller in the lower layer, and the resist pattern after development becomes thicker and narrower toward the bottom, becoming a trapezoidal shape, and sufficient resolution can be obtained. There were problems such as not being able to. Further, when the resist pattern after development has a trapezoidal shape, a desired dimensional accuracy cannot be achieved in the next step, that is, in performing etching or ion implantation, which has been a problem. In addition, if the shape of the upper part of the resist pattern is not rectangular, the rate of disappearance of the resist by dry etching is increased, and there is a problem that it is difficult to control the etching conditions. On the other hand, the shape of the resist pattern can be improved by increasing the radiation transmittance of the resist film. For example, a (meth) acrylate resin represented by polymethyl methacrylate has high transparency even with far ultraviolet rays and is a very preferable resin from the viewpoint of radiation transmittance. A chemically amplified resist using a methacrylate resin has been proposed. However, although this resist is excellent in terms of fine processing performance, it does not have an aromatic ring, and thus has a drawback of low dry etching resistance. In this case, it is difficult to perform high-precision etching. Therefore, it cannot be said that it has both transparency to radiation and dry etching resistance.

As one of measures for improving the dry etching resistance of a chemically amplified resist without impairing the transparency to radiation, an alicyclic ring is used instead of an aromatic ring as a resin component in the resist. A method for introduction is known. For example, JP-A-7-234511 proposes a chemically amplified resist using a (meth) acrylate resin having an alicyclic ring. However,
In this resist, as the acid dissociable functional group of the resin component, a group that is relatively easily dissociated by a conventional acid (for example, an acetal-based functional group such as a tetrahydropyranyl group) or a group that is relatively hard to be dissociated by an acid (for example, , T-butyl ester groups, t-butyl carbonate groups, and other t-butyl-based functional groups). In the case of the former resin having an acid-dissociable functional group, the basic physical properties of the resist, particularly the sensitivity and pattern shape Is good, but there is a drawback in the storage stability of the composition, and in the case of the latter resin having an acid dissociable functional group, on the contrary, the storage stability is good, but the basic physical properties of the resist, especially sensitivity And that the pattern shape is impaired. Furthermore, since the resin component has an alicyclic ring, the hydrophobicity of the resin itself is extremely high, and there is a problem in terms of adhesiveness to the substrate. Furthermore, acid diffusion has the effect of controlling the diffusion phenomenon of the acid generated from the radiation-sensitive acid generator in the resist film, and suppressing undesired chemical reactions in the non-irradiated area with respect to the chemically amplified resist. By blending the control agent, the storage stability as a composition is improved, the resolution as a resist is also improved, and the fluctuation in the withdrawal time (PED) from irradiation to heating after irradiation is caused. It is known that a change in the line width of the resist pattern can be suppressed, and the process stability is also improved. However, conventional acid diffusion controlling agents have not always been able to sufficiently improve storage stability and the like. Therefore, it has high transparency to radiation represented by far ultraviolet rays, has excellent sensitivity, resolution, pattern shape, etc., has further improved storage stability as a composition, and has sufficient adhesion to a substrate. There is a strong demand for the development of radiation-sensitive resin compositions useful as chemically amplified resists.

[0005]

An object of the present invention is to provide a KrF excimer laser (wavelength: 248 nm) or A
Effectively sensitive to far ultraviolet rays typified by rF excimer laser (wavelength 193 nm), high in transparency to radiation, excellent in basic physical properties as a resist such as sensitivity, resolution and pattern shape, and storage stability as a composition An object of the present invention is to provide a radiation-sensitive composition which has excellent properties and is useful as a chemically amplified resist maintaining sufficient adhesiveness to a substrate.

[0006]

According to the present invention, the object is to provide (A) a compound comprising at least one hydrogen atom having at least one amino group bonded to a nitrogen atom, wherein the hydrogen atom bonded to the nitrogen atom is A low molecular weight compound in which at least one of the above is substituted with a t-butoxycarbonyl group, (B) a radiation-sensitive acid generator, and (C) an alicyclic structure in the main chain and / or side chain, and An alkali-insoluble or sparingly alkali-soluble resin containing an acid-dissociable group having a carboxylic acid anhydride structure in the chain, comprising a resin which becomes alkali-soluble when the acid-dissociable group is dissociated. Radiation-sensitive resin composition.

Hereinafter, the present invention will be described in detail. (A) Component The (A) component in the present invention is the above-mentioned nitrogen atom of a compound having at least one amino group in which at least one hydrogen atom is bonded to a nitrogen atom (hereinafter, referred to as “amino compound (a)”). (Hereinafter, referred to as “compound (A)”) in which at least one hydrogen atom bonded to is substituted with a t-butoxycarbonyl group. The “amino group” in the amino compound (a) includes an amino group bonded to a carbonyl group. In the compound (A), when the amino compound (a) has two or more amino groups in which at least one hydrogen atom is bonded to a nitrogen atom and has two or more t-butoxycarbonyl groups, The t-butoxycarbonyl groups can be attached to the same or different nitrogen atoms. The present inventors have conducted intensive studies on the relationship between the resin component and the acid diffusion controller for the radiation-sensitive resin composition containing the radiation-sensitive acid generator, and found that the alicyclic structure and the carboxylic anhydride structure When an acid-dissociable group-containing resin having the formula (1), a low-molecular compound in which a basic amino group is protected with an acid-dissociable t-butoxycarbonyl group is used as an acid diffusion controlling agent, so that various properties as a resist can be obtained. Has been found to be significantly improved, and the present invention has been achieved. As the amino compound (a), for example, the following general formula (4)

[0008]

Embedded image

[In the general formula (4), R ¹² and R ¹³
Each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group or an aralkyl group;
These alkyl group, aryl group and aralkyl group may be substituted respectively. (Hereinafter, referred to as "nitrogen-containing compound (a1)"), a compound having two nitrogen atoms in the same molecule (hereinafter, referred to as "nitrogen-containing compound (a2)"), and a nitrogen atom. A compound having three or more (hereinafter, referred to as "nitrogen-containing compound (a3)");
Examples include amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds.

As the nitrogen-containing compound (a1), for example,
monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and cyclohexylamine; di-n-
Butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine, etc. Dialkylamines; aniline, N-methylaniline, 2-methylaniline, 3-methylaniline,
4-methylaniline, 4-nitroaniline, diphenylamine, 1-naphthylamine, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2-
Aromatic amines such as (4-aminophenyl) -2- (4-hydroxyphenyl) propane; ethanolamine;
Alkanolamines such as diethanolamine, 1-
Adamantylamine, N-methyl-1-adamantylamine and the like can be mentioned.

As the nitrogen-containing compound (a2), for example,
Ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-
Diaminooctane, 1,9-diaminononane, 1,10
-Diaminodecane, 1,12-diaminododecane, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 2,2-bis (4-aminophenyl) propane,
-(3-aminophenyl) -2- (4-aminophenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1
-(4-aminophenyl) -1-methylethyl] benzene and the like. Examples of the nitrogen-containing compound (a3) include, for example, 4,4′-diaminodiphenylamine,
Examples thereof include polymers of polyallylamine, polymethallylamine, and N- (2-aminoethyl) acrylamide.

Examples of the amide group-containing compound include formamide, N-methylformamide, acetamide, N-methylacetamide, propionamide, benzamide, and pyrrolidone. As the urea compound, for example, urea, methyl urea,
1,1-dimethylurea, 1,3-dimethylurea,
Examples thereof include 1,3-diphenylurea and tri-n-butylthiourea. Examples of the nitrogen-containing heterocyclic compound, for example, imidazole, benzimidazole,
2-methylimidazole, 4-methylimidazole, 2
-Phenylimidazole, 4-phenylimidazole,
2-phenyl-4-methylimidazole, 2-methyl-
In addition to imidazoles such as 4-phenylimidazole, 2-methylbenzimidazole and 2-phenylbenzimidazole, indole, pyrrole, pyrazole, adenine, guanine, purine, pyrrolidine, piperidine, morpholine, piperazine and the like can be mentioned.

Of these amino compounds (a), nitrogen-containing compounds (a1), nitrogen-containing compounds (a2) and nitrogen-containing heterocyclic compounds are preferred. Further, among the nitrogen-containing compounds (a1), dialkylamines and 1-adamantylamines are more preferable, and in particular, di-n-octylamine, di-n-nonylamine, di-n-decylamine, dicyclohexylamine, -Adamantylamine, N-methyl-1-adamantylamine and the like are preferable, and among the nitrogen-containing compounds (a2), hexamethylenediamine, 1,7-
Diaminoheptane, 1,8-diaminooctane, 1,9
-Diaminononane, 1,10-diaminodecane, 1,1
2-Diaminododecane, 4,4′-diaminodiphenylmethane and the like are more preferable, and among nitrogen-containing heterocyclic compounds, imidazoles are more preferable, and benzimidazole, 2-methylimidazole, 2-phenylbenzimidazole and the like are particularly preferable. . Further, the amino compound (a) preferably has a pKa (measuring temperature 25 ° C .; the same applies hereinafter) of its conjugate acid of 0 or more. In this case, if a compound having a pKa of the conjugate acid less than 0, such as an imide compound, is used instead of the amino compound (a), the resolution and pattern shape of the obtained resist may be impaired.

Particularly preferred compound (A) in the present invention
Specifically, Nt-butoxycarbonyldi-n
-Octylamine, Nt-butoxycarbonyldi-n
-Nonylamine, Nt-butoxycarbonyldi-n-
Decylamine, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, N, N-di-t-butoxycarbonyl- 1-adamantylamine, N, N-di-tert-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4'-
Diaminodiphenylmethane, N, N'-di-t-butoxycarbonylhexamethylenediamine, N, N, N '
N'-tetra-t-butoxycarbonylhexamethylenediamine, N, N'-di-t-butoxycarbonyl-
1,7-diaminoheptane, N, N'-di-t-butoxycarbonyl-1,8-diaminooctane, N, N'-
Di-tert-butoxycarbonyl-1,9-diaminononane, N, N'-di-tert-butoxycarbonyl-1,10
-Diaminodecane, N, N'-di-t-butoxycarbonyl-1,12-diaminododecane, N, N'-di-t
-Butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole and the like. Can be. The molecular weight of the compound (A) is usually from 100 to 3,000, preferably from 200 to 2,000, particularly preferably from 250 to 1,
000.

In the present invention, the compound (A) can be used alone or as a mixture of two or more. The amount of the compound (A) used in the present invention is usually 0.001 to 15 based on 100 parts by weight of the resin (C) described below.
Parts by weight, preferably 0.005 to 10 parts by weight, more preferably 0.01 to 5 parts by weight. In this case, if the amount of the compound (A) used is less than 0.001 part by weight, the resolution and pattern shape as a resist tend to decrease,
On the other hand, if it exceeds 15 parts by weight, the sensitivity and developability of the resist tend to decrease.

Component (B) In the present invention, the component (B) may be irradiated with radiation (hereinafter referred to as “radiation”).
This is called "exposure". ), The radiation-sensitive acid generator (hereinafter, referred to as “acid generator (B)”).
The acid generator (B) dissociates an acid-dissociable group present in the resin (C) described below by the action of an acid generated by exposure, and preferably forms a carboxyl group in the resin (C), As a result, the exposed portion of the resist film becomes easily soluble in the alkali developing solution, and has an effect of forming a positive resist pattern. Examples of such an acid generator (B) include an onium salt compound, a halogen-containing compound, a diazoketone compound, a sulfone compound, and a sulfonic acid compound. Examples of these acid generators (B) include the following.

Onium salt compounds: Examples of onium salt compounds include iodonium salts, sulfonium salts (including tetrahydrothiophenium salts), phosphonium salts, diazonium salts, pyridinium salts and the like. Specific examples of preferred onium salt compounds include
Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-
n-octanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate,
Bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n -Butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 10-camphorsulfonate,
Cyclohexyl-2-oxocyclohexylmethylsulfonium trifluoromethanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium trifluoromethane Sulfonate, 4-cyano-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-1-
Naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-nitro-1
-Naphthyl diethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate,

4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4
-Hydroxy-1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate, 4-hydroxy-1-naphthyltetrahydrothiophenium perfluoro-n-octanesulfonate, 4-methoxy-1
-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxy-1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate, 4-methoxy-1-naphthyltetrahydrothiophenium perfluoro-n-octanesulfonate,
4-ethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxy-1
-Naphthyltetrahydrothiophenium nonafluoro-
n-butanesulfonate, 4-ethoxy-1-naphthyltetrahydrothiophenium perfluoro-n-octanesulfonate, 4-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-butoxy-1-naphthyl Tetrahydrothiophenium nonafluoro-n-butanesulfonate, 4
-N-butoxy-1-naphthyltetrahydrothiophenium perfluoro-n-octanesulfonate, 4-methoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxymethoxy-1-naphthyltetrahydrothiophenium nonafluoro -N-butanesulfonate, 4-methoxymethoxy-1-naphthyltetrahydrothiophenium perfluoro-n-octanesulfonate, 4-ethoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxymethoxy-1
-Naphthyltetrahydrothiophenium nonafluoro-
n-butanesulfonate, 4-ethoxymethoxy-1-
Naphthyltetrahydrothiophenium perfluoro-n
-Octane sulfonate,

4- (1-methoxyethoxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (1-methoxyethoxy) -1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate, 4- ( 1-methoxyethoxy) -1
-Naphthyltetrahydrothiophenium perfluoro-
n-octanesulfonate, 4- (2-methoxyethoxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-methoxyethoxy) -1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate, 4 -(2-methoxyethoxy) -1-naphthyltetrahydrothiophenium perfluoro-n-octanesulfonate, 4-methoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxycarbonyloxy-1-naphthyltetrahydro Thiophenium nonafluoro-n-butanesulfonate, 4-
Methoxycarbonyloxy-1-naphthyltetrahydrothiophenium perfluoro-n-octanesulfonate, 4-ethoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxycarbonyloxy-1-naphthyltetrahydrothiophenium nona Fluoro-n-butanesulfonate, 4-ethoxycarbonyloxy-1-naphthyltetrahydrothiophenium perfluoro-n-octanesulfonate, 4-n-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n -Propoxycarbonyloxy-1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate, 4-n-propoxycarbonyloxy Shi-1-naphthyl tetrahydrothiophenium perfluoro -n- octane sulfonate,
4-i-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-i-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate, 4-i-propoxycarbonyloxy- 1-naphthyltetrahydrothiophenium perfluoro-n-octanesulfonate,

4-n-butoxycarbonyloxy-1-
Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-butoxycarbonyloxy-
1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate, 4-n-butoxycarbonyloxy-1-naphthyltetrahydrothiophenium perfluoro-n-octanesulfonate, 4-t-butoxycarbonyloxy-1-naphthyltetrahydro Thiophenium trifluoromethanesulfonate, 4-t-
Butoxycarbonyloxy-1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate, 4-tert-butoxycarbonyloxy-1-naphthyltetrahydrothiophenium perfluoro-n-octanesulfonate, 4- (2-tetrahydrofuranyloxy ) -1-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-tetrahydrofuranyloxy) -1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate, 4- (2
-Tetrahydrofuranyloxy) -1-naphthyltetrahydrothiophenium perfluoro-n-octanesulfonate, 4- (2-tetrahydropyranyloxy)-
1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-tetrahydropyranyloxy) -1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate, 4- (2-tetrahydropyranyloxy) -1- Naphthyltetrahydrothiophenium perfluoro-n-octanesulfonate, 4-benzyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-benzyloxy-1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate, -Benzyloxy-1-naphthyltetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (1-naphthylacetomethyl) tetrahydrothiophenium trifluoromethanes Honeto, 1- (1-naphthyl acetamide methyl) tetrahydrothiophenium nonafluoro -
n-butanesulfonate, 1- (1-naphthylacetomethyl) tetrahydrothiophenium perfluoro-n-
Octanesulfonate, 1- (3,5-dimethyl-4-
(Hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (3
5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate.

Halogen-containing compound: Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound. Specific examples of preferred halogen-containing compounds include phenylbis (trichloromethyl) -s-triazine and 4-methoxyphenylbis (trichloromethyl)-
(Trichloromethyl) -s- such as s-triazine and 1-naphthylbis (trichloromethyl) -s-triazine
Examples thereof include a triazine derivative and 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane. Diazoketone compound: Examples of the diazoketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, and a diazonaphthoquinone compound. Specific examples of preferred diazoketones include 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 1,2-naphtho of 2,3,4,4'-tetrahydroxybenzophenone. Quinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-
5-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester of 1,1,1-tris (4-hydroxyphenyl) ethane, 1,2-naphthoquinonediazide-5-sulfonic acid ester, and the like. Can be.

Sulfone compound: Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds of these compounds. Specific examples of preferable sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenylsulfonyl) methane. Sulfonic acid compound: Examples of the sulfonic acid compound include an alkylsulfonic acid ester, an alkylsulfonic acid imide, a haloalkylsulfonic acid ester, an arylsulfonic acid ester, and an iminosulfonate. Specific examples of preferred sulfonic acid compounds include benzoin tosylate, tris (trifluoromethanesulfonate) of pyrogallol, nitrobenzyl-
9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2.2.
1] Hept-5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo [2.2.
1] Hept-5-ene-2,3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide nonafluoro-n-butanesulfonate, N-hydroxysuccinimide perfluoro- n-octanesulfonate, 1,8-
Examples include naphthalenedicarboxylic acid imide trifluoromethanesulfonate.

Among these acid generators (B), diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-
n-octanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate,
Bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n -Butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, cyclohexyl-2-oxocyclohexylmethylsulfonium trifluoromethanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, 4
-Hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate,

4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
-Hydroxy-1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate, 4-hydroxy-1-naphthyltetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (1-naphthylacetomethyl) tetrahydrothiophenium Trifluoromethanesulfonate, 1- (1-naphthylacetomethyl) tetrahydrothiophenium nonafluoro-n-
Butanesulfonate, 1- (1-naphthylacetomethyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3 , 5-dimethyl-
4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (3,5
-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate,

Trifluoromethanesulfonylbicyclo [
2.2.1] Hept-5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo [
2.2.1] Hept-5-ene-2,3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo
[2.2.1] Hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide nonafluoro-n-butanesulfonate, N-hydroxysuccinimide Perfluoro-n-octanesulfonate, 1,
8-Naphthalenedicarboxylic acid imide trifluoromethanesulfonate and the like are preferred.

In the present invention, the acid generator (B) can be used alone or in combination of two or more. The amount of the acid generator (B) used in the present invention is usually 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 100 parts by weight of the resin (C) described below. 0.5 to 7 parts by weight. In this case, if the amount of the acid generator (B) used is less than 0.1 part by weight, the sensitivity and resolution as a resist tend to decrease, while if it exceeds 15 parts by weight, the applicability as a resist and the pattern shape are reduced. Tends to decrease.

Component (C) In the present invention, the component (C) has an alicyclic structure in the main chain and / or the side chain, and has a carboxylic acid anhydride structure in the side chain. It is a resin containing an acid-dissociable group, which is alkali-soluble when the acid-dissociable group is dissociated (hereinafter, referred to as “resin (C)”). Examples of the alicyclic structure in the resin (C) include an alicyclic structure having a bridged skeleton such as an adamantane skeleton, a norbornane skeleton, a tricyclodecane skeleton, and a tetracyclododecane skeleton, having 4 to 20 carbon atoms; cyclobutane; Examples thereof include alicyclic structures having 4 to 20 carbon atoms derived from cycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane. Among these alicyclic structures, an alicyclic structure having a bridged skeleton is preferable, and in particular, an alicyclic structure having a skeleton selected from the group consisting of an adamantane skeleton, a norbornane skeleton, a tricyclodecane skeleton and a tetracyclododecane skeleton. The structure is preferred. The “carboxylic anhydride structure” in the resin (C) refers to “—CO—O—CO— formed by removing one molecule of water from two carboxyl groups.
"The structure" means that the structure may be directly bonded to a carbon atom constituting the main chain of the resin (C), or may be bonded via an appropriate organic group. Further, even if the carboxylic acid anhydride structure is present only in the alicyclic structure portion in the resin (C),
It may be present only in the other structural parts, or may be present simultaneously in both of these structural parts. The resin (C) in the present invention is not particularly limited as long as it satisfies the above-mentioned requirements, and may have any polymerization form such as an addition polymerization resin, a polycondensation resin, a polyaddition resin, and a ring-opening polymerization resin. However, it is preferably an addition polymerization resin. As the resin (C) in the present invention, from the viewpoint of transparency to radiation, a resin having no aromatic ring or containing as little aromatic ring as possible is preferable.

Preferred examples of the resin (C) according to the present invention include an alkali-insoluble or alkali-soluble acid-dissociable group-containing resin having a repeating unit (I) and a repeating unit (II) represented by the following general formula (1). A resin which becomes alkali-soluble when the acid-dissociable group is dissociated (hereinafter, referred to as “resin (C1)”);

[0029]

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[In the general formula (1), R ¹ and R ² independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a linear or branched alkyl group having 1 to 10 carbon atoms. R ³ and R ⁴ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, A fluorinated alkyl group, a monovalent oxygen atom-containing polar group or a monovalent nitrogen atom-containing polar group,
Alternatively, R ³ and R ⁴ together form a carboxylic anhydride group, and n is an integer of 0 to 2. ];

The repeating unit (I) and the repeating unit (II) represented by the general formula (1), and the repeating unit (III) represented by the following general formula (2) and / or the repeating unit represented by the following general formula (3) (IV) a resin containing an alkali-insoluble or sparingly-soluble acid-dissociable group, which becomes alkali-soluble when the acid-dissociable group is dissociated (hereinafter referred to as “resin (C2)”);

[0032]

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[In the general formula (2), R ⁵ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxyl group having 1 to 4 carbon atoms or a carbon atom. A represents a linear or branched hydroxyalkyl group of Formulas 1 to 4, A represents a single bond, a methylene group or a linear or branched alkylene group having 2 to 4 main chain carbon atoms, and R ⁶ represents Formula (i) (where R ⁷ represents a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, and X ¹ represents a monovalent oxygen-containing polar group or a monovalent nitrogen-containing polar group) Wherein R ⁸ represents a trivalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, and X ² represents a divalent oxygen-containing polar group or a divalent nitrogen-containing polar group. ) Or the formula (ii
i) (provided that R ⁹ represents a tetravalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, and X ³ represents a trivalent oxygen-containing polar group or a trivalent nitrogen-containing polar group)

[0034]

Embedded image Represents a group represented by ]

[0035]

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[In the general formula (3), R ¹⁰ represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxyl group having 1 to 4 carbon atoms or a carbon atom. A linear or branched hydroxyalkyl group of the formulas 1 to 4; each R ¹¹ independently of each other, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, And at least one of R ¹¹ is the alicyclic hydrocarbon group or a derivative thereof, or any two R ¹¹ are bonded to each other to form together bonded to that carbon atom to form a divalent alicyclic hydrocarbon group or a derivative thereof having 4 to 20 carbon atoms, the remaining R ¹¹ are carbon atoms 4-2
0 represents a monovalent alicyclic hydrocarbon group or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms. And the like.

Hereinafter, these preferred resins (C) will be described. In the repeating unit (I) of the resin (C1) and the resin (C2), as the linear or branched alkyl group having 1 to 10 carbon atoms of R ¹ , R ² , R ³ and R ⁴ , for example, methyl Group, ethyl group, n-propyl group,
i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, Examples thereof include a 2-ethylhexyl group, an n-nonyl group, and an n-decyl group. Among these alkyl groups, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group and the like are preferable.

The linear or branched fluorinated alkyl group having 1 to 10 carbon atoms for R ¹ , R ² , R ³ and R ⁴ includes, for example, fluoromethyl group, difluoromethyl group, trifluoromethyl Group, 1-fluoroethyl group, 1,1-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 1-fluoro-n-propyl group, 1,1-difluoro-n-propyl Group, 3,3,3-trifluoro-n-propyl group,
3,3,3,2,2-pentafluoro-n-propyl group, perfluoro-n-propyl group, 1-fluoro-i
-Propyl group, 2-trifluoro-i-propyl group, perfluoro-i-propyl group, 1-fluoro-n-butyl group, 1,1-difluoro-n-butyl group, 4,4,4
-Trifluoro-n-butyl group, 4,4,4,3,3-
Pentafluoro-n-butyl group, 4,4,4,3,3
2,2-heptafluoro-n-butyl group, perfluoro-n-butyl group, 2-fluoro-2-methylpropyl group, 1-fluoro-1-methylpropyl group, 1-fluoro-n-pentyl group, 1 , 1-Difluoro-n-pentyl group, 5,5,5-trifluoro-n-pentyl group, 1
-Fluoro-n-hexyl group, 1,1-difluoro-n
-Hexyl group, 6,6,6-trifluoro-n-hexyl group, 1-fluoro-n-heptyl group, 1,1-difluoro-n-heptyl group, 7,7,7-trifluoro-n
-Heptyl group, 1-fluoro-n-octyl group, 1,1
-Difluoro-n-octyl group, 8,8,8-trifluoro-n-octyl group, 2-fluoro-2-ethylhexyl group, 1-fluoro-n-nonyl group, 1,1-difluoro-n-nonyl group , 9,9,9-trifluoro-n-
Examples include a nonyl group, a 1-fluoro-n-decyl group, a 1,1-difluoro-n-decyl group, a 10,10,10-trifluoro-n-decyl group, and the like. Among these fluorinated alkyl groups, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 1,1-difluoroethyl group, 2,2,2-trifluoroethyl group, 1-
A fluoro-i-propyl group and the like are preferred.

The monovalent oxygen atom-containing polar groups represented by R ³ and R ⁴ include, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i
-Propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n
-Pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-decyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, 4-t-butylcyclohexyl 1 carbon atom such as an oxycarbonyl group, a cycloheptyloxycarbonyl group, a cyclooctyloxycarbonyl group, etc.
Straight-chain, branched or cyclic alkoxycarbonyl group having 1 to 11 carbon atoms; aryloxycarbonyl group having 7 to 11 carbon atoms such as phenoxycarbonyl group, 4-t-butylphenoxycarbonyl group, 1-naphthyloxycarbonyl group; benzyloxy Carbonyl group, 4-t-butylbenzyloxycarbonyl group, phenethyloxycarbonyl group, 4
An aralkyloxycarbonyl group having 8 to 12 carbon atoms, such as -t-butylphenethyloxycarbonyl group;

1-methoxyethoxycarbonyl group, 1-
Ethoxyethoxycarbonyl group, 1-n-propoxyethoxycarbonyl group, 1-i-propoxyethoxycarbonyl group, 1-n-butoxyethoxycarbonyl group, 1
-(2-methylpropoxy) ethoxycarbonyl group, 1
-(1-methylpropoxy) ethoxycarbonyl group, 1
Linear, branched or cyclic 1-alkyl having 4 to 13 carbon atoms, such as -t-butoxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 1- (4-t-butylcyclohexyloxy) ethoxycarbonyl group, etc. Oxyethoxycarbonyl group; 1-phenoxyethoxycarbonyl group, 1- (4-t-butylphenoxy)
1-aryloxyethoxycarbonyl group having 9 to 13 carbon atoms, such as ethoxycarbonyl group and 1- (1-naphthyloxy) ethoxycarbonyl group; 1-benzyloxyethoxycarbonyl group, 1- (4-t-butylbenzyloxy) C10-14 carbon atoms such as an ethoxycarbonyl group, a 1-phenethyloxyethoxycarbonyl group and a 1- (4-t-butylphenethyloxy) ethoxycarbonyl group;
An aralkyloxyethoxycarbonyl group;

Methoxycarbonylmethoxycarbonyl, ethoxycarbonylmethoxycarbonyl, n-propoxycarbonylmethoxycarbonyl, i-propoxycarbonylmethoxycarbonyl, n-butoxycarbonylmethoxycarbonyl, 2-methylpropoxycarbonylmethoxycarbonyl, 1- A linear, branched or cyclic group having 4 to 14 carbon atoms such as a methylpropoxycarbonylmethoxycarbonyl group, a t-butoxycarbonylmethoxycarbonyl group, a cyclohexyloxycarbonylmethoxycarbonyl group, and a 4-t-butylcyclohexyloxycarbonylmethoxycarbonyl group. Alkoxycarbonylmethoxycarbonyl group; methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl Group, i- propoxycarbonyl methyl group, n- butoxycarbonyl methyl group, 2-methyl propoxycarbonyl methyl group, 1-methyl propoxycarbonyl methyl group, t-butoxycarbonyl methyl group, cyclohexyloxy carbonyl methyl group, 4-t
Linear, branched or cyclic alkoxycarbonylmethyl group having 3 to 12 carbon atoms such as -butylcyclohexyloxycarbonylmethyl group; phenoxycarbonylmethyl group, 4-t-butylphenoxycarbonylmethyl group, 1
8 to 1 carbon atoms such as a naphthyloxycarbonylmethyl group
Aralkyl having 9 to 18 carbon atoms such as a benzyloxycarbonylmethyl group, a 4-t-butylbenzyloxycarbonylmethyl group, a phenethyloxycarbonylmethyl group, a 4-t-butylphenethyloxycarbonylmethyl group; An oxycarbonylmethyl group;

2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl, 2-i-propoxycarbonylethyl, 2-n-butoxycarbonylethyl, 2- (2-
Methylpropoxy) carbonylethyl group, 2- (1-methylpropoxy) carbonylethyl group, 2-t-butoxycarbonylethyl group, 2-cyclohexyloxycarbonylethyl group, 2- (4-t-butylcyclohexyloxycarbonyl) ethyl group Linear, branched or cyclic 2-alkoxycarbonylethyl group having 4 to 14 carbon atoms; 2-phenoxycarbonylethyl group, 2- (4
-T-butylphenoxycarbonyl) ethyl group, 2-
2-aryloxycarbonylethyl group having 9 to 17 carbon atoms such as (1-naphthyloxycarbonyl) ethyl group;
A carbon number of 10 such as a benzyloxycarbonylethyl group, a 2- (4-t-butylbenzyloxycarbonyl) ethyl group, a 2-phenethyloxycarbonylethyl group, a 2- (4-t-butylphenethyloxycarbonyl) ethyl group;
To 19 to 2-aralkyloxycarbonylethyl group; tetrahydrofuranyloxycarbonyl group, tetrahydropyranyloxycarbonyl group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n- C2-C9 linear such as butoxycarbonyloxy group, cyclohexyloxycarbonyloxy group,
A branched or cyclic alkoxycarbonyloxy group;
Methoxycarbonyloxymethyl group, ethoxycarbonyloxymethyl group, n-propoxycarbonyloxymethyl group, i-propoxycarbonyloxymethyl group, n
An acid dissociable group such as a linear, branched or cyclic C 3-10 alkoxycarbonyloxyalkyl group such as a -butoxycarbonyloxymethyl group or a cyclohexyloxycarbonyloxymethyl group (hereinafter referred to as “acid dissociable group ( B)).

Hydroxyl group; carboxyl group; hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2 A straight-chain, branched or cyclic hydroxyalkyl group having 1 to 8 carbon atoms such as -hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, 3-hydroxycyclopentyl group, 4-hydroxycyclohexyl group; methoxy Group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, cyclopentyloxy group, cyclohexyloxy group, etc. 8 linear, branched or cyclic alkoxyl groups; Kishimechiru group, ethoxymethyl group,
n-propoxymethyl group, i-propoxymethyl group, n
A linear, branched or cyclic alkoxyalkyl group having 2 to 10 carbon atoms, such as -butoxymethyl group, t-butoxymethyl group, cyclopentyloxymethyl group, cyclohexyloxymethyl group; 1-methoxyethoxy group, 1-ethoxy Ethoxy group, 1-n-propoxyethoxy group, 1
-N-butoxyethoxy group, 1-cyclopentyloxyethoxy group, 1-cyclohexyloxyethoxy group, 1
Linear, branched or cyclic 1-C2-C10 groups such as -methoxypropoxy and 1-ethoxypropoxy;
Alkoxyalkoxyl group;

A (1-methoxyethoxy) methyl group, (1
-Ethoxyethoxy) methyl group, (1-n-propoxyethoxy) methyl group, (1-n-butoxyethoxy) methyl group, (1-cyclopentyloxyethoxy) methyl group, (1-cyclohexyloxyethoxy) methyl group,
A linear, branched or cyclic (1-alkoxyalkoxy) alkyl group having 3 to 11 carbon atoms such as a (1-methoxypropoxy) methyl group and a (1-ethoxypropoxy) methyl group; a tetrahydrofuranyloxy group, a tetrahydropyrani A luoxy group, a tetrahydrofuranyloxymethyl group, a tetrahydropyranyloxymethyl group; a group represented by the following general formula (5) (hereinafter, referred to as an “oxygen atom-containing polar group (5)”)

[0045]

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[In the general formula (5), R ¹⁴ represents a hydrogen atom, a monovalent acid dissociable group (hereinafter referred to as “acid dissociable group (b)”), and a carbon number having no acid dissociable group. 1-6 straight, branched or cyclic alkyl group or an acid-dissociable group to have no carbon number 2-7 linear, branched or cyclic alkyl group, R ¹⁵ is the number of carbon atoms 1 to 10
A linear or branched alkyl group (excluding the group contained in the acid-dissociable group (b)) or a carbon number of 1 to 10
Represents a linear or branched fluorinated alkyl group of
m is an integer of 0 to 3. And the like.

As the acid dissociating property (a), a group which dissociates with an acid to form a carboxyl group in the repeating unit (I) is preferable, and more preferably a group -COOR '[wherein
R 'represents a linear, branched or cyclic alkyl group having 1 to 19 carbon atoms. Or a group —COOCH ₂ COO
R "[where R" represents a linear, branched or cyclic alkyl group having 1 to 17 carbon atoms. And particularly preferably a 1-methylpropoxycarbonyl group, a t-butoxycarbonyl group, a t-butoxycarbonylmethoxycarbonyl group and the like.

In the oxygen-containing polar group (5), R ¹⁴
Examples of the acid dissociable group (b) include a tertiary alkyl group, a group forming an acetal group together with an oxygen atom in the oxygen atom-containing polar group (5) (hereinafter, referred to as an “acetal forming group”), and substitution. Methyl group, 1-substituted ethyl group, 1-substituted propyl group, 1-branched alkyl group (excluding tertiary alkyl group), silyl group, germyl group, alkoxycarbonyl group, acyl group, cyclic acid dissociation And the like.

In the acid dissociable group (b), examples of the tertiary alkyl group include t-butyl, 1,1-dimethylpropyl, 1-methyl-1-ethylpropyl,
1-dimethylbutyl group, 1-methyl-1-ethylbutyl group, 1,1-dimethylpentyl group, 1-methyl-1-ethylpentyl group, 1,1-dimethylhexyl group, 1,1
-Dimethylheptyl group, 1,1-dimethyloctyl group and the like. Examples of the acetal-forming group include, for example, methoxymethyl group, ethoxymethyl group, n
-Propoxymethyl group, i-propoxymethyl group, n-
Butoxymethyl group, t-butoxymethyl group, n-pentyloxymethyl group, n-hexyloxymethyl group, cyclopentyloxymethyl group, cyclohexyloxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group,
1-n-propoxyethyl group, 1-i-propoxyethyl group, 1-n-butoxyethyl group, 1-t-butoxyethyl group, 1-n-pentyloxyethyl group, 1-n-hexyloxyethyl group, 1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, (cyclohexyl) (methoxy) methyl group, (cyclohexyl) (ethoxy) methyl group, (cyclohexyl) (n-propoxy)
A methyl group, a (cyclohexyl) (i-propoxy) methyl group, a (cyclohexyl) (cyclohexyloxy) methyl group, a 1-methoxypropyl group, a 1-ethoxypropyl group, a 1-benzyloxyethyl group, a 1-phenoxyethyl group, and the like. Can be mentioned.

Examples of the substituted methyl group include methoxyethoxymethyl, phenacyl, bromophenacyl, methoxyphenacyl, methylthiophenacyl, α-methylphenacyl, cyclopropylmethyl, benzyl, diphenyl Methyl group, triphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl group, methylthiobenzyl group, ethoxybenzyl group, ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n
-Propoxycarbonylmethyl group, i-propoxycarbonylmethyl group, n-butoxycarbonylmethyl group, t
-Butoxycarbonylmethyl group and the like. Examples of the 1-substituted ethyl group include 1,1
-Diphenoxyethyl group, 1-cyclopropylethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group, 1-i-propoxycarbonylethyl group, 1-n
-Butoxycarbonylethyl group, 1-t-butoxycarbonylethyl group and the like.

Examples of the 1-branched alkyl group include i-propyl, sec-butyl, 1-methylbutyl and the like. Examples of the silyl group include, for example, a trimethylsilyl group, an ethyldimethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group,
i-propyldimethylsilyl group, methyldi-i-propylsilyl group, tri-i-propylsilyl group, t-butyldimethylsilyl group, methyldi-t-butylsilyl group, tri-t-butylsilyl group, phenyldimethylsilyl group,
Examples thereof include a methyldiphenylsilyl group and a triphenylsilyl group. Examples of the germyl group include a trimethylgermyl group, an ethyldimethylgermyl group, a methyldiethylgermyl group, a triethylgermyl group, an i-propyldimethylgermyl group, and a methyldi-i- group.
Propylgermyl group, tri-i-propylgermyl group,
Examples thereof include a t-butyldimethylgermyl group, a methyldi-t-butylgermyl group, a tri-t-butylgermyl group, a phenyldimethylgermyl group, a methyldiphenylgermyl group, and a triphenylgermyl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an i-propoxycarbonyl group, a t-butoxycarbonyl group, and the like.

As the acyl group, for example, an acetyl group, a propionyl group, a butyryl group, a heptanoyl group,
Hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauryloyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoil group , Acryloyl group, propioyl group, methacryloyl group,
Crotonoyl, oleoyl, maleoyl, fumaroyl, mesaconoyl, camphoroyl, benzoyl, phthaloyl, isophthaloyl, terephthaloyl, naphthoyl, toluoyl, hydroatropoyl, atropoyl, cinnamoyl, floyl Group, thenoyl group, nicotinoyl group, isonicotinoyl group, p-
Examples thereof include a toluenesulfonyl group and a mesyl group. Further, examples of the cyclic acid dissociable group include a 3-oxocyclohexyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, a tetrahydrothiofuranyl group, a 3-bromotetrahydropyranyl group, and a 4-bromotetrahydropyranyl group. Methoxytetrahydropyranyl group, 2-
Oxo-4-methyl-4-tetrahydropyranyl group, 4
-Methoxytetrahydrothiopyranyl group, 3-tetrahydrothiophen-1,1-dioxide group and the like.

Of these acid dissociable groups (b), t-butyl, 1-methoxyethoxy, 1-ethoxyethoxy, 1-cyclohexyloxyethoxy, methoxymethyl, t-butoxycarbonylmethyl, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1
-Ethoxypropyl, trimethylsilyl, t-butoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl and the like are preferred.

The alkyl group having 1 to 6 carbon atoms which does not have an acid dissociable group for R ¹⁴ can be linear, branched or cyclic, and examples thereof include a methyl group and an ethyl group. , N-propyl group, n-butyl group, i-butyl group, n
-Pentyl, n-hexyl, cyclopentyl, cyclohexyl and the like. Among these alkyl groups, a methyl group, an ethyl group, an n-propyl group, a cyclohexyl group and the like are particularly preferable.

The C 2-7 alkylcarbonyl group having no acid-dissociable group of R ¹⁴ can be linear, branched or cyclic, and examples thereof include a methylcarbonyl group, Ethylcarbonyl group, n-propylcarbonyl group, n-butylcarbonyl group, i-butylcarbonyl group, n-pentylcarbonyl group, i-pentylcarbonyl group, n-hexylcarbonyl group, i-hexylcarbonyl group, cyclohexylcarbonyl group, etc. Can be mentioned. Among these alkylcarbonyl groups, a methylcarbonyl group, an ethylcarbonyl group and the like are particularly preferable.

R ¹⁴ in the oxygen atom-containing polar group (5) is particularly preferably a hydrogen atom, the preferred acid dissociable group (b), a methyl group, an ethyl group, a methylcarbonyl group, an ethylcarbonyl group and the like.

Next, examples of the linear or branched alkyl group having 1 to 10 carbon atoms for R ¹⁵ include a methyl group,
Ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group , N-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like. Among these alkyl groups, a methyl group, an ethyl group, an n-propyl group, an n-hexyl group and the like are preferable.

The linear or branched fluorinated alkyl group having 1 to 10 carbon atoms for R ¹⁵ includes, for example, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 1-fluoroethyl group, , 1-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 1-fluoro-n-propyl group, 1,
1-difluoro-n-propyl group, 3,3,3-trifluoro-n-propyl group, 3,3,3,2,2-pentafluoro-n-propyl group, perfluoro-n-propyl group, 1 -Fluoro-i-propyl group, 2-trifluoro-i-propyl group, perfluoro-i-propyl group,
1-fluoro-n-butyl group, 1,1-difluoro-n
-Butyl group, 4,4,4-trifluoro-n-butyl group, 4,4,4,3,3-pentafluoro-n-butyl group, 4,4,4,3,3,2,2- Heptafluoro-n
-Butyl group, perfluoro-n-butyl group, 2-fluoro-2-methylpropyl group, 1-fluoro-1-methylpropyl group, 1-fluoro-n-pentyl group, 1,1-
Difluoro-n-pentyl group, 5,5,5-trifluoro-n-pentyl group, 1-fluoro-n-hexyl group,
1,1-difluoro-n-hexyl group, 6,6,6-trifluoro-n-hexyl group, 1-fluoro-n-heptyl group, 1,1-difluoro-n-heptyl group, 7,
7,7-trifluoro-n-heptyl group, 1-fluoro-n-octyl group, 1,1-difluoro-n-octyl group, 8,8,8-trifluoro-n-octyl group, 2-
Fluoro-2-ethylhexyl group, 1-fluoro-n-
Nonyl group, 1,1-difluoro-n-nonyl group, 9,
9,9-trifluoro-n-nonyl group, 1-fluoro-
n-decyl group, 1,1-difluoro-n-decyl group, 1
0,10,10-trifluoro-n-decyl group and the like can be mentioned. Of these fluorinated alkyl groups,
Fluoromethyl group, difluoromethyl group, trifluoromethyl group, 1,1-difluoroethyl group, 2,2,2-
A trifluoroethyl group, a 1-fluoro-1-methylethyl group and the like are preferable.

R ¹⁵ in the oxygen atom-containing polar group (5) is particularly preferably a hydrogen atom, a methyl group, a trifluoromethyl group or the like. Further, m in the oxygen atom-containing polar group (5) is preferably 0 or 1. N in the repeating unit (I) is preferably 0 or 1.

Examples of the monomer that gives the repeating unit (I) include a compound represented by the following general formula (6) (hereinafter, referred to as “norbornene derivative (I)”).

[0061]

Embedded image [In the general formula (6), R ¹ , R ² , R ³ , R ⁴ and n represent R ¹ , R ² ,
It is synonymous with R ³ , R ⁴ and n. ]

Examples of the norbornene derivative (I) include norbornene (that is, bicyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2.1] hept-2-ene, -Ethylbicyclo [2.2.1] hept-2-ene, 5-fluoromethylbicyclo [2.
2.1] Hept-2-ene, 5-difluoromethylbicyclo [2.2.1] hept-2-ene, 5-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5
-Methyl-5-trifluoromethylbicyclo [2.2.
1] hept-2-ene, 5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5
6-bis (trifluoromethyl) bicyclo [2.2.1
] Hept-2-ene, 5,5,6-tris (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5-methoxycarbonylbicyclo [2.
2.1] Hept-2-ene, 5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-n-propoxycarbonylbicyclo [2.2.1] hept-2-
Ene, 5-i-propoxycarbonylbicyclo [2.
2.1] Hept-2-ene, 5-n-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5- (2
-Methylpropoxy) carbonylbicyclo [2.2.1
] Hept-2-ene, 5- (1-methylpropoxy) carbonylbicyclo [2.2.1] hept-2-ene, 5
-T-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5- (4-t
-Butylcyclohexyloxy) carbonylbicyclo [
2.2.1] Hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-
(1-ethoxyethoxy) carbonylbicyclo [2.
2.1] Hept-2-ene, 5- (1-cyclohexyloxyethoxy) carbonylbicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylmethoxycarbonylbicyclo [2.2.1] Hept-2-ene,
5-tetrahydrofuranyloxycarbonylbicyclo [
2.2.1] Hept-2-ene, 5-tetrahydropyranyloxycarbonylbicyclo [2.2.1] hept-
2-ene,

5-methoxycarbonyloxybicyclo [
2.2.1] hept-2-ene, 5-ethoxycarbonyloxybicyclo [2.2.1] hept-2-ene, 5
-N-propoxycarbonyloxybicyclo [2.2.
1] Hept-2-ene, 5-n-butoxycarbonyloxybicyclo [2.2.1] hept-2-ene, 5-methoxycarbonyloxymethylbicyclo [2.2.1]
Hept-2-ene, 5-ethoxycarbonyloxymethylbicyclo [2.2.1] hept-2-ene, 5-n-
Propoxycarbonyloxymethylbicyclo [2.2.
1] hept-2-ene, 5-n-butoxycarbonyloxymethylbicyclo [2.2.1] hept-2-ene,

5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5
-Ethoxycarbonylbicyclo [2.2.1] hept-
2-ene, 5-methyl-5-n-propoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-i-propoxycarbonylbicyclo [2.2.1]
] Hept-2-ene, 5-methyl-5-n-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5
-Methyl-5- (2-methylpropoxy) carbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-
5- (1-methylpropoxy) carbonylbicyclo [
2.2.1] Hept-2-ene, 5-methyl-5-t-
Butoxycarbonylbicyclo [2.2.1] hept-2
-Ene, 5-methyl-5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5- (4-t-butylcyclohexyloxy) carbonylbicyclo [2.2.1] Hept-2-ene, 5
-Methyl-5-phenoxycarbonylbicyclo [2.
2.1] Hept-2-ene, 5-methyl-5- (1-ethoxyethoxy) carbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5- (1-cyclohexyloxyethoxy) Carbonylbicyclo [2.2.1]
Hept-2-ene, 5-methyl-5-t-butoxycarbonylmethoxycarbonylbicyclo [2.2.1] Hept-2-ene, 5-methyl-5-tetrahydrofuranyloxycarbonylbicyclo [2.2.1] Hept-2-
Ene, 5-methyl-5-tetrahydropyranyloxycarbonylbicyclo [2.2.1] hept-2-ene,

5-methyl-5-methoxycarbonyloxybicyclo [2.2.1] hept-2-ene, 5-methyl-5-ethoxycarbonyloxybicyclo [2.2.
1] Hept-2-ene, 5-methyl-5-n-propoxycarbonyloxybicyclo [2.2.1] hept-2
-Ene, 5-methyl-5-n-butoxycarbonyloxybicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonyloxymethylbicyclo [
2.2.1] Hept-2-ene, 5-methyl-5-ethoxycarbonyloxymethylbicyclo [2.2.1] Hept-2-ene, 5-methyl-5-n-propoxycarbonyloxymethylbicyclo [ 2.2.1] Hept-2
-Ene, 5-methyl-5-n-butoxycarbonyloxymethylbicyclo [2.2.1] hept-2-ene,

5,6-di (methoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (ethoxycarbonyl) bicyclo [2.2.1] hept-2-
Ene, 5,6-di (n-propoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (i-
Propoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (n-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2- 1. methylpropoxycarbonyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-di (1-methylpropoxycarbonyl) bicyclo [2.2.1] hept-
2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1]
] Hept-2-ene, 5,6-di (4-t-butylcyclohexyloxycarbonyl) bicyclo [2.2.1]
Hept-2-ene, 5,6-di (phenoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6
-Di (1-ethoxyethoxycarbonyl) bicyclo [
2.2.1] Hept-2-ene, 5,6-di (1-cyclohexyloxyethoxycarbonyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-di (t-butoxycarbonylmethoxycarbonyl) bicyclo [2.2.1
] Hept-2-ene, 5,6-di (tetrahydrofuranyloxycarbonyl) bicyclo [2.2.1] hept-
2-ene, 5,6-di (tetrahydropyranyloxycarbonyl) bicyclo [2.2.1] hept-2-ene,

5,6-dimethoxycarbonyloxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxycarbonyloxybicyclo [2.2.1] hept-
2-ene, 5,6-di-n-propoxycarbonyloxybicyclo [2.2.1] hept-2-ene, 5,6-
Di-n-butoxycarbonyloxybicyclo [2.2.
1] Hept-2-ene, 5,6-di (methoxycarbonyloxymethyl) bicyclo [2.2.1] hept-2-
Ene, 5,6-di (ethoxycarbonyloxymethyl)
Bicyclo [2.2.1] hept-2-ene, 5,6-di (n-propoxycarbonyloxymethyl) bicyclo [
2.2.1] Hept-2-ene, 5,6-di (n-butoxycarbonyloxymethyl) bicyclo [2.2.1]
Hept-2-ene,

5-Hydroxybicyclo [2.2.1] hept-2-ene, 5-carboxybicyclo [2.2.1]
] Hept-2-ene, 5-hydroxymethylbicyclo
[2.2.1] hept-2-ene, 5- (2-hydroxyethyl) bicyclo [2.2.1] hept-2-ene,
5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene
Ene, 5- (1-methoxyethoxy) bicyclo [2.
2.1] Hept-2-ene, 5- (1-ethoxyethoxy) bicyclo [2.2.1] hept-2-ene, 5-
(1-n-propoxyethoxy) bicyclo [2.2.1
] Hept-2-ene, 5- (1-n-butoxyethoxy) bicyclo [2.2.1] hept-2-ene, 5-
(1-cyclohexyloxyethoxy) bicyclo [2.
2.1] Hept-2-ene, 5- (1-methoxyethoxy) methylbicyclo [2.2.1] hept-2-ene,
5- (1-ethoxyethoxy) methylbicyclo [2.
2.1] Hept-2-ene, 5- (1-n-propoxyethoxy) methylbicyclo [2.2.1] hept-2-
Ene, 5- (1-n-butoxyethoxy) methylbicyclo [2.2.1] hept-2-ene, 5- (1-cyclohexyloxyethoxy) methylbicyclo [2.2.1]
] Hept-2-ene, 5-tetrahydrofuranyloxybicyclo [2.2.1] hept-2-ene, 5-tetrahydropyranyloxybicyclo [2.2.1] hept-
2-ene, 5-tetrahydrofuranyloxymethylbicyclo [2.2.1] hept-2-ene, 5-tetrahydropyranyloxymethylbicyclo [2.2.1] hept-2-ene,

5-methyl-5-hydroxybicyclo [
2.2.1] hept-2-ene, 5-methyl-5-carboxybicyclo [2.2.1] hept-2-ene, 5-
Methyl-5-hydroxymethylbicyclo [2.2.1]
Hept-2-ene, 5-methyl-5- (2-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5
-Methyl-5-methoxybicyclo [2.2.1] hept-2-ene, 5-methyl-5-ethoxybicyclo [2.
2.1] Hept-2-ene, 5-methyl-5- (1-methoxyethoxy) bicyclo [2.2.1] hept-2-
Ene, 5-methyl-5- (1-ethoxyethoxy) bicyclo [2.2.1] hept-2-ene, 5-methyl-5
-(1-n-propoxyethoxy) bicyclo [2.2.
1] Hept-2-ene, 5-methyl-5- (1-n-butoxyethoxy) bicyclo [2.2.1] hept-2-
Ene, 5-methyl-5- (1-cyclohexyloxyethoxy) bicyclo [2.2.1] hept-2-ene, 5
-Methyl-5- (1-methoxyethoxy) methylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-
(1-ethoxyethoxy) methylbicyclo [2.2.1
] Hept-2-ene, 5-methyl-5- (1-n-propoxyethoxy) methylbicyclo [2.2.1] hept-2-ene, 5-methyl-5- (1-n-butoxyethoxy) Methylbicyclo [2.2.1] hept-2-ene, 5-methyl-5- (1-cyclohexyloxyethoxy) methylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-tetrahydrofura Nyloxybicyclo [2.2.1] hept-2-ene, 5-methyl-5
-Tetrahydropyranyloxybicyclo [2.2.1]
Hept-2-ene, 5-methyl-5-tetrahydrofuranyloxymethylbicyclo [2.2.1] hept-2-
Ene, 5-methyl-5-tetrahydropyranyloxymethylbicyclo [2.2.1] hept-2-ene,

5-hydroxy-6-methylbicyclo [
2.2.1] Hept-2-ene, 5-carboxy-6-
Methylbicyclo [2.2.1] hept-2-ene, 5-
Hydroxymethyl-6-methylbicyclo [2.2.1]
Hept-2-ene, 5- (2-hydroxyethyl) -6
-Methylbicyclo [2.2.1] hept-2-ene, 5
-Methoxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-ethoxy-6-methylbicyclo [2.
2.1] Hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5 ,
6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2-hydroxyethyl)
Bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene,
5,6-diethoxybicyclo [2.2.1] hept-2
-Ene, 5,6-di (1-methoxyethoxy) bicyclo
[2.2.1] Hept-2-ene, 5,6-di (1-ethoxyethoxy) bicyclo [2.2.1] hept-2-
Ene, 5,6-di (1-n-propoxyethoxy) bicyclo [2.2.1] hept-2-ene, 5,6-di (1
-N-butoxyethoxy) bicyclo [2.2.1] hept-2-ene, 5,6-di (1-cyclohexyloxyethoxy) bicyclo [2.2.1] hept-2-ene,

5,6-di [(1-methoxyethoxy) methyl] bicyclo [2.2.1] hept-2-ene, 5,
6-di [(1-ethoxyethoxy) methyl] bicyclo [
2.2.1] Hept-2-ene, 5,6-di [(1-n
-Propoxyethoxy) methyl] bicyclo [2.2.1
] Hept-2-ene, 5,6-di [(1-n-butoxyethoxy) methyl] bicyclo [2.2.1] hept-2
-Ene, 5,6-di [(1-cyclohexyloxyethoxy) methyl] bicyclo [2.2.1] hept-2-ene, 5,6-di (tetrahydrofuranyloxy) bicyclo [2.2.1] Hept-2-ene, 5,6-di (tetrahydropyranyloxy) bicyclo [2.2.1] hept-2-ene, 5,6-di (tetrahydrofuranyloxymethyl) bicyclo [2.2.1] Hept-2-ene,
5,6-di (tetrahydropyranyloxymethyl) bicyclo [2.2.1] hept-2-ene,

5- (2,2,2-trifluoro-1-hydroxyethyl) bicyclo [2.2.1] hept-2-
Ene, 5- (2,2,2-trifluoro-1-methyl-
1-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5- (2,2,2-trifluoro-1-trifluoromethyl-1-hydroxyethyl) bicyclo [
2.2.1] Hept-2-ene, 5- (2,2,2-trifluoro-1-methoxyethyl) bicyclo [2.2.
1] Hept-2-ene, 5- (2,2,2-trifluoro-1-methyl-1-methoxyethyl) bicyclo [2.
2.1] Hept-2-ene, 5- (2,2,2-trifluoro-1-trifluoromethyl-1-methoxyethyl) bicyclo [2.2.1] hept-2-ene, 5-
(2,2,2-trifluoro-1-methylcarbonyloxyethyl) bicyclo [2.2.1] hept-2-ene, 5- (2,2,2-trifluoro-1-methyl-1)
-Methylcarbonyloxyethyl) bicyclo [2.2.
1] Hept-2-ene, 5- (2,2,2-trifluoro-1-trifluoromethyl-1-methylcarbonyloxyethyl) bicyclo [2.2.1] hept-2-ene, 5- ( 2,2,2-trifluoro-1-t-butoxycarbonyloxyethyl) bicyclo [2.2.1] hept-2-ene, 5- (2,2,2-trifluoro-1
-Methyl-1-t-butoxycarbonyloxyethyl)
Bicyclo [2.2.1] hept-2-ene, 5- (2,
2,2-trifluoro-1-trifluoromethyl-1-
1. t-butoxycarbonyloxyethyl) bicyclo [2.
2.1] Hept-2-ene,

5- (2-trifluoromethyl-2-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5- (2-trifluoromethyl-2-methyl-2-
(Hydroxyethyl) bicyclo [2.2.1] hept-2
-Ene, 5- [2,2-di (trifluoromethyl) -2
-Hydroxyethyl] bicyclo [2.2.1] hept-
2-ene, 5- (2-trifluoromethyl-2-methoxyethyl) bicyclo [2.2.1] hept-2-ene,
5- (2-trifluoromethyl-2-methyl-2-methoxyethyl) bicyclo [2.2.1] hept-2-ene, 5- [2,2-di (trifluoromethyl) -2-methoxyethyl ] Bicyclo [2.2.1] hept-2-ene, 5- [2-trifluoromethyl-2-methylcarbonyloxyethyl] bicyclo [2.2.1] hept-2
-Ene, 5- (2-trifluoromethyl-2-methyl-
1. 2-methylcarbonyloxyethyl) bicyclo [2.
2.1] Hept-2-ene, 5- [2,2-di (trifluoromethyl) -2-methylcarbonyloxyethyl]
Bicyclo [2.2.1] hept-2-ene, 5- [2-
Trifluoromethyl-2-t-butoxycarbonyloxyethyl] bicyclo [2.2.1] hept-2-ene,
5- (2-trifluoromethyl-2-methyl-2-t-
Butoxycarbonyloxyethyl) bicyclo [2.2.
1] hept-2-ene, 5- [2,2-di (trifluoromethyl) -2-t-butoxycarbonyloxyethyl] bicyclo [2.2.1] hept-2-ene,

5-Cyanobicyclo [2.2.1] hept-2-ene, 5-cyanomethylbicyclo [2.2.1]
] Hept-2-ene, 5- (2-cyanoethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dicyanobicyclo [2.2.1] hept-2-ene, 5,6 -Di (cyanomethyl) bicyclo [2.2.1] hept-2-
Ene, 5,6-di (2-cyanoethyl) bicyclo [2.
2.1] Hept-2-ene, 5-cyano-5-methylbicyclo [2.2.1] hept-2-ene, 5-cyano-
5-ethylbicyclo [2.2.1] hept-2-ene,
5-cyanomethyl-5-methylbicyclo [2.2.1]
Hept-2-ene, 5-cyanomethyl-5-ethylbicyclo [2.2.1] hept-2-ene, 5- (2-cyanoethyl) -5-methylbicyclo [2.2.1] hept-2- Ene, 5- (2-cyanoethyl) -5-ethylbicyclo [2.2.1] hept-2-ene, 5-cyano-
6-methylbicyclo [2.2.1] hept-2-ene,
5-cyanomethyl-6-methylbicyclo [2.2.1]
Hept-2-ene, 5- (2-cyanoethyl) -6-methylbicyclo [2.2.1] hept-2-ene, 5,6
-Dicarboxybicyclo [2.2.1] hept-2-
Bicyclo [2] such as ene anhydride (hymic acid anhydride);
2.1] Hept-2-ene or derivatives thereof;

Tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-methyltetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-
Ethyltetracyclo [4.4.0.1 ^2,5 . [ ^17,10 ] dodec-3-ene, 8-fluoromethyltetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-
Difluoromethyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10] dodeca-3-ene, 8-trifluoromethyl-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] Dodeca-3
-Ene, 8-methyl-8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,8-bis (trifluoromethyl) tetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-bis (trifluoromethyl) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,
8,9-tris (trifluoromethyl) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,
8,9,9-Tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,

8-methoxycarbonyltetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-
Ethoxycarbonyltetracyclo [4.4.0.
^12.5 . 1 ^7,10] dodeca-3-ene, 8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5.} 1
^7,10 ] dodec-3-ene, 8-i-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-butoxycarbonyltetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8
-(2-methylpropoxy) carbonyltetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-
(1-methylpropoxy) carbonyltetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-
t-butoxycarbonyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10] dodeca-3-ene, 8-cyclohexyl oxycarbonyl tetracyclo [4.4.0.1 ^{2, 5.}
[ ^1,7,10 ] dodec-3-ene, 8- (4-t-butylcyclohexyloxy) carbonyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-phenoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5.} 1
^7,10 ] dodeca-3-ene,

8- (1-ethoxyethoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene, 8- (1-cyclohexyloxyethoxy)
Carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] Dodeca-3-ene, 8-t-butoxycarbonylmethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-tetrahydrofuranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-tetrahydropyranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-methoxycarbonyloxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-ethoxycarbonyloxy-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene,
8-n-propoxycarbonyloxytetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-
n-butoxycarbonyloxytetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-methoxycarbonyloxy-methyl tetracyclo [4.4.0.1
^2,5 . 1 ^7,10] dodeca-3-ene, 8-ethoxycarbonyloxymethyl tetracyclo [4.4.0.1 ^{2, 5.}
1 ^7,10] dodeca-3-ene, 8-n-propoxycarbonyl oxymethyl tetracyclo [4.4.0.1 ^{2, 5.}
1 ^7,10] dodeca-3-ene, 8-n-butoxycarbonyl-oxymethyl tetracyclo [4.4.0.1 ^{2, 5.} 1
^7,10 ] dodeca-3-ene,

8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-
Ene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-Methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-Methyl-8-i-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-n-butoxycarbonyltetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8
-Methyl-8- (2-methylpropoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3
-Ene, 8-methyl-8- (1-methylpropoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Dodeca-3-ene, 8-methyl-8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-methyl-8-cyclohexyl oxycarbonyl tetracyclo [4.4.0.1 ^{2, 5.} 1
^7,10 ] dodec-3-ene, 8-methyl-8- (4-t-
Butylcyclohexyloxy) carbonyltetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8
-Methyl-8-phenoxycarbonyltetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-
Methyl-8- (1-ethoxyethoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-
Ene, 8-methyl-8- (1-cyclohexyloxyethoxy) carbonyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-
t-butoxycarbonylmethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-Methyl-8-tetrahydrofuranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-methyl-8-tetrahydropyranyloxy carbonyl tetracyclo [4.4.0.1 ^{2, 5.} 1
^7,10 ] dodeca-3-ene,

8-methyl-8-methoxycarbonyloxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-methyl-8-ethoxycarbonyloxy-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene, 8-methyl -8-n-propoxycarbonyl oxymethyl tetracyclo [4.4.0.1 ^{2, 5.} 1
^7,10 ] dodeca-3-ene, 8-methyl-8-n-butoxycarbonyloxytetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-
Methoxycarbonyloxymethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-ethoxycarbonyloxymethyltetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8
-Methyl-8-n-propoxycarbonyloxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene, 8-methyl-8-n-butoxycarbonyloxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] Dodeca-3-ene,

8,9-di (methoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,9-di (ethoxycarbonyl) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,
9-di (n-propoxycarbonyl) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,
9-di (i-propoxycarbonyl) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,
9-di (n-butoxycarbonyl) tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-
Di (2-methylpropoxycarbonyl) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,
9-di (1-methylpropoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-di (t-butoxycarbonyl) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,
9-di (cyclohexyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-di (4-t-butylcyclohexyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Dodeca-3-ene, 8,9-di (phenoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,9-di (1-ethoxyethoxycarbonyl) tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ]
Dodeca-3-ene, 8,9-di (1-cyclohexyloxyethoxycarbonyl) tetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (t-
Butoxycarbonylmethoxycarbonyl) tetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-di (tetrahydrofuranyloxycarbonyl)
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene, 8,9-di (tetrahydropyranyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] Dodeca-3-ene,

8,9-Dimethoxycarbonyloxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-
Ene, 8,9-diethoxycarbonyloxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-di-n-propoxycarbonyloxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,9-di -n- butoxycarbonyloxy tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene, 8,9-di (methoxycarbonyloxy methyl) tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] Dodeca-3
-Ene, 8,9-di (ethoxycarbonyloxymethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,9-di (n- propoxycarbonyl oxymethyl) tetracyclo [4.4.0.1 ^{2, 5.} 1
^[7,10 ] dodec-3-ene, 8,9-di (n-butoxycarbonyloxymethyl) tetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodec-3-ene,

8-Hydroxytetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-carboxy-tetracyclo [4.4.0.1 ^{2, 5.} [ ^17,10 ] dodec-3-ene, 8-hydroxymethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8- (2
-Hydroxyethyl) tetracyclo [4.4.0.1
^2,5 . 1 ^7,10] dodeca-3-ene, 8-methoxy-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene, 8-ethoxy tetracyclo [4.4.0.1 ^{2, 5.}
1 ^7,10] dodeca-3-ene, 8- (1-methoxyethoxy) tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene, 8- (1-ethoxyethoxy) tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene, 8- (1-n-propoxyethoxy) tetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8
-(1-n-butoxyethoxy) tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8- (1
-Cyclohexyloxyethoxy) tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,

8- (1-methoxyethoxy) methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-
Ene, 8- (1-ethoxyethoxy) methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8- (1-n-propoxyethoxy) methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8- (1-n-butoxyethoxy) methyltetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8
-(1-cyclohexyloxyethoxy) methyltetracyclo [4.4.0.1 ^2,5 . [ ^17,10 ] dodec-3-ene, 8-tetrahydrofuranyloxytetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-
Tetrahydropyranyloxytetracyclo [4.4.
0.1 ^2,5 . [ ^1,7,10 ] dodec-3-ene, 8-tetrahydrofuranyloxymethyltetracyclo [4.4.0.
^12.5 . 1 ^7,10] dodeca-3-ene, 8-tetrahydropyranyloxymethyl tetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodec-3-ene,

8-methyl-8-hydroxytetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8
-Methyl-8-carboxytetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-
Hydroxymethyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10] dodeca-3-ene, 8-methyl-8- (2-hydroxyethyl) tetracyclo [4.4.0.1 ^{2, 5.}
1 ^7,10] dodeca-3-ene, 8-methyl-8-methoxy-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] Dodeca
3-ene, 8-methyl-8-ethoxytetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-
Methyl-8- (1-methoxyethoxy) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-
Methyl-8- (1-ethoxyethoxy) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-
Methyl-8- (1-n-propoxyethoxy) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-methyl-8-(1-n-butoxyethoxy) tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] Dodeca-3
-Ene, 8-methyl-8- (1-cyclohexyloxyethoxy) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] Dodeca-3-ene,

8-methyl-8- (1-methoxyethoxy) methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] Dodec-3-ene, 8-methyl-8- (1-ethoxyethoxy) methyltetracyclo [4.4.0.1 ^2,5 .
[ ^17,10 ] dodec-3-ene, 8-methyl-8- (1-n
-Propoxyethoxy) methyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-
8- (1-n-butoxyethoxy) methyltetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8
-Methyl-8- (1-cyclohexyloxyethoxy)
Methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-methyl-8-tetrahydrofuranyloxy tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ]
Dodeca-3-ene, 8-methyl-8-tetrahydropyranyloxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] Dodeca-3-ene, 8-methyl-8-tetrahydrofuranyloxymethyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-
3. Tetrahydropyranyloxymethyltetracyclo [4.
4.0.1 ^2,5 . [ ^1,7,10 ] dodec-3-ene, 8-hydroxy-9-methyltetracyclo [4.4.0.
^12.5 . 1 ^7,10] dodeca-3-ene, 8-carboxyl-9-methyl-tetracyclo [4.4.0.1 ^{2, 5.} 1
^7,10 ] dodec-3-ene, 8-hydroxymethyl-9-
Methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2-hydroxyethyl) -9-
Methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-methoxy-9-methyl-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene,
8-ethoxy-9-methyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodec-3-ene,

8,9-dihydroxytetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-
Dicarboxytetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8,9-di (hydroxymethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,9-di (2-hydroxyethyl) tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] Dodeca-3
-Ene, 8,9-dimethoxytetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,9-diethoxy-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene, 8,9-di (1-methoxyethoxy)
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene, 8,9-di (1-ethoxyethoxy) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,9-di (1-n-propoxy-ethoxy) tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene, 8,9-di (1-n-butoxyethoxy) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,9-di (1-cyclohexyloxy-ethoxy)
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene, 8,9-di [(1-methoxyethoxy) methyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di [(1-ethoxyethoxy)
Methyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Dodeca-3-ene, 8,9-di [(1-n-propoxyethoxy) methyl] tetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodec-3-ene, 8,9-di [(1
-N-butoxyethoxy) methyl] tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-
Di [(1-cyclohexyloxyethoxy) methyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3
-Ene, 8,9-di (tetrahydrofuranyloxy) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3
-Ene, 8,9-di (tetrahydropyranyloxy) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3
-Ene, 8,9-di (tetrahydrofuranyloxymethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,9-di (tetrahydropyranyloxymethyl) tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10
] Dodeca-3-ene,

8- (2,2,2-trifluoro-1-hydroxyethyl) tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10] dodeca-3-ene, 8- (2,2,2-trifluoro-1-methyl-1-hydroxyethyl) tetracyclo [4.4.0.1 ^{2, 5.} [ ^1,7,10 ] dodec-3-ene, 8- (2,2,2-trifluoro-1-trifluoromethyl-1-hydroxyethyl) tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-
(2,2,2-trifluoro-1-methoxyethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3
-Ene, 8- (2,2,2-trifluoro-1-methyl-1-methoxyethyl) tetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2,2,2-
Trifluoro-1-trifluoromethyl-1-methoxyethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Dodeca-3-ene, 8- (2,2,2-trifluoro-
1-methylcarbonyloxyethyl) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-
(2,2,2-trifluoro-1-methyl-1-methylcarbonyloxyethyl) tetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodec-3-ene, 8- (2,2,2
-Trifluoro-1-trifluoromethyl-1-methylcarbonyloxyethyl) tetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodec-3-ene, 8- (2,2,2
-Trifluoro-1-t-butoxycarbonyloxyethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2,2,2-trifluoro-1
-Methyl-1-t-butoxycarbonyloxyethyl)
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene, 8- (2,2,2-trifluoro-1-trifluoromethyl-1-t-butoxycarbonyloxyethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,

8- (2-trifluoromethyl-2-hydroxyethyl) tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8- (2-trifluoromethyl-2-methyl-2-hydroxyethyl) tetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8
-[2,2-bis (trifluoromethyl) -2-hydroxyethyl] tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8- (2-trifluoromethyl-2-methoxyethyl) tetracyclo [4.4.0.
^12.5 . 1 ^7,10] dodeca-3-ene, 8- (2-trifluoromethyl-2-methyl-2-methoxyethyl) tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodeca-3-
Ene, 8- [2,2-di (trifluoromethyl) -2-
Methoxyethyl] tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10] dodeca-3-ene, 8- [2-trifluoromethyl-2-methyl carbonyloxy ethyl] tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene,
8- (2-trifluoromethyl-2-methyl-2-methylcarbonyloxyethyl) tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8- [2,2
-Di (trifluoromethyl) -2-methylcarbonyloxyethyl] tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8- [2-trifluoromethyl-2-t-butoxycarbonyloxyethyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2-trifluoromethyl-2-methyl-2-
t-butoxycarbonyloxyethyl) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-
[2,2-di (trifluoromethyl) -2-t-butoxycarbonyloxyethyl] tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,

8-cyanotetracyclo [4.4.0.1
^2,5 . 1 ^7,10] dodeca-3-ene, 8-cyanomethyl tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] Dodeca-3
-Ene, 8- (2-cyanoethyl) tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-
Dicyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Dodeca-3-ene, 8,9-di (cyanomethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,9-di (2-cyanoethyl) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-
Cyano-8-methyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodec-3-ene, 8-cyano-8-
Ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-cyanomethyl-8-methyl-tetracyclo [4.4.0.1 ^{2, 5.} [ ^17,10 ] dodec-3-ene, 8-cyanomethyl-8-ethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8- (2
-Cyanoethyl) -8-methyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2'-
(Cyanoethyl) -8-ethyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-cyano-
9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] Dodec-3-ene, 8-cyanomethyl-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3
-Ene, 8- (2-cyanoethyl) -9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,9-dicarboxylate tetracyclo [4.4.0.
^12.5 . Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene anhydride and the like. [ ^1,7,10 ] dodec-3-ene or derivatives thereof.

Among these norbornene derivatives (I), preferred compounds are norbornene, 5-t-
Butoxycarbonylbicyclo [2.2.1] hept-
2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.
2.1] Hept-2-ene, 5-methyl-5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5
-Carboxybicyclo [2.2.1] hept-2-ene,

Tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene, 8-hydroxytetracyclo [4.4.0.
^12.5 . 1 ^7,10] dodeca-3-ene, 8-hydroxymethyl-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene, 8-methyl-8-hydroxymethyl-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodeca-3-
Ene, 8-carboxytetracyclo [4.4.0.1
^2,5 . [ ^1,7,10 ] dodec-3-ene and the like. In the resin (C1) and the resin (C2), the repeating unit (I) may be used alone or in combination of two or more.

Next, the repeating unit (II) in the resin (C1) and the resin (C2) is a unit derived from maleic anhydride. Maleic anhydride has good copolymerizability with the norbornene derivative (I) and other alicyclic unsaturated compounds described below. Can be as large as

Next, in the repeating unit (III) of the resin (C2), examples of the linear or branched alkyl group having 1 to 4 carbon atoms for R ⁵ include a methyl group, an ethyl group, and an n-type alkyl group.
-Propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like. Examples of the linear or branched alkoxyl group having 1 to 4 carbon atoms for R ⁵ include a methoxy group, an ethoxy group, an n-propoxy group, and an i-
Examples include a propoxy group, an n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group, and a t-butoxy group. Examples of the linear or branched hydroxyalkyl group having 1 to 4 carbon atoms for R ⁵ include a hydroxymethyl group, a 1-hydroxyethyl group,
-Hydroxyethyl group, 1-hydroxypropyl group, 2
-Hydroxypropyl group, 3-hydroxypropyl group,
1-hydroxybutyl group, 2-hydroxybutyl group, 3
-Hydroxybutyl group, 4-hydroxybutyl group and the like. R ⁵ in the repeating unit (III) is particularly preferably a hydrogen atom, a methyl group, a hydroxymethyl group or the like.

Examples of the linear or branched alkylene group having 2 to 4 carbon atoms in the main chain of A include a methylene group, an ethylene group, a 1-methyl-1,1-ethylene group, a propylene group and a trimethylene group. And a tetramethylene group. A in the repeating unit (III) is particularly preferably a single bond or a methylene group.

Further, R ⁷ , R ⁸ and R ⁹ in R ⁶
Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms include a bridged skeleton such as an adamantane skeleton, a norbornane skeleton, a tricyclodecane skeleton, and a tetracyclododecane skeleton; cyclobutane; cyclopentane; cyclohexane;
Groups having a cycloalkane skeleton such as cycloheptane and cyclooctane; these groups are, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-methylpropyl, 1- Methylpropyl group, t
And a group having an alicyclic skeleton such as a group substituted with one or more linear or branched or cyclic alkyl groups having 1 to 10 carbon atoms such as -butyl group. Among these alicyclic hydrocarbon groups, a group having a bridged skeleton is preferable, and a group having a skeleton selected from the group consisting of an adamantane skeleton, a norbornane skeleton, a tricyclodecane skeleton, and a tetracyclododecane skeleton is particularly preferable.

Further, among X ¹ , X ² and X ³ , 1 to
Examples of the trivalent oxygen-containing polar group include a hydroxyl group; a carboxyl group; an oxy group (that is, an 基 O group); an ald group (that is, a —CHO group);
Hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-
Hydroxypropyl group, 1-hydroxybutyl group, 2-
A hydroxyalkyl group having 1 to 4 carbon atoms such as a hydroxybutyl group, a 3-hydroxybutyl group and a 4-hydroxybutyl group; a methoxy group, an ethoxy group, an n-propoxy group, i
-An alkoxyl group having 1 to 4 carbon atoms such as -propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, etc .; Examples of the polar group include a cyano group; a cyanoalkyl group having 2 to 5 carbon atoms such as a cyanomethyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, and a 4-cyanobutyl group. Among these oxygen-containing polar groups and nitrogen-containing polar groups, particularly, a hydroxyl group, an oxy group, an ald group, a hydroxymethyl group,
Preferred are a cyano group, a cyanomethyl group and the like. In the repeating unit (III), the carboxylic acid ester structure has acid dissociation. Hereinafter, the carboxylic acid ester structure (—COO-A-R ⁶ ) in the repeating unit (III) is referred to as “acid dissociable group (c)”.

The monomer giving the repeating unit (III) is a compound in which the hydrogen atom at the α-position in acrylic acid is substituted with a group R ⁵ and the hydrogen atom of a carboxyl group is substituted with a group —A—R ⁶ . (Hereinafter referred to as “acrylic acid derivative (III)”).

Specific examples of the acrylic acid derivative (III) include compounds represented by the following formulas (III-1) to (III-127).

[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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Among these acrylic acid derivatives (III),
In particular, the formulas (III-1), (III-2), (III-4), (III-5), (III-7), (III-9), (III-1)
2), Formula (III-14), Formula (III-28) or Formula (III-35)
And the like are preferred. In the resin (C2), the repeating unit (III) may be present alone or in combination of two or more.

Next, in the repeating unit (IV) of the resin (C2), examples of the linear or branched alkyl group having 1 to 4 carbon atoms for R ¹⁰ include a methyl group, an ethyl group and an n-type alkyl group.
-Propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like. Examples of the linear or branched alkoxyl group having 1 to 4 carbon atoms for R ¹⁰ include a methoxy group, an ethoxy group, an n-propoxy group, an i-
Examples include a propoxy group, an n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group, and a t-butoxy group. Examples of the linear or branched hydroxyalkyl group having 1 to 4 carbon atoms for R ¹⁰ include a hydroxymethyl group, a 1-hydroxyethyl group,
-Hydroxyethyl group, 1-hydroxypropyl group, 2
-Hydroxypropyl group, 3-hydroxypropyl group,
1-hydroxybutyl group, 2-hydroxybutyl group, 3
-Hydroxybutyl group, 4-hydroxybutyl group and the like. R ¹⁰ in the repeating unit (IV) is particularly preferably a hydrogen atom, a methyl group, or the like.

Further, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms for R ^{11 and} a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms formed by bonding any two R ¹¹ to each other. Examples of the hydrocarbon group include an adamantane skeleton, a norbornane skeleton,
A group having a bridged skeleton such as a tricyclodecane skeleton or a tetracyclododecane skeleton or a cycloalkane skeleton such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, or cyclooctane; these groups include, for example, a methyl group and an ethyl group; , N-propyl group, i-propyl group, n
Substituted with one or more or one or more linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms such as -butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like. And groups having an alicyclic skeleton such as a group. Among these alicyclic hydrocarbon groups, a group having a bridged skeleton is preferable, and a group having a skeleton selected from the group consisting of an adamantane skeleton, a norbornane skeleton, a tricyclodecane skeleton, and a tetracyclododecane skeleton is particularly preferable.

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms for R ¹¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and a 2-alkyl group. -Methylpropyl group, 1-methylpropyl group, t
-Butyl group and the like. Among these alkyl groups, a methyl group, an ethyl group and the like are particularly preferable. The carboxylic acid ester structure of the repeating unit (IV) has acid dissociation properties. In the following, the repeating unit (IV)
Carboxylic acid ester structure (-COO-C (R ¹¹ ) ₃ )
Is referred to as “acid-labile group (d)”.

[0137] monomers which provide the repeating unit (IV) is replaced in the acrylic acid α- position of a hydrogen atom in the group R ^10, and substituting the hydrogen atom of a carboxyl group with a group -C (R ¹¹⁾ ₃ (Hereinafter referred to as “acrylic acid derivative (IV)”) ”.

Specific examples of the acrylic acid derivative (IV) include compounds represented by the following formulas (IV-1) to (IV-30).

[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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Among these acrylic acid derivatives (IV),
Formula (IV-1), Formula (IV-2), Formula (IV-3), Formula (IV-5), Formula (IV-6), Formula (IV-7) or Formula (IV-9) And the like are preferred. In the resin (C2)), the repeating unit (IV) may be present alone or in combination of two or more.

The resin (C1) and the resin (C2) may have one or more types of repeating units other than those described above (hereinafter, referred to as “other repeating units”). Examples of the monomer that provides another repeating unit (hereinafter, referred to as “other monomer”) include, for example, 5-fluorobicyclo [2.2.1] hept-2-ene, 5,5-difluorobicyclo [2.
2.1] Hept-2-ene, 5,6-difluorobicyclo [2.2.1] hept-2-ene, 5,5,6-trifluorobicyclo [2.2.1] hept-2-ene ,
5,5,6,6-tetrafluorobicyclo [2.2.1
] Hept-2-ene, 5,5-difluoro-6,6-di (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,6-difluoro-5,6-di (tri Fluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,5,6-trifluoro-6-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5,5
6-trifluoro-6-trifluoromethoxybicyclo
[2.2.1] Hept-2-ene, 5,5,6-trifluoro-6-pentafluoro-n-propoxybicyclo
[2.2.1] Hept-2-ene, 5-fluoro-5-
Pentafluoroethyl-6,6-di (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,6
-Difluoro-5-heptafluoro-i-propyl-6
-Trifluoromethylbicyclo [2.2.1] hept-
2-ene, 5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene, 5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [
2.2.1] Hept-2-ene, 5- (2,2,2-trifluorocarbethoxy) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (2,2 , 2-trifluorocarboethoxy) bicyclo [2.2.1] hept-2-ene,

8-Fluorotetracyclo [4.4.0.
^12.5 . 1 ^7,10] dodeca-3-ene, 8,8-difluoro-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene, 8,9-difluoro-tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,8,
9-trifluorotetracyclo [4.4.0.1 ^2,5 .
1 ^7,10] dodeca-3-ene, 8,8,9,9- tetrafluoro-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene, 8,8-difluoro-9,9-di (trifluoromethyl) tetracyclo [4.4.0.
^12.5 . 1 ^7,10] dodeca-3-ene, 8,9-difluoro-8,9-di (trifluoromethyl) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,
8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,8,9- trifluoro-9-trifluoromethoxy-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene, 8,8,9- trifluoro-9-pentafluoro -n- propoxy tetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodec-3-ene, 8-fluoro-8
-Pentafluoroethyl-9,9-di (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,9-difluoro-8-heptafluoro--i- propyl-9-trifluoromethyl-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene, 8-chloro -8,9,9- trifluoro tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene,
8,9-dichloro-8,9-di (trifluoromethyl)
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene, 8- (2,2,2-trifluorocarboethoxy) tetracyclo [4.4.0.1 ^2,5 . [ ^1,7,10 ] dodec-3-ene, 8-methyl-8- (2,2,2-trifluorocarboethoxy) tetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodec-3-ene,

Dicyclopentadiene, tricyclo [5.
2.1.0 ^2,6 ] deca-8-ene, tricyclo [5.
2.1.0 ^2,6 ] deca-3-ene, tricyclo [4.
4.0.1 ^2,5 ] undec-3-ene, tricyclo [
6.2.1.0 ^1,8 ] undec-9-ene, tricyclo
[6.2.1.0 ^1,8 ] undec-4-ene, tetracyclo [4.4.0.1 ^2,5 . ^17,10 . 0 ^1,6 ] Dodeca
3-ene, 8-methyltetracyclo [4.4.0.1
^2,5 . ^17,10 . 0 ^1,6 ] dodeca-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . [ ^1,7,12 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.
0.1 ^2,5 . ^17,10 . 0 ^1,6 ] dodeca-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-4-ene, pentacyclo [7.4.0.1
^2,5 . ^19,12 . 0 ^8,13] pentadeca-3 other alicyclic unsaturated compounds such as ene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-methylpropyl (meth) acrylate, (meth) acrylic acid 2-hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) Cyclohexenyl acrylate, 4-methoxycyclohexyl (meth) acrylate, 2-cyclopropyloxycarbonylethyl (meth) acrylate, 2-cyclopentyloxycarbonylethyl (meth) acrylate, (meth)
2-cyclohexyloxycarbonylethyl acrylate, 2-cyclohexenyloxycarbonylethyl (meth) acrylate, 2- (4'-methoxycyclohexyl) oxycarbonylethyl (meth) acrylate, norbornyl (meth) acrylate, (meth) acrylate Isobornyl acrylate, tricyclodecanyl (meth) acrylate,
Tetracyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, adamantyl methyl (meth) acrylate,
(Meth) acrylates such as 1-methyladamantyl (meth) acrylate; methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, n-propyl α-hydroxymethyl acrylate, α
Α-hydroxymethyl acrylates such as n-butyl hydroxymethyl acrylate;

Α- (meth) acryloyloxy-β-methoxycarbonyl-γ-butyrolactone, α- (meth)
Acryloyloxy-β-ethoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-
n-propoxycarbonyl-γ-butyrolactone, α-
(Meth) acryloyloxy-β-i-propoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-n-butoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β- (2-
Methylpropoxy) carbonyl-γ-butyrolactone,
α- (meth) acryloyloxy-β- (1-methylpropoxy) carbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-t-butoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β -Cyclohexyloxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β- (4
-T-butylcyclohexyloxy) carbonyl-γ-
Butyrolactone, α- (meth) acryloyloxy-β
-Phenoxycarbonyl-γ-butyrolactone, α-
(Meth) acryloyloxy-β- (1-ethoxyethoxy) carbonyl-γ-butyrolactone, α- (meth)
Acryloyloxy-β- (1-cyclohexyloxyethoxy) carbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-t-butoxycarbonylmethoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-tetrahydrofuran Nyloxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-tetrahydropyranyloxycarbonyl-γ-butyrolactone,

Α-methoxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-ethoxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-n-propoxycarbonyl-β-
(Meth) acryloyloxy-γ-butyrolactone, α
-I-propoxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-n-butoxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α- (2-methylpropoxy) carbonyl-
β- (meth) acryloyloxy-γ-butyrolactone, α- (1-methylpropoxy) carbonyl-β-
(Meth) acryloyloxy-γ-butyrolactone, α
-T-butoxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-cyclohexyloxycarbonyl-β- (meth) acryloyloxy-γ-
Butyrolactone, α- (4-t-butylcyclohexyloxy) carbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-phenoxycarbonyl-β
-(Meth) acryloyloxy-γ-butyrolactone,
α- (1-ethoxyethoxy) carbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-
(1-cyclohexyloxyethoxy) carbonyl-β
-(Meth) acryloyloxy-γ-butyrolactone,
α-t-butoxycarbonylmethoxycarbonyl-β-
(Meth) acryloyloxy-γ-butyrolactone, α
(Meth) acryloyloxy having an acid dissociable group such as -tetrahydrofuranyloxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-tetrahydropyranyloxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone Lactone compounds;

Α- (meth) acryloyloxy-γ-butyrolactone, α- (meth) acryloyloxy-β-
Fluoro-γ-butyrolactone, α- (meth) acryloyloxy-β-hydroxy-γ-butyrolactone, α
-(Meth) acryloyloxy-β-methyl-γ-butyrolactone, α- (meth) acryloyloxy-β-ethyl-γ-butyrolactone, α- (meth) acryloyloxy-β, β-dimethyl-γ-butyrolactone, α −
(Meth) acryloyloxy-β-methoxy-γ-butyrolactone, β- (meth) acryloyloxy-γ-butyrolactone, α-fluoro-β- (meth) acryloyloxy-γ-butyrolactone, α-hydroxy-β-
(Meth) acryloyloxy-γ-butyrolactone, α
-Methyl-β- (meth) acryloyloxy-γ-butyrolactone, α-ethyl-β- (meth) acryloyloxy-γ-butyrolactone, α, α-dimethyl-β-
(Meth) acryloyloxy-γ-butyrolactone, α
-Methoxy-β- (meth) acryloyloxy-γ-butyrolactone, α- (meth) acryloyloxy-δ-
(Meth) acryloyloxylactone compounds having no acid-dissociable group such as mevalonolactone;

Vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; (meth) acrylonitrile, α-chloroacrylonitrile, crotononitrile,
Unsaturated nitrile compounds such as maleinitrile, fumalonitrile, mesaconnitrile, citraconitrile, itaconitrile; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleamide, fumaramid, mesaconamide, citraconamide, itacon Unsaturated amide compounds such as amides; N
-Other nitrogen-containing vinyl compounds such as -vinyl-ε-caprolactam, N-vinylpyrrolidone, vinylpyridine, vinylimidazole; (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride Unsaturated carboxylic acids (anhydrides) such as acid, citraconic acid, citraconic anhydride, and mesaconic acid; 2-carboxyethyl (meth) acrylate, (meth) acrylic acid 2
-Carboxypropyl, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, 4-carboxycyclohexyl (meth) acrylate, carboxytricyclodecanyl (meth) acrylate, (meth) acrylic acid Carboxyl group-containing esters of unsaturated carboxylic acids such as carboxytetracyclodecanyl; the carboxyl groups of the unsaturated carboxylic acids and the carboxyl group-containing esters of unsaturated carboxylic acids are converted into the following acid dissociable groups (e). Monofunctional monomer such as a compound (hereinafter, referred to as “an other acid-dissociable group-containing monomer”),

Methylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2,5-dimethyl-2,5-hexane Diol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate,
1,4-bis (2-hydroxypropyl) benzenedi (meth) acrylate, 1,3-bis (2-hydroxypropyl) benzenedi (meth) acrylate, 1,2-
Adamantanediol di (meth) acrylate, 1,3
-Adamantanediol di (meth) acrylate, 1,
Examples thereof include polyfunctional monomers such as 4-adamantanediol di (meth) acrylate and tricyclodecanyl dimethylol di (meth) acrylate.

Examples of the acid dissociable organic group (e) include, for example,
A hydrogen atom in the carboxyl group is replaced with a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group, a cyclic acid dissociable group (however, A compound in which a hydrogen atom of a carboxyl group is substituted with the cyclic acid dissociable group is an acrylic acid derivative
(III) or the case corresponding to the acrylic acid derivative (IV) is excluded. )) And the like. Examples of the substituted methyl group include a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group, a 2-methoxyethoxymethyl group, a benzyloxymethyl group, a benzylthiomethyl group, a phenacyl group, and a 4-bromophenacyl group. , 4-methoxyphenacyl, 4-methylthiophenacyl, α-methylphenacyl, cyclopropylmethyl, benzyl, diphenylmethyl, triphenylmethyl, 4-bromobenzyl, 4
-Nitrobenzyl group, 4-methoxybenzyl group, 4-methylthiobenzyl group, 4-ethoxybenzyl group, 4-ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, Examples thereof include an i-propoxycarbonylmethyl group, an n-butoxycarbonylmethyl group, and a t-butoxycarbonylmethyl group. Also,
Examples of the 1-substituted ethyl group include a 1-methoxyethyl group, a 1-methylthioethyl group, a 1,1-dimethoxyethyl group, a 1-ethoxyethyl group, a 1-ethylthioethyl group, and a 1,1-diethoxy group. Ethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropylethyl group, 1
-Phenylethyl group, 1,1-diphenylethyl group, 1
-Methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group,
Examples thereof include a 1-i-propoxycarbonylethyl group, a 1-n-butoxycarbonylethyl group, a 1-t-butoxycarbonylethyl group, and the like.

The 1-branched alkyl group includes
For example, i-propyl group, 1-methylpropyl group, t-
Examples thereof include a butyl group, a 1,1-dimethylpropyl group, a 1-methylbutyl group, and a 1,1-dimethylbutyl group. Examples of the silyl group include a trimethylsilyl group, an ethyldimethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group, an i-propyldimethylsilyl group, a methyldi-i-propylsilyl group, and a tri-i
-Propylsilyl group, t-butyldimethylsilyl group, methyldi-t-butylsilyl group, tri-t-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilyl group, triphenylsilyl group and the like.
Examples of the germyl group include a trimethylgermyl group, an ethyldimethylgermyl group, a methyldiethylgermyl group, a triethylgermyl group, an i-propyldimethylgermyl group, a methyldi-i-propylgermyl group,
Tri-i-propylgermyl group, t-butyldimethylgermyl group, methyldi-t-butylgermyl group, tri-t
-Butylgermyl group, phenyldimethylgermyl group, methyldiphenylgermyl group, triphenylgermyl group and the like. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an i-propoxycarbonyl group, and a t-butoxycarbonyl group.

Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a heptanoyl group, a hexanoyl group, a valeryl group, a pivaloyl group, an isovaleryl group, a lauryloyl group, a myristoyl group, a palmitoyl group, a stearoyl group, and an oxalyl group. Group, malonyl group, succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoil group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group,
Fumaroyl group, mesaconoyl group, camphoroyl group, benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, floyl group, tenoyl group, nicotinoyl group, isonicotinoyl group , P-toluenesulfonyl group, mesyl group and the like. Further, examples of the cyclic acid dissociable group include a 3-oxocyclohexyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, a tetrahydrothiofuranyl group, a 3-bromotetrahydropyranyl group, -Methoxytetrahydropyranyl group, 2-oxo-4-methyltetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, 3-tetrahydrothiophen-1,1-dioxide group and the like.

Among these acid dissociable groups (e), a 1-ethoxyethyl group, a t-butoxycarbonyl group, a tetrahydropyranyl group and the like are preferable.

In the resin (C2) of the present invention, R ⁶ in the repeating unit (III) is such that the alicyclic hydrocarbon group of R ⁷ has an adamantane skeleton, a norbornane skeleton, a tricyclodecane skeleton and a tetracyclododecane skeleton. A resin having a skeleton selected from the group and a resin represented by the formula (i) wherein X ¹ is a hydroxyl group; and a repeating unit (IV)
In particular, a resin in which each alicyclic hydrocarbon group or a derivative thereof in R ¹¹ is a group having a skeleton selected from the group of an adamantane skeleton, a norbornane skeleton, a tricyclodecane skeleton, and a tetracyclododecane skeleton independently of each other, preferable. When the resin (C2) has both the repeating unit (III) and the repeating unit (IV), both R ⁶ in the repeating unit (III) and R ^{11 in} the repeating unit (IV) satisfy the above requirements. Can be.

In the resin (C1), the repeating unit (I)
Is usually 5 to 95 mol%, preferably 10 to 70 mol%, and more preferably 20 to 50 mol%, based on all repeating units. In this case, the repeating unit (I)
If the content is less than 5 mol%, the dry etching resistance of the resist tends to decrease, while 95 mol%
If the ratio exceeds, the developability as a resist and the adhesion to a substrate tend to decrease. The content of the repeating unit (II) is usually 5 to 85 mol%,
Preferably 10 to 50 mol%, more preferably 10 to 50 mol%
45 mol%. In this case, if the content of the repeating unit (II) is less than 5 mol%, the adhesion to the substrate as a resist tends to decrease, while if it exceeds 85 mol%,
Dry etching resistance as a resist tends to decrease. The content of other repeating units is usually 20 mol% or less, preferably 10 mol% or less, based on all repeating units. However, when the repeating unit (I) does not have an acid-dissociable group in the resin (C1), it must contain a repeating unit derived from another acid-dissociable group-containing monomer as another repeating unit. Must. When the resin (C1) contains a repeating unit derived from another monomer having an acid-dissociable group, the total content of each repeating unit having an acid-dissociable group is usually 5% with respect to all the repeating units. ~ 85 mol%, preferably 10-70 mol%, more preferably 15-5 mol%
0 mol%. In this case, the total content is 5 mol%.
If the amount is less than the above, the resolution as a resist tends to decrease, while if it exceeds 85 mol%, the developability as the resist tends to decrease.

In the resin (C2), the repeating unit (I)
Is usually from 5 to 95 mol%, preferably from 10 to 70 mol%, more preferably from 20 to 50 mol%, based on all the repeating units, and the content of the repeating unit (II) is Usually, 5 to 85 mol%, preferably 10 to 50 mol%, more preferably 10 to 4 mol%, based on the repeating unit.
5 mol%, and the content of the repeating unit (III) and / or the repeating unit (IV) is usually 5 to 85 mol%, preferably 10 to 50 mol%, more preferably 10 to 50 mol%, based on all repeating units. 10 to 40 mol%. In this case, when the content of the repeating unit (I) is less than 5 mol%, the dry etching resistance as a resist tends to decrease,
On the other hand, if it exceeds 95 mol%, the developability as a resist and the adhesion to a substrate tend to decrease. If the content of the repeating unit (II) is less than 5 mol%, the adhesion to the substrate as a resist tends to decrease, while if it exceeds 85 mol%, the dry etching resistance as the resist tends to decrease. There is. Further, when the content of the repeating unit (III) and / or the repeating unit (IV) is less than 5 mol%, the resolution as a resist tends to decrease, while when it exceeds 85 mol%, the developability as a resist is deteriorated. Tends to decrease. Also, the content of other repeating units is:
It is usually at most 20 mol%, preferably at most 10 mol%, based on all repeating units. Further, in the resin (C2), the total content of each repeating unit having an acid-dissociable group is usually 5 to 85 mol%, preferably 10 to 70 mol%, more preferably 20 to all the repeating units. ~ 5
0 mol%. In this case, the total content is 5 mol%.
If the amount is less than the above, the resolution as a resist tends to decrease, while if it exceeds 85 mol%, the developability as the resist and the adhesion to the substrate tend to decrease.

The resin (C1) is a norbornene derivative (I)
And maleic anhydride, and the resin (C2) comprises a norbornene derivative (I), maleic anhydride and an acrylic acid derivative (III) and / or an acrylic acid derivative (IV), optionally together with other monomers. For example, by using a radical polymerization initiator such as hydroperoxides, dialkyl peroxides, diacyl peroxides, and azo compounds, and copolymerizing in an appropriate solvent in the presence of a chain transfer agent if necessary. Can be manufactured. As the solvent used for the copolymerization, for example, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n
-Alkanes such as decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; chlorobutanes, bromohexanes and dichloroethanes And halogenated hydrocarbons such as hexamethylene dibromide and chlorobenzene; saturated carboxylic esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate; tetrahydrofuran, dimethoxyethane, diethoxyethane and the like And the like.
These solvents can be used alone or in combination of two or more. The reaction temperature in the copolymerization is usually 40 to 120 ° C, preferably 50 to 90 ° C, and the reaction time is usually 1 to 48 hours, preferably 1 to 48 hours.
~ 24 hours.

The weight average molecular weight (hereinafter, referred to as “Mw”) of the resin (C) in terms of polystyrene measured by gel permeation chromatography (GPC) is usually 3,0.
00 to 300,000, preferably 4,000 to 20
000, more preferably 4,000 to 100,0
00. In this case, Mw of the resin (C) is 3,000.
If it is less than 30, the heat resistance as a resist tends to decrease, while if it exceeds 300,000, the developability as a resist tends to decrease. The resin (C) is preferably as low as possible in impurities such as halogen and metal, whereby the sensitivity, resolution, process stability, pattern shape, and the like as a resist can be further improved. As a method for purifying the resin (C), for example, chemical purification methods such as washing with water and liquid-liquid extraction, and those chemical purification methods and ultrafiltration,
Combination with a physical purification method such as centrifugation can be mentioned. In the present invention, the resin (C) can be used alone or in combination of two or more.

Additives The radiation-sensitive resin composition of the present invention may optionally contain an acid diffusion controller other than the compound (A) (hereinafter referred to as "another acid diffusion controller") and an alicyclic group. Various additives such as additives and surfactants can be blended. As other acid diffusion controlling agents, for example, the following general formula (7)

[0167]

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[In the general formula (7), R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group or an aralkyl group; The groups, aryl groups and aralkyl groups may each be substituted. (Hereinafter, referred to as "nitrogen-containing compound (b1)"), a compound having two nitrogen atoms in the same molecule (hereinafter, referred to as "nitrogen-containing compound (b2)"), and a nitrogen atom. Compounds having three or more (hereinafter, referred to as “nitrogen-containing compound (b3)”), amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds can be given.

As the nitrogen-containing compound (b1), in addition to the nitrogen-containing compound (a1) exemplified as the amino compound (a), for example, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-butylamine, n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, tricyclohexylamine, etc. And alkanolamines such as ethanolamine, diethanolamine and triethanolamine.

The nitrogen-containing compound (b2) includes the nitrogen-containing compound (a) exemplified as the amino compound (a).
In addition to 2), for example, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetrakis (2-hydroxyethyl) ethylenediamine,
N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine and the like can be mentioned. As the nitrogen-containing compound (b3), in addition to the nitrogen-containing compound (a3) exemplified as the amino compound (a), for example, polyethyleneimine, N- (2-dimethylaminoethyl)
Acrylamide polymers and the like can be mentioned.

Examples of the amide group-containing compound include, in addition to the amide group-containing compound exemplified as the amino compound (a), N, N-dimethylformamide, N, N
N-dimethylacetamide, N-methylpyrrolidone and the like can be mentioned. Examples of the urea compound include, in addition to the urea compounds exemplified as the amino compound (a), for example, 1,1,3,3-tetramethylurea and the like. As the nitrogen-containing heterocyclic compound, in addition to the nitrogen-containing heterocyclic compound exemplified as the amino compound (a), for example, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine,
Pyridines such as ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, and acridine; pyrazine; pyridazine; quinosaline , 4-methylmorpholine,
Examples include 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, and the like.

Of these other acid diffusion controllers, nitrogen-containing compounds (b1), nitrogen-containing compounds (b2) and nitrogen-containing heterocyclic compounds are preferred. The other acid diffusion control agents can be used alone or in combination of two or more. The amount of the other acid diffusion controlling agent is usually 90% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, based on the total of the compound (A) and the other acid diffusion controlling agent. It is. In this case, if the amount of the other acid diffusion controller exceeds 90% by weight, the intended effect in the present invention may be impaired.

The alicyclic additive is a component having an effect of further improving dry etching resistance, pattern shape, adhesion to a substrate, and the like. Such alicyclic additives include, for example, t-butyl 1-adamantanecarboxylate, t-butoxycarbonylmethyl 1-adamantanecarboxylate, di-t- 1,3-adamantanedicarboxylate
-Butyl, t-butyl 1-adamantaneacetate, t-butoxycarbonylmethyl 1-adamantaneacetate, 1,3-
Adamantane derivatives such as di-t-butyl adamantane diacetate; t-butyl deoxycholate, t-butoxycarbonylmethyl deoxycholate, deoxycholic acid 2
-Deoxycholate esters such as ethoxyethyl, 2-cyclohexyloxyethyl deoxycholate, 3-oxocyclohexyl deoxycholate, tetrahydropyranyl deoxycholate, mevalonolactone deoxycholate; t-butyl lithocholic acid, lithocole T-butoxycarbonylmethyl acid, lithocholic acid 2-
Examples thereof include lithocholic acid esters such as ethoxyethyl, 2-cyclohexyloxyethyl lithocholic acid, 3-oxocyclohexyl lithocholic acid, tetrahydropyranyl lithocholic acid, and mevalonolactone lithocholic acid ester. These alicyclic additives can be used alone or in combination of two or more. The amount of the alicyclic additive is based on 100 parts by weight of the resin (C).
Usually, it is 50 parts by weight or less, preferably 30 parts by weight or less. In this case, if the amount of the alicyclic additive exceeds 50 parts by weight, the heat resistance of the resist tends to decrease.

The surfactant is a component having an effect of improving the coating property, the developing property and the like. Examples of such a surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, and polyoxyethylene n
-In addition to nonionic surfactants such as nonylphenyl ether, polyethylene glycol dilaurate and polyethylene glycol distearate, KP3
Polyflow No. 41 (manufactured by Shin-Etsu Chemical Co., Ltd.) 7
5, the same No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF301, EF303, and EF352 (manufactured by Tochem Products Inc.), Megafax F171, and F1
73 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard F
C430, FC431 (manufactured by Sumitomo 3M Limited),
Asahi Guard AG710, Surflon S-382, S
C-101, SC-102, SC-103, SC
-104, SC-105 and SC-106 (manufactured by Asahi Glass Co., Ltd.). These surfactants can be used alone or in combination of two or more. The amount of the surfactant is usually 2 parts by weight or less based on 100 parts by weight of the resin (C). Further, as additives other than the above, a sensitizer, an antihalation agent,
Adhesion aids, storage stabilizers, defoamers and the like can be mentioned.

Preparation of Composition Solution The radiation-sensitive resin composition of the present invention is usually used such that the total solid content is usually 5 to 50% by weight, preferably 10 to 25% by weight. After dissolving in a solvent, the composition is prepared as a composition solution by filtering through, for example, a filter having a pore size of about 0.2 μm. As the solvent used for preparing the composition solution, for example, 2-
Butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone,
Linear or branched ketones such as -methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone and 2-octanone; cyclopentanone, 3-methylcyclopentanone, cyclohexanone, -Methylcyclohexanone, 2,6-dimethylcyclohexanone,
Cyclic ketones such as isophorone; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n-butyl ether acetate; Propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol mono-t-
Propylene glycol monoalkyl ether acetates such as butyl ether acetate; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate;
N-propyl 2-hydroxypropionate, i-propyl 2-hydroxypropionate, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, sec-butyl 2-hydroxypropionate, 2
Alkyl 2-hydroxypropionates such as t-butyl-hydroxypropionate; 3-alkoxypropion such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate In addition to alkyl acid salts,

N-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, ethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl ether,
Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, toluene, xylene, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-
Methyl hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, N-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzyl ethyl ether, -N-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid,
Examples thereof include 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, and propylene carbonate.

These solvents can be used alone or as a mixture of two or more. Among them, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates are preferred. And alkyl 2-hydroxypropionates and alkyl 3-alkoxypropionates.

Method for Forming Resist Pattern The radiation-sensitive resin composition of the present invention is particularly useful as a chemically amplified resist. In the chemically amplified resist, an acid dissociable group (a), an acid dissociable group (b), and an acid dissociable group in the resin (C) are caused by the action of an acid generated from the acid generator (B) upon exposure. (C) acid dissociable groups such as acid dissociable group (d) and acid dissociable group (e) are dissociated to form a carboxyl group, and as a result, the exposed portion of the resist is exposed to an alkali developing solution. The solubility becomes higher, and the exposed portion is dissolved and removed by an alkali developer to obtain a positive resist pattern. When forming a resist pattern from the radiation-sensitive resin composition of the present invention, the composition solution, by a suitable application means such as spin coating, casting coating, roll coating, for example, silicon wafer, coated with aluminum A resist film is formed by applying the resist film on a substrate such as a wafer which has been subjected to a heat treatment (hereinafter, referred to as “PB”) in some cases, and then the resist film is formed so as to form a predetermined resist pattern. Expose. As the radiation used at that time, visible light, ultraviolet light, far ultraviolet light, X-ray, charged particle beam, etc. are appropriately selected and used depending on the type of the acid generator (B) used. ArF excimer laser (wavelength 193 nm) or KrF excimer laser (wavelength 248 nm) is preferable. In the present invention, a heat treatment (hereinafter referred to as “P
EB ". ) Is preferably performed. By this PEB, the dissociation reaction of the acid dissociable group in the resin (C) proceeds smoothly. The PEB heating conditions vary depending on the composition of the radiation-sensitive resin composition, but are usually 30 to 200 ° C, preferably 50 to 170 ° C.

In the present invention, in order to maximize the potential of the radiation-sensitive resin composition, for example,
As disclosed in Japanese Patent No. 12452 or the like, an organic or inorganic antireflection film can be formed on a substrate to be used, and the influence of basic impurities and the like contained in an environmental atmosphere can be reduced. To prevent this, see, for example, JP-A-5-18
As disclosed in Japanese Patent No. 8598 and the like, a protective film can be provided on a resist film, or these techniques can be used in combination. Next, a predetermined resist pattern is formed by developing the exposed resist film. Examples of the developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, and di-n-propylamine. , Triethylamine,
Methyl diethylamine, ethyl dimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4. An alkaline aqueous solution in which at least one alkaline compound such as 3.0] -5-nonene is dissolved. The concentration of the alkaline aqueous solution is usually
10% by weight or less. In this case, if the concentration of the alkaline aqueous solution exceeds 10% by weight, unexposed portions may be dissolved in the developer, which is not preferable.

Further, for example, an organic solvent can be added to the developer comprising the alkaline aqueous solution. Examples of the organic solvent include acetone, methyl ethyl ketone, methyl i-butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, 2,6
Linear, branched or cyclic ketones such as dimethylcyclohexanone; methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, Alcohols such as 1,4-hexanediol and 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate, n-butyl acetate and i-amyl acetate; fragrances such as toluene and xylene Group hydrocarbons, phenol, acetonylacetone, dimethylformamide and the like. These organic solvents can be used alone or in combination of two or more. The amount of the organic solvent used is preferably 100% by volume or less based on the alkaline aqueous solution. In this case, if the amount of the organic solvent used exceeds 100% by volume, the developability may be reduced and the undeveloped portion of the exposed portion may be increased. Also,
An appropriate amount of a surfactant or the like can be added to the developer composed of the alkaline aqueous solution. After development with a developing solution composed of an alkaline aqueous solution, the film is generally washed with water and dried.

[0181]

Embodiments of the present invention will be described below more specifically with reference to examples. However, the present invention is not limited to these embodiments. Here, parts are by weight unless otherwise specified. Each measurement and evaluation in Examples and Comparative Examples was performed in the following manner. Mw: Tosoh Corporation GPC column (G2000HXL 2
Permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analytical conditions of flow rate 1.0 ml / min, elution solvent tetrahydrofuran, column temperature 40 ° C., using G3000HXL and G4000HXL. It was measured. Radiation transmittance: The composition solution was applied on quartz glass by spin coating, and PB was performed on a hot plate maintained at 90 ° C. for 60 seconds to form a 1 μm-thick resist film. The transmittance was calculated and used as a measure of transparency in the far ultraviolet region.

Sensitivity: As a substrate, a film having a thickness of 520 ° was formed on the surface.
Using a silicone wafer (ARC) on which a DeepUV30 (manufactured by BrewerScience) film was formed, a composition solution was applied on each substrate by spin coating, and on a hot plate under the conditions shown in Table 2. A 0.3 µm-thick resist film formed by PB
Exposure was performed through a mask pattern using a Nikon ArF excimer laser exposure apparatus (lens numerical aperture 0.55, exposure wavelength 193 nm). Then, under the conditions shown in Table 2, PE
B, and then a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (Examples 1 to 8) or 2.
It was developed with a 38 × 1/50% by weight aqueous solution of tetramethylammonium hydroxide (Comparative Example 1) at 25 ° C. for 1 minute, washed with water and dried to form a positive resist pattern. At this time, an exposure amount for forming a line-and-space pattern (1L1S) having a line width of 0.18 μm with a line width of 1: 1 was set as an optimum exposure amount, and the optimum exposure amount was set as a sensitivity. Resolution: The minimum dimension of the resist pattern resolved at the optimal exposure amount was defined as the resolution.

Pattern shape: The lower side dimension Lb and the upper side dimension Lt of a rectangular cross section of a line and space pattern (1L1S) having a line width of 0.20 μm are measured by a scanning electron microscope, and the equation 0.85 ≦ Lt / When Lb ≦ 1 was satisfied and the pattern shape did not have a tail, it was determined that the pattern shape was “good”. Storage stability After the preparation, when a resist film was formed under the above conditions using a composition solution stored at 23 ° C. and evaluated, the resolution and pattern shape were reduced as compared with the case of using the composition solution immediately after preparation. No change was observed, the rate of change in sensitivity was less than 5%, and the increase in the thickness of the resist film formed by coating and drying under the same conditions as when the composition solution immediately after preparation was used was less than 50 °. The storage stability was evaluated based on the maximum number of storage days in which the condition (1) was maintained.

Synthesis Example 1 5-t-butoxycarbonylbicyclo [2.2.1] was placed in a separable flask equipped with a reflux tube under a nitrogen stream.
] Hept-2-ene 135.2 g, maleic anhydride 6
After charging 8.3 g, 77.4 g of 3-hydroxy-1-adamantyl acrylate, 28 g of azobisisobutyronitrile and 280 g of n-butyl acetate, polymerization was carried out at 70 ° C. for 6 hours. After completion of the polymerization, the reaction solution was cooled to room temperature, poured into a large amount of a mixed solution of n-butyl acetate / n-hexane (weight ratio = 1/4) to coagulate the resin, and the coagulated resin was poured into n-hexane. After washing several times with, the content of each repeating unit represented by the following formula is 40 mol% of the repeating unit (Ia), 40 mol% of the repeating unit (II) and 20 mol% of the repeating unit (IIIa). And Mw is 7,0
00 resin was obtained with a yield of 70% by weight. This resin is referred to as resin (C-1).

[0185]

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Synthesis Example 2 Bicyclo [2.2.1] hept-2-ene 16.2 was placed in a separable flask equipped with a reflux tube under a nitrogen stream.
g, 8-hydroxytetracyclo [4.4.0.
^12.5 . 1 ^7,10] dodeca-3-ene 46.3 g, maleic anhydride 45.1 g, 2-methyl-2-adamantyl methacrylate 92.4 g, after charged with azobisisobutyronitrile 40g and acetate n- butyl 200g ,
Polymerization was performed at 70 ° C. for 6 hours. After completion of the polymerization, the reaction solution was cooled to room temperature, poured into a large amount of a mixed solution of n-butyl acetate / n-hexane (weight ratio = 1/4) to coagulate the resin, and the coagulated resin was poured into n-hexane. After washing several times with
After vacuum drying, the content of each repeating unit represented by the following formula,
15 mol% of repeating unit (Ib), repeating unit (Ic) 2
A resin having 0 mol%, 35 mol% of the repeating unit (II) and 30 mol% of the repeating unit (IVa) and having Mw of 6,500 was obtained in a yield of 65% by weight. This resin is referred to as resin (C-2)
And

[0187]

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Synthesis Example 3 In a separable flask equipped with a reflux tube, under a nitrogen stream, 8-hydroxymethyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodeca-3-ene 50.3 g, 5-t
-Butoxycarbonylbicyclo [2.2.1] hept-
38.5 g of 2-ene, 45.3.3 g of maleic anhydride,
After charging 65.9 g of 2- (2-acryloyloxy-2′-propyl) bicyclo [2.2.1] heptane, 20 g of azobisisobutyronitrile and 200 g of n-butyl acetate, polymerize at 70 ° C. for 6 hours. did. After polymerization,
The reaction solution was cooled to room temperature, and a large amount of n-butyl acetate /
Pour into the n-hexane mixed solution (weight ratio = 1/4),
After coagulating the resin and washing the coagulated resin several times with n-hexane, the resin was vacuum-dried, and the content of each repeating unit represented by the following formula was 20 mol% for the repeating unit (Id) and 20% for the repeating unit (Ia). 15 mol%, 35 mol% of the repeating unit (II) and 30 mol% of the repeating unit (IVb), and Mw of 9,
000 resin was obtained in a yield of 75% by weight. This resin is referred to as resin (C-3).

[0189]

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Synthesis Example 4 8-t-butoxycarbonyltetracyclo [4. In a separable flask equipped with a reflux tube under a nitrogen stream.
4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene 89.3
g, 33.6 g of maleic anhydride, 77.1 g of the compound represented by the formula (III-1), azobisisobutyronitrile 2
After charging 0 g and 200 g of n-butyl acetate, 7 g
Polymerization was carried out at 0 ° C. for 6 hours. After completion of the polymerization, the reaction solution was cooled to room temperature, poured into a large amount of a mixed solution of n-butyl acetate / n-hexane (weight ratio = 1/4) to coagulate the resin,
After washing the coagulated resin several times with n-hexane, the resin is vacuum dried, and the content of each repeating unit represented by the following formula is 35 mol% of the repeating unit (Ie), 35 mol% of the repeating unit (II) and 35 mol% of the repeating unit. A resin having a unit (IIIb) of 30 mol% and Mw of 5,500 was obtained at a yield of 60% by weight. This resin is referred to as resin (C-4).

[0191]

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[0192]

EXAMPLES Examples 1 to 8 and Comparative Example 1 Various evaluations were made on each composition solution comprising the components shown in Table 1. Table 3 shows the evaluation results. The components other than the resins (C-1) to (C-4) in Table 1 are as follows. Acid diffusion controller compound (A) A-1: Nt-butoxycarbonyldicyclohexylamine A-2: Nt-butoxycarbonyl-2-phenylbenzimidazole A-3: Nt-butoxycarbonyldi-N- Octylamine A-4: Nt-butoxycarbonyl-4,4'-diaminodiphenylmethane Other compounds α-1: 1-piperidineethanol

Acid generator (B) B-1: triphenylsulfonium nonafluoro-n-
Butanesulfonate B-2: Bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate Other additives D-1: Di-t-butyl 1,3-adamantanedicarboxylate D-2: Deoxycholic acid t-butoxycarbonylmethyl solvent E-1: 2-heptanone E-2: cyclohexanone E-3: propylene glycol monoethyl ether acetate

[0194]

[Table 1]

[0195]

[Table 2]

[0196]

[Table 3]

[0197]

According to the radiation-sensitive composition of the present invention, a specific compound (A) is used in combination with a specific resin (C) as an acid diffusion controlling agent, and particularly a KrF excimer laser (wavelength: 248 nm) or ArF Effectively sensitive to far ultraviolet rays typified by excimer laser (wavelength 193 nm), high in transparency to radiation, excellent in basic properties such as sensitivity, resolution and pattern shape as resist, and storage stability as a composition In addition, it has a sufficient adhesiveness to a substrate, and can be used very suitably in the manufacture of semiconductor devices in which further miniaturization is expected in the future.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/027 H01L 21/30 502R (72) Inventor Akimasa Seiyano 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Tohru Kajita 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Tsutomu Shimokawa 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Co., Ltd. F term (reference) 2H025 AA01 AA02 AA03 AA14 AB16 AC08 AD03 BE00 BE10 BG00 CB10 CB41 CC20 4J002 BG071 BH021 BK001 EB127 EN026 EN036 EN066 EN076 EP016 EQ017 ET016 EU026 EU036 EU116 EU136 EU187 EU236 EV126 EV217 EV217 EV217

Claims (4)

[Claims] (A) A compound having at least one amino group having at least one hydrogen atom bonded to a nitrogen atom, wherein at least one hydrogen atom bonded to the nitrogen atom is substituted with a t-butoxycarbonyl group. (B) a radiation-sensitive acid generator, and (C) an alkali-insoluble or alkali having an alicyclic structure in a main chain and / or a side chain and a carboxylic acid anhydride structure in a side chain. A radiation-sensitive resin composition, comprising a resin containing a hardly soluble acid-dissociable group, the resin being alkali-soluble when the acid-dissociable group is dissociated. 2. An acid-dissociable group containing a repeating unit (I) and a repeating unit (II) represented by the following general formula (1): The radiation-sensitive resin composition according to claim 1, wherein the resin is a resin that becomes alkali-soluble when the acid-dissociable group is dissociated. Embedded image [In the general formula (1), R ¹ and R ² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a linear or branched alkyl group having 1 to 10 carbon atoms. R ³ and R ⁴ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched fluorine group having 1 to 10 carbon atoms, A hydrogenated alkyl group, a monovalent oxygen atom-containing polar group or a monovalent nitrogen atom-containing polar group,
³ and R ⁴ together form a carboxylic anhydride group, and n is an integer of 0 to 2. ] 3. The resin having an acid dissociable group as the component (C) comprises a repeating unit (I) and a repeating unit (II) represented by the following general formula (1) and a repeating unit (II) represented by the following general formula (2): III) and / or an alkali-insoluble or sparingly alkali-soluble acid-dissociable group-containing resin having a repeating unit (IV) represented by the following general formula (3), wherein the resin is alkali-soluble when the acid-dissociable group is dissociated. The radiation-sensitive resin composition according to claim 1, wherein the resin is a resin. Embedded image [In the general formula (1), R ¹ and R ² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a linear or branched alkyl group having 1 to 10 carbon atoms. R ³ and R ⁴ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched fluorine group having 1 to 10 carbon atoms, A hydrogenated alkyl group, a monovalent oxygen atom-containing polar group or a monovalent nitrogen atom-containing polar group,
³ and R ⁴ together form a carboxylic anhydride group, and n is an integer of 0 to 2. [Chemical formula 3] [In the general formula (2), R ⁵ is a hydrogen atom and has 1 to 1 carbon atoms.
4 linear or branched alkyl groups, having 1 to 4 carbon atoms
Represents a straight-chain or branched alkoxyl group or a straight-chain or branched hydroxyalkyl group having 1 to 4 carbon atoms, and A represents a single bond, a methylene group or a main chain having 2 to 2 carbon atoms.
4 represents a linear or branched alkylene group, R ⁶
Represents the following formula (i) (where R ⁷ represents a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, and X ¹ represents a monovalent oxygen-containing polar group or a monovalent nitrogen-containing polar group) ), Formula (ii) (where R ⁸ represents a trivalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, and X ² represents a divalent oxygen-containing polar group or a divalent nitrogen-containing polar group. Or (iii) wherein R ⁹ represents a tetravalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, and X ³ represents 3
And a trivalent oxygen-containing polar group or a trivalent nitrogen-containing polar group. ) Represents a group represented by [Chemical formula 5] [In the general formula (3), R ¹⁰ is a hydrogen atom and has 1 to 1 carbon atoms.
4 linear or branched alkyl groups, having 1 to 4 carbon atoms
A linear or branched alkoxyl group or a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, and each R ¹¹ is independently a monovalent alicyclic group having 4 to 20 carbon atoms. A hydrocarbon group or a derivative thereof, or having 1 to 1 carbon atoms
4 represents a linear or branched alkyl group;
^At least one of R ¹¹ is the alicyclic hydrocarbon group or a derivative thereof, or any two R ¹¹ are bonded to each other to form a divalent group having 4 to 20 carbon atoms together with the carbon atom to which each is bonded. Wherein R ¹¹ is a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched C 1 to C 4 aliphatic hydrocarbon group or a derivative thereof. Represents an alkyl group. ] 4. A component (C) an acid-dissociable group-containing resin, R ⁶ in the repeating unit (III) is an alicyclic hydrocarbon group adamantane skeleton of the R ^7, norbornane skeleton, tricyclodecane skeleton, and A group having a skeleton selected from the group of tetracyclododecane skeletons, wherein X ¹ is a hydroxyl group, or a group represented by the formula (i), or each of the fats at R ¹¹ in the repeating unit (IV) The cyclic hydrocarbon group or a derivative thereof is a group having a bridged skeleton selected from the group of an adamantane skeleton, a norbornane skeleton, a tricyclodecane skeleton, and a tetracyclododecane skeleton independently of each other, Item 4. The radiation-sensitive resin composition according to Item 3.