JP2002202609A - Resist material and pattern forming method - Google Patents

Abstract

(57) Abstract: A resist material comprising, as a base resin, a hydrogenated product of a ring-opening metathesis polymer represented by the following formula. Embedded image The hydrogenated product of the ring-opening metathesis polymer used in the present invention is a polymer which is excellent in heat resistance, heat decomposition resistance, light transmittance and the like and is suitable for a photoresist for semiconductor fine processing using ultraviolet rays or far ultraviolet rays. And is extremely valuable industrially.
The resist material of the present invention using this as a base resin is sensitive to high energy rays and is excellent in sensitivity, resolution and etching resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resist material using a hydrogenated product of a novel ring-opening metathesis polymer as a base resin. And a pattern forming method using the resist material.

[0002]

2. Description of the Related Art In recent years, integration of semiconductor integrated circuits has been advanced, and large-scale integrated circuits (LSI) and very large-scale integrated circuits (VLS) have been developed.
I) has been put to practical use, and the minimum pattern of the integrated circuit has reached the sub-micron region along with it, and will tend to be further miniaturized in the future. To form a fine pattern, the target substrate on which the thin film has been formed is coated with a resist, selective exposure is performed to form a latent image of the desired pattern, and then development is performed to create a resist pattern, which is then used as a mask for dry etching. It is essential to use a lithography technique to obtain a desired pattern by removing the resist thereafter.

As an exposure light source used in this lithography technique, ultraviolet rays of g-line (wavelength: 436 nm) and i-line (wavelength: 365 nm) are used. , Vacuum ultraviolet light, electron beam (EB), X-ray and the like have been used as light sources. Particularly recently, an excimer laser (KrF laser having a wavelength of 248 nm, a wavelength of 193 n
m ArF laser) is attracting attention as an exposure light source, and is expected to be effective for forming fine patterns.

As a polymer or a copolymer used for a resist material for forming a submicron pattern using exposure light in a vacuum ultraviolet region having a shorter wavelength, for example, an ester portion is desorbed by an adamantane skeleton and an acid. A polymer or copolymer of an acrylate ester or an α-substituted acrylate ester having a protective group (see JP-A-4-39665); Polymers or copolymers of α-substituted acrylic acid esters
No. 257281), a polymer or copolymer of cyclohexylmaleimide (see Japanese Patent Application Laid-Open No. 5-257285), and a polymer compound containing a cellulose skeleton in the main chain, which is cleaved by an acid (Japanese Patent Application Laid-Open No. -342212
Many polymers and copolymers have been proposed, such as polyvinyl alcohol or a derivative of polyvinyl alcohol (see JP-A-7-333850).

However, dry etching resistance, transparency to far ultraviolet rays, solubility in resist solvents,
Polymers and copolymers that satisfy all properties necessary for use as a resist material, such as wettability to a developing solution, adhesion to a substrate such as silicon, and solubility in a release agent, etc., and are still easy to synthesize, are still available. No further development is required.

On the other hand, an aliphatic cyclic hydrocarbon is used as a main chain,
Having a cyclic skeleton having a functional group that decomposes by heat
Photoresist composition comprising a compound (WO97 / 33
198, JP-A-9-230595, JP-A-9-24
4247, JP-A-10-254139).
Such cyclic polymers have excellent dry etching resistance.
And has excellent transparency to far ultraviolet rays.
Solubility in resist solvents, wetting in developer
And poor adhesion to the silicon substrate.
Was.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and is sensitive to high energy rays, excellent in sensitivity, resolution and etching resistance, and useful for fine processing by electron beams or far ultraviolet rays. It is an object of the present invention to provide a novel resist material and a pattern forming method using the same.

[0008]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that the above-mentioned various materials necessary for use as a base polymer for a resist material are obtained. Performance, more specifically, for semiconductor microfabrication using ultraviolet light or far ultraviolet light (including excimer laser, etc.), it has excellent light transmittance, etc., has high sensitivity and high resolution, and has affinity for alkali developing solutions. Highly reactive, a hydrogenated hydrogenated ring-opening metathesis polymer having a narrow molecular weight distribution as a polymer that satisfies all of the properties required to be used as a base polymer for a positive photoresist composition capable of obtaining a good pattern. It has been found that it is effective to use it as a base resin. That is, as a hydrogenated product of a ring-opening metathesis polymer of a cyclic olefin monomer, used as a base polymer for a resist material having excellent optical properties, electrical properties, high rigidity, heat resistance, substrate adhesion and weather resistance. After intensive study of the possibilities, a novel ring-opening metathesis polymer having a specific structural unit, that is, an aliphatic cyclic compound as a main chain and having a structural unit containing an oxygen atom as a part of the cyclic structure, has been proposed. The inventor has found that the combined hydrogenated product satisfies the above-mentioned properties as a resist material, and has completed the present invention.

That is, the present invention provides the following resist material and pattern forming method. Claim 1: At least the following general formula [1]

Embedded image (Wherein at least one of R ^{1 to} R ⁴ is represented by the following general formula [2]

Embedded image (In the formula, a chain line represents a bond. R ⁵ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms. alkoxyalkyl group, or a straight, is .R ⁶ in which branched or cyclic acyl group .W ¹ of a straight, branched or cyclic alkyl group having 1 to 10 carbon atoms Represents a single bond or a k + divalent hydrocarbon group having 1 to 10 carbon atoms, Z represents a divalent hydrocarbon group having 2 to 15 carbon atoms, and forms a single ring or a crosslinked ring together with the carbon atoms to be bonded. k is 0 or 1
It is. ) Is a functional group having a tertiary ester group of a cyclic alkyl, and the others are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a halogen atom, a carbon atom A linear, branched or cyclic halogenated alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, 2 to 20 carbon atoms
Linear, branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkylcarbonyloxy group having 2 to 20 carbon atoms, an arylcarbonyloxy group having 6 to 20 carbon atoms, 1 to 20 carbon atoms A linear, branched or cyclic alkylsulfonyloxy group, an arylsulfonyloxy group having 6 to 20 carbon atoms, a linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms, or a C3 to C2
Of 20 linear, selected from alkoxycarbonyl alkyl group branched or cyclic, ^{X 1} is -O- or ^-CR _{7 2} -
(R ⁷ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), which may be the same or different. j represents 0 or an integer of 1 to 3. ) And the following general formula [3]

Embedded image(Where R⁸~ R¹¹Are each independently a hydrogen atom or
Is a linear, branched or cyclic alkyl having 1 to 10 carbons
X²Is -O- or -CR¹² ₂− (R ¹²Is
A hydrogen atom or a linear or branched alkyl having 1 to 10 carbon atoms
Represents a kill group), and may be the same or different. m is
Represents an integer of 0 or 1 to 3. ) Structural unit
[B] and / or the following general formula [4]

Embedded image (Wherein, R ^{13 to} R ¹⁶ are each independently a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and X ³ is —O— or —CR ¹⁷ ₂ —. (R ¹⁷
Represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), which may be the same or different. Y
¹ and Y ² are each — (C ＝ O) — and the other is
—CR ¹⁸ ₂ — (R ¹⁸ is a hydrogen atom or a group having 1 to 10 carbon atoms.
Represents a linear or branched alkyl group). n represents 0 or an integer of 1 to 3. It is composed of structural units [C] represented by), and, X of the general formula X ¹ in the structural unit [A] represented by ^[1], general formula [3] structural units represented by [B] ² and at least one of X ^{3 in} the structural unit [C] represented by the general formula [4] is —O—, and the constituent molar ratio [A] / ([B] + [C]) is 20. / 80
As a base resin, a hydrogenated product of a ring-opening metathesis polymer having a weight average molecular weight Mw and a number average molecular weight Mn (Mw / Mn) of 1.0 to 2.0. A resist material comprising: Claim 2: The functional group having a tertiary ester group of the cyclic alkyl represented by the general formula [2] selected as at least one of R ^{1 to} R ⁴ of the general formula [1] is a 1-alkylcyclopentyl ester The resist material according to claim 1, which is a 2-alkyl-2-norbornyl ester or a 2-alkyl-2-adamantyl ester. Claim 3: The hydrogenated product of the ring-opening metathesis polymer further has the following general formula [5]:

Embedded image (Wherein at least one of R ^{19 to} R ²² is represented by the following general formula [6]

Embedded image (In the formula, a chain line represents a bond. R ²³ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms. Represents an alkoxyalkyl group or a linear, branched or cyclic acyl group having 1 to 10 carbon atoms, and W ² is a single bond or 1 to 10 carbon atoms.
Represents a k + divalent hydrocarbon group. q is 0 or 1. ) Is a functional group having a carboxylic acid group represented by
Others are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a halogen atom,
C1-C20 linear, branched or cyclic halogenated alkyl group, C1-C20 linear, branched or cyclic alkoxy group, C2-C20 linear or branched Or a cyclic alkoxyalkyl group, a linear, branched or cyclic alkylcarbonyloxy group having 2 to 20 carbon atoms, an arylcarbonyloxy group having 6 to 20 carbon atoms,
-20 linear, branched or cyclic alkylsulfonyloxy group, a C6-C20 arylsulfonyloxy group, a C2-C20 linear, branched or cyclic alkoxycarbonyl group, or 3-20 linear, selected from alkoxycarbonyl alkyl group branched or cyclic, ^{X 4} is -O- or ^{-CR ₂₄} 2 - ^(R ₂₄ represents a linear hydrogen atom or a C1-10 or Represents a branched alkyl group), and may be the same or different. p represents 0 or an integer of 1 to 3. 3. The resist material according to claim 1, which comprises a structural unit [D] represented by the formula: Claim 4: In the hydrogenated product of the ring-opening metathesis polymer contained as the base resin, the structural unit [A] represented by the general formula [1] and the structural unit [B] represented by the general formula [3]
And the structural molar ratio of the structural unit [D] represented by the general formula [5] to the structural unit [C] represented by the general formula [4] ([A] + [B] + [C]) / [D Is 100 / 0-2
The resist material according to claim 3, wherein the ratio is 0/80. Claim 5: The hydrogenated product of the ring-opening metathesis polymer further has a general formula [7]

Embedded image (Wherein at least one of R ^{25 to} R ²⁸ is represented by the following general formula [8]

Embedded image(In the formula, a chain line indicates a bond. R²⁹Is a hydrogen atom, carbon
A linear, branched or cyclic alkyl group of the formulas 1 to 10;
Linear, branched or cyclic alkoxya having a prime number of 2 to 10
Alkyl group, or linear, branched or cyclic C 1-10
Represents an acyl group. R³⁰Is a linear chain having 1 to 10 carbon atoms
, Branched or cyclic alkyl groups having 2 to 10 carbon atoms
Chain, branched or cyclic alkoxyalkyl group, or charcoal
A linear, branched or cyclic halogenated amine having a prime number of 1 to 20;
Represents a alkyl group. W³Is a single bond or k having 1 to 10 carbon atoms
+ Represents a divalent hydrocarbon group. s is 0 or 1. )so
It is a functional group having a carboxylic acid ester group represented,
Others are each independently a hydrogen atom, having 1 to 20 carbon atoms.
Linear, branched or cyclic alkyl group, halogen atom,
Linear, branched or cyclic halogenation having 1 to 20 carbon atoms
Alkyl group, C1-C20 linear, branched or cyclic
An alkoxy group, having 2 to 20 carbon atoms, linear, branched or
Cyclic alkoxyalkyl group, straight chain having 2 to 20 carbon atoms
, Branched or cyclic alkylcarbonyloxy group, charcoal
An arylcarbonyloxy group having a prime number of 6 to 20, having 1 carbon atom
-20 linear, branched or cyclic alkylsulfonyl
Oxy group, arylsulfonyloxy having 6 to 20 carbon atoms
Group, a linear, branched or cyclic alcohol having 2 to 20 carbon atoms
Xycarbonyl group or C3-C20 linear, branched
Selected from linear or cyclic alkoxycarbonylalkyl groups
X⁵Is -O- or CR³¹ ₂− (R³¹Is a hydrogen atom
Or a linear or branched alkyl group having 1 to 10 carbon atoms
) And may be the same or different. r is 0 or 1
Represents an integer of 1 to 3. ) Contains the structural unit [E]
The resist material according to claim 1. Claim 6: Ring-opening metathesis weight contained as a base resin
In the combined hydrogenated product, the structure represented by the general formula [1] is used.
Structural unit [A], structural unit [B] represented by general formula [3]
And the structural unit [C] represented by the general formula [4]
Constituent molar ratio of structural unit [E] represented by general formula [7]
([A] + [B] + [C]) / [E] is 100/0 to 4
The resist material according to claim 5, wherein the ratio is 0/60. Claim 7: Ring-opening metathesis weight contained as a base resin
In terms of polystyrene measured by GPC of the combined hydrogenated product
Has a number average molecular weight Mn of 500 to 200,000.
The laser according to any one of claims 1 to 6, characterized in that:
Zyst material. Claim 8: Ring-opening metathesis weight contained as a base resin
In terms of polystyrene measured by GPC of the combined hydrogenated product
Has a number average molecular weight Mn of 3,000 to 20,000.
The resist material according to claim 7, wherein: Claim 9: The cash register according to any one of claims 1 to 8
Process of applying a test material on a substrate and photo
Exposure with high energy beam or electron beam through mask
Process and, if necessary, heat treatment, and then
Patterning, comprising the steps of:
Method.

Hereinafter, the present invention will be described in more detail.
The resist material of the present invention comprises, as a base resin, a structural unit [A] represented by the following general formula [1], a structural unit [B] represented by the following general formula [3], and / or the following general formula [3] [4] A hydrogenated product of a ring-opening metathesis polymer containing a structural unit represented by the following formula:

[0011]

Embedded image

Here, in the general formula [1] of the present invention,
At least one of R ^{1 to} R ⁴ is represented by the following general formula [2]
Is a tertiary ester group of a cyclic alkyl represented by

[0013]

Embedded image (In the formula, a chain line represents a bond. R ⁵ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms. alkoxyalkyl group, or a straight, is .R ⁶ in which branched or cyclic acyl group .W ¹ of a straight, branched or cyclic alkyl group having 1 to 10 carbon atoms Represents a single bond or a k + divalent hydrocarbon group having 1 to 10 carbon atoms, Z represents a divalent hydrocarbon group having 2 to 15 carbon atoms, and forms a single ring or a crosslinked ring together with the carbon atoms to be bonded. k is 0 or 1
It is. )

In R ⁵ , a linear group having 1 to 10 carbon atoms;
Examples of the branched or cyclic alkyl group include methyl,
Ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, 1-ethylcyclopentyl, 1-ethylcyclohexyl and the like, and are straight-chain, branched or cyclic having 2 to 10 carbon atoms. Examples of the alkoxyalkyl group include methoxymethyl, 1-ethoxyethyl, 1-tert-
Butoxyethyl, 1-cyclohexyloxyethyl, 1
-Ethoxypropyl, 1-ethoxy-1-methylethyl, tetrahydrofuran-2-yl, tetrahydropyran-2-yl and the like, and a straight-chain, branched or cyclic acyl group having 1 to 10 carbon atoms includes For example, formyl, acetyl, pivaloyl, cyclohexylcarbonyl and the like. Among these R ⁵ , C 1 to C 1
A linear or branched alkyl group having 6 to 7 carbon atoms, a linear or branched alkoxyalkyl group having 2 to 7 carbon atoms, and a linear or branched acyl group having 2 to 7 carbon atoms are preferable,
In particular, a hydrogen atom, methyl, ethyl, methoxymethyl, 1-
Ethoxyethyl, tetrahydrofuran-2-yl and acetyl are preferred.

In R ⁶ , a linear group having 1 to 10 carbon atoms;
Examples of the branched or cyclic alkyl group include methyl,
Ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, cyclooctyl, norbornyl, 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-methylnorbonyl And 1-ethylnorbonyl, among which methyl, ethyl, propyl, isopropyl,
Preferred are n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, norbornyl, 1-ethylcyclopentyl and 1-ethylcyclohexyl.

In W ¹ , as a k + divalent hydrocarbon group having 1 to 10 carbon atoms, when k is 0, 1 to 10 carbon atoms
Is a linear, branched or cyclic divalent hydrocarbon group,
For example, methylene, dimethylmethylene, ethylidene, propylidene, butylidene, ethylene, 1-methylethylene, 2-methylethylene, 1-ethylethylene, 2-ethylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 2, 2-dimethylethylene, 1-ethyl-2-methylethylene, trimethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, tetramethylene, pentamethylene, 1,1-
Cyclopentylene, 1,2-cyclopentylene, 1,3
-Cyclopentylene, 1,1-cyclohexylene, 1,
2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene and the like can be mentioned. Of these, methylene, ethylidene, ethylene, 1-methylethylene, 2-methylethylene, trimethylene, and 2-methyltrimethylene are preferred. In the case where k is 1, for example, a bond other than one hydrogen atom at an arbitrary position on the hydrocarbon group mentioned in the case where k is 0 is used as a bond.

Z is a divalent hydrocarbon group having 2 to 15 carbon atoms and forms a monocyclic or bridged ring together with the carbon atoms to be bonded. That is

Embedded image As the group represented by, for example, the following general formula [13]

Embedded image (In the formula, R ⁶ is as defined above. R ^{32 to} R ³⁷ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. B is 0 or 1 to 6 And when b is 2 to 6, a plurality of R ³⁴ and R ³⁵ may be the same or different.) 1-alkylcycloalkyl group represented by the following general formula [1
4]

Embedded image (Wherein, R ⁶ is as defined above; R ^{38 to} R ⁴⁷ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms). Examples thereof include an alkyl-2-norbonyl group and a 2-alkyl-2-adamantyl group such as 2-methyl-2-adamantyl and 2-ethyl-2-adamantyl.

Specific examples of the general formula [13] include 1-methylcyclopropyl, 1-methylcyclobutyl, 1-ethylcyclobutyl, 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, -Iso-propylcyclopentyl, 1-ter
t-butylcyclopentyl, 1-cyclopentylcyclopentyl, 1-cyclohexylcyclopentyl, 1-norbornylcyclopentyl, 1-methylcyclohexyl,
1-ethylcyclohexyl, 1-methylcycloheptyl, 1-ethylcycloheptyl, 1-methylcyclooctyl, 1-methylcyclononyl, and the like, among which 1-methylcyclopentyl, 1-ethylcyclopentyl, n-propylcyclopentyl, 1-i
so-propylcyclopentyl, 1-tert-butylcyclopentyl, 1-cyclopentylcyclopentyl,
The following chemical formulas [15-1] to [15] such as 1-cyclohexylcyclopentyl and 1-norbornylcyclopentyl
-8]

Embedded image Is preferable, and 1-methylcyclopentyl [15-1] and 1-ethylcyclopentyl [15-2] are more preferable.

Specific examples of the general formula [14] include the following chemical formulas [16-1] to [16-11].

Embedded image And the like, and among these, [16-1], [16-2], and [16-3]
And [16-4] are preferred.

Others among R ^{1 to} R ⁴ are each independently a hydrogen atom, methyl or ethyl having 1 to 20 carbon atoms,
A linear, branched or cyclic alkyl group such as propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or menthyl; a halogen atom such as a chlorine atom, a bromine atom, an iodine atom or a fluorine atom; A linear, branched or cyclic halogenated alkyl group such as fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl or tribromomethyl, having 1 carbon atom
Linear, branched or cyclic alkoxy groups such as methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy or mentoxy, methoxymethyl having 2 to 20 carbon atoms, methoxyethyl, tert-butoxymethyl, linear, branched or cyclic alkoxyalkyl groups such as tert-butoxyethyl or methoxymenthol, or containing alkoxy sugars such as methyl glucose,
A linear, branched or cyclic alkylcarbonyloxy group such as acetoxy having 2 to 20 carbon atoms, an arylcarbonyloxy group such as naphthoyloxy having 6 to 20 carbon atoms, and a straight chain such as mesyloxy having 1 to 20 carbon atoms. , Branched or cyclic alkylsulfonyloxy group, arylsulfonyloxy group such as tosyloxy having 6 to 20 carbon atoms, 2 to 2 carbon atoms
20 methoxycarbonyl, ethoxycarbonyl, n-
Propoxycarbonyl, isopropoxycarbonyl, n
-Butoxycarbonyl, tert-butoxycarbonyl, or a linear chain such as cyclohexyloxycarbonyl,
Branched or cyclic alkoxycarbonyl group, having 3 to 3 carbon atoms
20 methoxycarbonylmethyl, 2- (methoxycarbonyl) ethyl, 1- (methoxycarbonyl) ethyl,
Linear, branched or cyclic such as ethoxycarbonylmethyl, 2- (ethoxycarbonyl) ethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, n-butoxycarbonylmethyl, tert-butoxycarbonylmethyl, or cyclohexyloxycarbonylmethyl Are specific examples. Of these, a hydrogen atom and a carbon number of 1 to 1
20 linear, branched or cyclic alkyl groups, 1 carbon atom
Linear, branched or cyclic alkoxy group having 2 to 20 carbon atoms, linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, linear, branched or cyclic alkoxy group having 2 to 20 carbon atoms A carbonyl group, and a straight-chain having 3 to 20 carbon atoms,
A branched or cyclic alkoxycarbonylalkyl group is preferable, and more preferably a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched alkoxycarbonyl group having 2 to 10 carbon atoms. , And 3 or more carbon atoms
And 10 linear or branched alkoxycarbonylalkyl groups.

[0021] ^{X 1} is -O- or ^-CR ₇ 2 - is a ^{(R 7} represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms). j is 0 or an integer of 1 to 3,
When j is 1 to 3, X ¹ may be the same or different. R
⁷ is a hydrogen atom, or methyl, ethyl, n-propyl, isopropyl, n-butyl or t-carbon having 1 to 10 carbon atoms
Specific examples include a linear or branched alkyl group such as tert-butyl. X ¹ is preferably -O-
Or -CH ₂ -, more preferably all of ^{X 1} is -
O- or -CH ₂ - is either. j is preferably 0 or 1.

Specific examples of the general formula [1] include structural units [A] represented by the following chemical formulas [17-1-1] to [17-4-16].

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

In the general formula [3], R⁸~ R
¹¹Are each independently a hydrogen atom or a group having 1 to 10 carbon atoms.
Methyl, ethyl, n-propyl, isopropyl, n-
Butyl, tert-butyl, cyclohexyl or mench
Specific examples are linear, branched or cyclic alkyl groups such as
It is mentioned. X²Is -O- or -CR¹² ₂− (R
¹²Is a hydrogen atom or a straight or branched chain having 1 to 10 carbon atoms
Represents alkyl). m is 0 or an integer of 1 to 3
Yes, if m is 1-3, X²May be the same or different
No. R¹²As a hydrogen atom or a C 1-10
Chill, ethyl, n-propyl, isopropyl, n-butyl
Linear or branched alkyl such as
A specific example is a hydroxyl group. X²As preferred
Is -O- or -CH₂-, More preferably all
X²Is -O- or -CH₂-Any of m
And preferably 0 or 1.

Specific examples of the general formula [3] include structural units [B] represented by the following chemical formulas [18-1] to [18-16].

[0029]

Embedded image

In the general formula [4], R ^{13 to} R
¹⁶ are each independently a hydrogen atom or a group having 1 to 1 carbon atoms.
0 methyl, ethyl, n-propyl, isopropyl, n
Specific examples include a linear, branched or cyclic alkyl group such as -butyl, tert-butyl, cyclohexyl or menthyl. X ³ is -O- or ^{-CR 17} ₂ -
(R ¹⁷ represents a hydrogen atom or a linear or branched alkyl having 1 to 10 carbon atoms). n is 0 or an integer of 1 to 3, and when n is 1 to 3, X ³ may be the same or different. R ¹⁷ is a hydrogen atom or a C 1-10
Methyl, ethyl, n-propyl, isopropyl, n-
A specific example is a linear or branched alkyl group such as butyl or tert-butyl. X ³ is preferably —O— or —CH ₂ —, and more preferably all X ³ are either —O— or —CH ₂ —. Y
¹ and Y ² are each — (C ＝ O) — and the other is
—CR ¹⁸ ₂ — (R ¹⁸ is a hydrogen atom or a group having 1 to 10 carbon atoms.
Represents a linear or branched alkyl group). R
¹⁸ is a hydrogen atom or methyl having 1 to 10 carbons,
Specific examples include linear or branched alkyl groups such as ethyl, n-propyl, isopropyl, n-butyl and tert-butyl. One of Y ¹ and Y ² is preferably — (C ＝ O) —, and the other is —CH ₂ —. n is preferably 0 or 1.

Specific examples of the general formula [4] include structural units [C] represented by the following chemical formulas [19-1] to [19-16].

[0032]

Embedded image

The hydrogenated product of the ring-opening metathesis polymer used in the present invention includes X ¹ of the structural unit [A] represented by the general formula [1] and the structural unit [B] represented by the general formula [3]. X ² ,
And a hydrogenated product of a ring-opening metathesis polymer in which at least one of X ³ of the structural unit [C] represented by the general formula [4] is —O—, and thus the oxygen atom is a main chain. By being present in the aliphatic cyclic compound, adhesion to a substrate to be processed such as a silicon substrate, improvement in wetting tension during development with an alkaline aqueous solution, ketones used in a step of applying a resist agent to a silicon wafer, This has the effect of further improving the solubility in polar organic solvents such as alcohols, improving the affinity for water, and improving the developability with a release agent (or developer) such as an aqueous alkali solution after exposure. Preferably, X ¹ of the structural unit [A] represented by the general formula [1], X ² of the structural unit [B] represented by the general formula [3], and the structure represented by the general formula [4] It is a hydrogenated product of a ring-opening metathesis polymer in which at least one of X ^{3 in} the unit [C] is —O— and the other is —CH ₂ —. The amount of -O- units to the total sum unit amount of X ^{1, X 2} and ^{X 3} is 1 to 99 mol%, preferably from 2 to 95 mol%, more preferably 5 to 80 mol% , Most preferably from 10 to 70 mol%.

In the present invention, the structural unit [A] represented by the general formula [1] and the structural unit [B] represented by the general formula [3] and / or the structural unit represented by the general formula [4] The molar ratio [A] / ([B] + [C]) of [C] is 20/8
0 to 99/1, and it is essential that a certain amount of the structural unit [B] and / or [C] be present in addition to the structural unit [A]. Here, the structural unit [A] includes a tertiary ester group of a cyclic alkyl represented by the general formula [2], that is, a group which is decomposed by an acid generated from a photosensitizer upon exposure to generate a carboxylic acid. After exposure, it is necessary to develop with an aqueous alkali solution to form a resist pattern. In addition, the structural units [B] and / or [C] are necessary for developing adhesion to a substrate to be processed such as a silicon substrate. The molar ratio [A] / ([B] + [C]) is 20/80.
When the ratio is less than the above, the development becomes insufficient, and when it exceeds 99/1, the adhesion to the substrate to be processed does not appear. Preferably, the molar ratio [A] / ([B] + [C]) is 20/80 to 95/5.
, More preferably 25/75 to 90/10, and most preferably 30/70 to 85/15. Having these structural units in this range is suitable for preparing a resist composition, and together with a highly polar photosensitizer,
For example, it is extremely important as a resist material that is dissolved in a polar solvent such as 2-heptanone and applied to a substrate to be processed such as a silicon substrate. That is, a uniform smooth coating film can be formed by increasing the solubility or dissolution rate of a hydrogenated product of the ring-opening metathesis polymer in a polar solvent when preparing a resist material.

In the hydrogenated product of the ring-opening metathesis polymer used in the present invention, at least one of the structural units [B] and [C] is essential, and in addition to the structural unit [A], the structural unit [B] Or a terpolymer composed of [C], but is preferably a structural unit [B] or [C].
Is a binary copolymer composed of only one of the above.

The hydrogenated product of the ring-opening metathesis polymer used in the present invention is limited to a narrow molecular weight distribution in which the ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight is 1.0 to 2.0. . The molecular weight distribution greatly affects the resolution when used as a resist material, and the narrower the molecular weight distribution, the higher the resolution of the pattern. Preferably it is in the range of 1.0 to 1.8, more preferably 1.0 to 1.6. The molecular weight of the hydrogenated product of the ring-opening metathesis polymer of the present invention usually has a number average molecular weight Mn of 500 to 200,000. It is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, and still more preferably 3,000.
~ 20,000. The number average molecular weight and weight average molecular weight described in the present specification are gel permeation chromatography (GP) in terms of polystyrene.
C).

The hydrogenated products of these ring-opening metathesis polymers have structural units [A], [B] and / or [C]
Each of the structural units may be composed of one type of structural unit, or any or all of the structural units may be composed of two or more types of structural units. For example, when the structural unit [A] is represented by the following general formulas [1-1] and [1-2]

Embedded image (In the formula, at least one of R ^{48 to} R ⁵¹ is a functional group having a tertiary ester group of a cyclic alkyl represented by the general formula [2], and the others are each independently a hydrogen atom, a carbon atom 1 ~ 20 linear, branched or cyclic alkyl groups, halogen, C1-20 linear, branched or cyclic halogenated alkyl groups, C1-20 linear, branched or A cyclic alkoxy group, a linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, a linear, branched or cyclic alkylcarbonyloxy group having 2 to 20 carbon atoms, Arylcarbonyloxy group, C1-C20 linear, branched or cyclic alkylsulfonyloxy group, C6-C20 arylsulfonyloxy group, C2-C20 linear, branched or cyclic Alcoqui Carbonyl group, or a carbon number 3-2
It is selected from 0 linear, branched or cyclic alkoxycarbonylalkyl groups, and j1 represents 0 or an integer of 1 to 3. )

Embedded image (In the formula, at least one of R ^{52 to} R ⁵⁵ is a functional group having a tertiary ester group of a cyclic alkyl represented by the general formula [2], and the others are each independently a hydrogen atom, a carbon atom 1 group. ~ 20 linear, branched or cyclic alkyl groups, halogen, C1-20 linear, branched or cyclic halogenated alkyl groups, C1-20 linear, branched or A cyclic alkoxy group, a C2-20 linear, branched or cyclic alkoxyalkyl group, a C2-20 linear, branched or cyclic alkylcarbonyloxy group, a C6-20 Arylcarbonyloxy group, C1-C20 linear, branched or cyclic alkylsulfonyloxy group, C6-C20 arylsulfonyloxy group, C2-C20 linear, branched or cyclic Alcoqui Carbonyl group, or a carbon number 3-2
It is selected from 0 linear, branched or cyclic alkoxycarbonylalkyl groups, and j2 represents 0 or an integer of 1 to 3. )) And the structural units [A-1] and [A-2]
And the structural unit [B] is represented by the following general formulas [3-1] and [3-
2]

Embedded image (In the formula, R ^{56 to} R ⁵⁹ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and m1 represents an integer of 0 or 1 to 3. )

Embedded image (In the formula, R ^{60 to} R ⁶³ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and m2 represents an integer of 0 or 1 to 3. The structural units [B-1] and [B-2] and / or the structural unit [C] represented by the following general formulas [4-1] and [4-2]

Embedded image (Wherein, R ^{64 to} R ⁶⁷ are each independently a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and one of Y ³ and Y ⁴ is-(C = O)-and the other is -CH2-, and n1 represents 0 or an integer of 1 to _3. )

Embedded image (Wherein, R ^{68 to} R ⁷¹ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and one of Y ⁵ and Y ⁶ is-(C = O) - and is the other is -CH ₂ -. a, n2 represents an integer of 0 or 1 to 3) structural units [C-1] represented by and [C-
2], which is a hydrogenated product of the ring-opening metathesis polymer.

The hydrogenated product of the ring-opening metathesis copolymer used in the present invention has the following general formula [5] in addition to the structural units [A] and [B] and / or [C].

Embedded image (Wherein at least one of R ^{19 to} R ²² is represented by the following general formula [6]

Embedded image (In the formula, a chain line represents a bond. R ²³ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms. Represents an alkoxyalkyl group or a linear, branched or cyclic acyl group having 1 to 10 carbon atoms, and W ² is a single bond or 1 to 10 carbon atoms.
Represents a k + divalent hydrocarbon group. q is 0 or 1. ) Is a functional group having a carboxylic acid group represented by
Others are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a halogen atom,
C1-C20 linear, branched or cyclic halogenated alkyl group, C1-C20 linear, branched or cyclic alkoxy group, C2-C20 linear or branched Or a cyclic alkoxyalkyl group, a linear, branched or cyclic alkylcarbonyloxy group having 2 to 20 carbon atoms, an arylcarbonyloxy group having 6 to 20 carbon atoms,
-20 linear, branched or cyclic alkylsulfonyloxy group, a C6-C20 arylsulfonyloxy group, a C2-C20 linear, branched or cyclic alkoxycarbonyl group, or 3-20 linear, selected from alkoxycarbonyl alkyl group branched or cyclic, ^{X 4} is -O- or ^{-CR ₂₄} 2 - ^(R ₂₄ represents a linear hydrogen atom or a C1-10 or Represents a branched alkyl group), and may be the same or different. p represents 0 or an integer of 1 to 3. It is preferable to further have the structural unit [D] represented by the formula (1) as a structural unit in order to further improve the substrate adhesion and the affinity for the developing solution.

R²³, A linear chain having 1 to 10 carbon atoms
As a branched, branched or cyclic alkyl group, for example, methyl
, Ethyl, propyl, isopropyl, n-butyl,
Sobutyl, tert-butyl, cyclopentyl, cyclo
Hexyl, 1-ethylcyclopentyl, and 1-ethyl
Cyclohexyl and the like, and a straight chain having 2 to 10 carbon atoms.
As a, branched or cyclic alkoxyalkyl group,
For example, methoxymethyl, 1-ethoxyethyl, 1-te
rt-butoxyethyl, 1-cyclohexyloxyethyl
1-ethoxypropyl, 1-ethoxy-1-methyl
Ethyl, tetrahydrofuran-2-yl, and tetrahi
Dropyran-2-yl and the like, having 1 to 10 carbon atoms
As the linear, branched or cyclic acyl group, for example,
Olmil, acetyl, pivaloyl, and cyclohexyl
Carbonyl and the like. These R ²³Out of carbon
A linear or branched alkyl group having 1 to 6 carbon atoms, 2 to 2 carbon atoms
7, a linear, branched or cyclic alkoxyalkyl group;
And a linear or branched acyl group having 2 to 7 carbon atoms is preferred.
Especially hydrogen, methyl, ethyl, methoxymethyl
, 1-ethoxyethyl, tetrahydrofuran-2-i
And acetyl are preferred.

In W ² , as q + 2 valent hydrocarbon group having 1 to 10 carbon atoms, when q is 0, 1 to 10 carbon atoms
Is a linear, branched or cyclic divalent hydrocarbon group,
For example, methylene, dimethylmethylene, ethylidene, propylidene, butylidene, ethylene, 1-methylethylene, 2-methylethylene, 1-ethylethylene, 2-ethylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 2, 2-dimethylethylene, 1-ethyl-2-methylethylene, trimethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, tetramethylene, pentamethylene, 1,1-
Cyclopentylene, 1,2-cyclopentylene, 1,3
-Cyclopentylene, 1,1-cyclohexylene, 1,
Examples include 2-cyclohexylene, 1,3-cyclohexylene, and 1,4-cyclohexylene. Of these, methylene, ethylidene, ethylene, 1-methylethylene, 2-methylethylene, trimethylene, and 2-
Methyl trimethylene is preferred. In the case where k is 1, for example, a bond other than one hydrogen atom at an arbitrary position on the hydrocarbon group mentioned in the case where k is 0 is used as a bond.
The most preferred W ² is a single bond.

The others of R ^{19 to} R ²² are each independently a hydrogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, tert-carbon having 1 to 20 carbon atoms.
Linear, branched or cyclic alkyl groups such as butyl, cyclohexyl or menthyl, halogens such as chlorine, bromine, iodine or fluorine, C1-C20 fluoromethyl, chloromethyl, bromomethyl, difluoromethyl Linear, branched or cyclic alkyl halide groups such as dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl or tribromomethyl, methoxy, ethoxy, isopropoxy having 1 to 12 carbon atoms, n
Linear, branched or cyclic alkoxy groups such as -butoxy, tert-butoxy or mentoxy, having 2 to 20 carbon atoms
Methoxymethyl, methoxyethyl, tert-butoxymethyl, tert-butoxyethyl or methoxymenthol or the like, or a linear, branched or cyclic alkoxyalkyl group containing an alkoxy sugar such as methyl glucose, having 2 to 20 carbon atoms Linear, branched or cyclic alkylcarbonyloxy group such as acetoxy, having 6 to 20 carbon atoms
Aryl carbonyloxy group such as naphthoyloxy,
A linear, branched or cyclic alkylsulfonyloxy group such as mesyloxy having 1 to 20 carbon atoms, an arylsulfonyloxy group such as tosyloxy having 6 to 20 carbon atoms, methoxycarbonyl having 2 to 20 carbon atoms, ethoxycarbonyl,
a linear, branched or cyclic alkoxycarbonyl group such as n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl, or cyclohexyloxycarbonyl; methoxycarbonylmethyl having 3 to 20 carbon atoms; (Methoxycarbonyl) ethyl, 1- (methoxycarbonyl) ethyl, ethoxycarbonylmethyl, 2- (ethoxycarbonyl) ethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, n-butoxycarbonylmethyl, tert-butoxycarbonylmethyl, or Specific examples include a linear, branched or cyclic alkoxycarbonylalkyl group such as cyclohexyloxycarbonylmethyl. Among them, hydrogen atom, carbon number 1
Linear, branched or cyclic alkyl group having from 20 to 20 carbon atoms, linear, branched or cyclic alkoxy group having from 1 to 20 carbon atoms, linear, branched or cyclic alkoxyalkyl having from 2 to 20 carbon atoms Group, a straight-chain, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms, and a straight-chain, branched or cyclic alkoxycarbonylalkyl group having 3 to 20 carbon atoms, more preferably a hydrogen atom, Carbon number 1-10
A linear or branched alkylcarbonyl group having 2 to 10 carbon atoms, and a linear or branched alkoxycarbonylalkyl group having 3 to 10 carbon atoms.

[0042] ^{X 4} is -O- or ^CR ₂₃ 2 - a ^{(R 23} represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), when p is 1 to 3, X ⁴ may be the same or different. As R ²³ is a hydrogen atom, or methyl having 1 to 10 carbon atoms, ethyl, n- propyl, isopropyl, straight or branched alkyl group such as n- butyl or tert- butyl can be given as specific examples. X ⁴
As preferably -O- or CH ₂ -, more preferably an all ^{X 4} is -O- or CH ₂ - is either. p is preferably 0 or 1.

Specific examples of the general formula [5] include structural units [D] represented by the following chemical formulas [20-1-1] to [20-4-16].

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

In a preferred embodiment of the present invention, the structural unit [A] represented by the general formula [1], the structural unit [B] represented by the general formula [3], and the general formula [4] The molar ratio of the structural unit [D] represented by the general formula [5] to the structural unit [C] ([A] + [B] + [C]) /
[D] is 100/0 to 20/80, and it is preferable that a certain amount of the structural unit [D] be present in addition to the structural units [A], [B], and [C]. Here, the structural unit [D] greatly enhances adhesion to a substrate to be processed such as a silicon substrate, and further improves affinity for a developer. Preferably, the molar ratio ([A] + [B] + [C]) / [D] is 98/2 to 50/50, more preferably 97/3.
６０60/40, most preferably 95/5 to 70/30. The hydrogenated product of the ring-opening metathesis copolymer used in the present invention may be a compound represented by the following general formula [7], in addition to the structural units [A] and [B] and / or [C], preferably [D].

Embedded image (Wherein at least one of R ^{25 to} R ²⁸ is represented by the following general formula [8]

Embedded image(In the formula, a chain line indicates a bond. R²⁹Is a hydrogen atom, carbon
A linear, branched or cyclic alkyl group of the formulas 1 to 10;
Linear, branched or cyclic alkoxya having a prime number of 2 to 10
Alkyl group, or linear, branched or cyclic C 1-10
Represents an acyl group. R³⁰Is a linear chain having 1 to 10 carbon atoms
, Branched or cyclic alkyl groups having 2 to 10 carbon atoms
Chain, branched or cyclic alkoxyalkyl group, or charcoal
A linear, branched or cyclic halogenated amine having a prime number of 1 to 20;
Represents a alkyl group. W³Is a single bond or k having 1 to 10 carbon atoms
+ Represents a divalent hydrocarbon group. s is 0 or 1. )so
It is a functional group having a carboxylic acid ester group represented,
Others are each independently a hydrogen atom, having 1 to 20 carbon atoms.
Linear, branched or cyclic alkyl group, halogen atom,
Linear, branched or cyclic halogenation having 1 to 20 carbon atoms
Alkyl group, C1-C20 linear, branched or cyclic
An alkoxy group, having 2 to 20 carbon atoms, linear, branched or
Cyclic alkoxyalkyl group, straight chain having 2 to 20 carbon atoms
, Branched or cyclic alkylcarbonyloxy group, charcoal
An arylcarbonyloxy group having a prime number of 6 to 20, having 1 carbon atom
-20 linear, branched or cyclic alkylsulfonyl
Oxy group, arylsulfonyloxy having 6 to 20 carbon atoms
Group, a linear, branched or cyclic alcohol having 2 to 20 carbon atoms
Xycarbonyl group or C3-C20 linear, branched
Selected from linear or cyclic alkoxycarbonylalkyl groups
X⁵Is -O- or CR³¹ ₂− (R³¹Is a hydrogen atom
Or a linear or branched alkyl group having 1 to 10 carbon atoms
) And may be the same or different. r is 0 or 1
Represents an integer of 1 to 3. ) Is further added to the structural unit [E]
You may have as a structural unit.

R²⁸, A linear chain having 1 to 10 carbon atoms
As a branched, branched or cyclic alkyl group, for example, methyl
, Ethyl, propyl, isopropyl, n-butyl,
Sobutyl, tert-butyl, cyclopentyl, cyclo
Hexyl, 1-ethylcyclopentyl, and 1-ethyl
Cyclohexyl and the like, and a straight chain having 2 to 10 carbon atoms.
As a, branched or cyclic alkoxyalkyl group,
For example, methoxymethyl, 1-ethoxyethyl, 1-te
rt-butoxyethyl, 1-cyclohexyloxyethyl
1-ethoxypropyl, 1-ethoxy-1-methyl
Ethyl, tetrahydrofuran-2-yl, and tetrahi
Dropyran-2-yl and the like, having 1 to 10 carbon atoms
As the linear, branched or cyclic acyl group, for example,
Olmil, acetyl, pivaloyl, and cyclohexyl
Carbonyl and the like. These R ²⁸Out of carbon
A linear or branched alkyl group having 1 to 6 carbon atoms, 2 to 2 carbon atoms
7, a linear, branched or cyclic alkoxyalkyl group;
And a linear or branched acyl group having 2 to 7 carbon atoms is preferred.
Especially hydrogen, methyl, ethyl, methoxymethyl
, 1-ethoxyethyl, tetrahydrofuran-2-i
And acetyl are preferred.

In R ²⁹ , examples of the linear or branched alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. 2 to 1 carbon atoms
0 linear, branched or cyclic alkoxyalkyl groups include, for example, methoxymethyl, 1-ethoxyethyl,
1-tert-butoxyethyl, 1-cyclohexyloxyethyl, 1-ethoxypropyl, 1-ethoxy-1
-Methylethyl, tetrahydrofuran-2-yl and tetrahydropyran-2-yl;
Examples of the linear, branched or cyclic halogenated alkyl group of -20 include fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl and tribromomethyl. Can be Among these ^{R 29,} preferably a linear or branched alkyl group having 1 to 10 carbon atoms, in particular methyl, ethyl, propyl, isopropyl, n- butyl, isobutyl, and tert- butyl are preferred.

In W ³ , the s + divalent hydrocarbon group having 1 to 10 carbon atoms, when s is 0, has 1 to 10 carbon atoms.
Is a linear, branched or cyclic divalent hydrocarbon group,
For example, methylene, dimethylmethylene, ethylidene, propylidene, butylidene, ethylene, 1-methylethylene, 2-methylethylene, 1-ethylethylene, 2-ethylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 2, 2-dimethylethylene, 1-ethyl-2-methylethylene, trimethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, tetramethylene, pentamethylene, 1,1-
Cyclopentylene, 1,2-cyclopentylene, 1,3
-Cyclopentylene, 1,1-cyclohexylene, 1,
Examples include 2-cyclohexylene, 1,3-cyclohexylene, and 1,4-cyclohexylene. Of these, methylene, ethylidene, ethylene, 1-methylethylene, 2-methylethylene, trimethylene, and 2-
Methyl trimethylene is preferred. In the case where s is 1, for example, there may be mentioned those in which one hydrogen atom at an arbitrary position on the hydrocarbon group mentioned above when s is 0 is removed and a bond is used.
The most preferred W ³ being a single bond.

The others of R ^{24 to} R ²⁷ are each independently a hydrogen atom, methyl having 1 to 20 carbon atoms, ethyl, propyl, isopropyl, n-butyl, tert-
Linear, branched or cyclic alkyl groups such as butyl, cyclohexyl or menthyl, halogens such as chlorine, bromine, iodine or fluorine, C1-C20 fluoromethyl, chloromethyl, bromomethyl, difluoromethyl Linear, branched or cyclic alkyl halide groups such as dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl or tribromomethyl, methoxy, ethoxy, isopropoxy having 1 to 12 carbon atoms, n
Linear, branched or cyclic alkoxy groups such as -butoxy, tert-butoxy or mentoxy, having 2 to 20 carbon atoms
Methoxymethyl, methoxyethyl, tert-butoxymethyl, tert-butoxyethyl or methoxymenthol or the like, or a linear, branched or cyclic alkoxyalkyl group containing an alkoxy sugar such as methyl glucose, having 2 to 20 carbon atoms Linear, branched or cyclic alkylcarbonyloxy group such as acetoxy, having 6 to 20 carbon atoms
Aryl carbonyloxy group such as naphthoyloxy,
A linear, branched or cyclic alkylsulfonyloxy group such as mesyloxy having 1 to 20 carbon atoms, an arylsulfonyloxy group such as tosyloxy having 6 to 20 carbon atoms, methoxycarbonyl having 2 to 20 carbon atoms, ethoxycarbonyl,
a linear, branched or cyclic alkoxycarbonyl group such as n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl, or cyclohexyloxycarbonyl; methoxycarbonylmethyl having 3 to 20 carbon atoms; (Methoxycarbonyl) ethyl, 1- (methoxycarbonyl) ethyl, ethoxycarbonylmethyl, 2- (ethoxycarbonyl) ethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, n-butoxycarbonylmethyl, tert-butoxycarbonylmethyl, or Specific examples include a linear, branched or cyclic alkoxycarbonylalkyl group such as cyclohexyloxycarbonylmethyl. Among them, hydrogen atom, carbon number 1
Linear, branched or cyclic alkyl group having from 20 to 20 carbon atoms, linear, branched or cyclic alkoxy group having from 1 to 20 carbon atoms, linear, branched or cyclic alkoxyalkyl having from 2 to 20 carbon atoms Group, a straight-chain, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms, and a straight-chain, branched or cyclic alkoxycarbonylalkyl group having 3 to 20 carbon atoms, more preferably a hydrogen atom, Carbon number 1-10
A linear or branched alkylcarbonyl group having 2 to 10 carbon atoms, and a linear or branched alkoxycarbonylalkyl group having 3 to 10 carbon atoms.

X ⁵ is —O— or CR ³⁰ ₂ — (R ³⁰ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), and when r is 1 to 3, X ⁵ may be the same or different. Specific examples of R ³⁰ include a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl. X ⁵
As preferably -O- or CH ₂ -, more preferably an all ^{X 5} is -O- or CH ₂ - is either. r is preferably 0 or 1.

Specific examples of the general formula [7] include structural units [E] represented by the following chemical formulas [21-1-1] to [21-4-16].

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

The hydrogenated product of the ring-opening metathesis copolymer used in the present invention comprises structural units [A] and [B] and / or [C], preferably [D], and in some cases [E]. In addition, the following general formula [22]

Embedded image (Wherein, R ^{72 to} R ⁷⁵ each independently represent a hydrogen atom, a linear or branched or cyclic alkyl group having 1 to 20 carbon atoms, a halogen, a linear or branched chain having 1 to 20 carbon atoms. Or a cyclic halogenated alkyl group, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, a hydroxyl group, 1 carbon atom Straight-chain, branched or cyclic hydroxyalkyl group, cyano group, straight-chain having 2 to 20 carbon atoms,
A branched or cyclic cyanoalkyl group, a linear, branched or cyclic alkylcarbonyloxy group having 2 to 20 carbon atoms, a linear, branched or cyclic alkylcarbonyloxyalkyl group having 3 to 20 carbon atoms, An arylcarbonyloxy group having 6 to 20 carbon atoms, a linear, branched or cyclic alkylsulfonyloxy group having 1 to 20 carbon atoms, 2 carbon atoms
20 straight, branched or cyclic alkylsulfonyloxy group, selected from arylsulfonyloxy group having 6 to 20 carbon atoms, ^{X 6} is -O- or ^{-CR 76} ₂
— (R ⁷⁶ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), which may be the same or different. v represents 0 or an integer of 1 to 3. )) May be further included as a structural unit. The introduction ratio of the structural unit [F] is from the structural unit [A] to the structural unit [A].
It can be 0 to 50 mol%, especially 0 to 30 mol%, based on the total of [E].

In the hydrogenated product of the ring-opening metathesis copolymer used in the present invention, the structural unit [A] represented by the general formula [1] and the structural unit [B] represented by the general formula [2] and / or
Alternatively, the molar ratio [A] / ([B] and [C]) of the structural unit of the structural unit [C] represented by the general formula [4] is from 20/80.
99/1. Here, the structural unit [A] contains a tertiary ester group of a cyclic alkyl, which is a group decomposed by an acid generated from a photosensitizing agent at the time of exposure. And the structural units [B] and [C] are necessary to develop adhesion to a substrate to be processed such as a silicon substrate.
These molar ratios [A] / ([B] and [C]) are 20 /
If it is less than 80, the development becomes insufficient, and if it exceeds 99/1, the adhesion to the substrate to be processed does not appear. In addition, the structural unit [D] represented by the general formula [6] contains a carboxylic acid group, and improves adhesion to a substrate to be processed such as a silicon substrate and improves solubility in a solvent. can do. Further, the molar ratio of the structural units [A], [B] and [C] to the structural unit [D] ([A] + [B] +
When [C]) / [D] is in the range of 100/0 to 20/80, it is preferable to improve the wetting tension at the time of development with an aqueous alkali solution after exposure and to solve uneven development. The presence of these structural units in this range is suitable for preparing a resist composition, and is dissolved in a polar solvent such as 2-heptanone together with a highly polar sensitizing agent, and is subjected to a treatment such as a silicon substrate. It is extremely important as a resist material applied to a substrate. In other words, a uniform smooth coating film can be formed by increasing the solubility or dissolution rate of a hydrogenated product of the ring-opening metathesis polymer in a polar solvent when preparing a resist composition. Further, when the structural unit [E] is included in addition to the structural units [A] and [B] and / or [C], the ester group included in the structural unit [A] may include an ester group having a different reactivity. This is useful because the decomposability at the time of exposure can be freely controlled. In this case, the preferable molar ratio of the structural unit ([A] + [B] + [C]) / [E] is 100/0 to 4
The range is 0/60.

In particular, the structural unit represented by the general formula [1]
X in position [A]¹, A structural unit represented by the general formula [3]
X of [B]²And a structural unit represented by general formula [4]
X of [C] ³At least one of which is -O-,
Is -CH₂Hydrogenation of the ring-opening metathesis polymer
Additives have good adhesion to substrates to be processed such as silicon substrates,
Improvement of wetting tension when developing with alkaline aqueous solution, resist
Used in the process of applying a coating agent to a silicon wafer
Solubility in polar organic solvents such as alcohols and alcohols
It has the effect of further improving. Also, the affinity for water
And remover (or developing agent) such as aqueous alkali solution after exposure
) Is also improved.

The hydrogenated product of the ring-opening metathesis copolymer used in the present invention includes a structural unit [A] represented by the general formula [1], a structural unit [B] represented by the general formula [3] and / or
Alternatively, the structural unit [C] represented by the general formula [4], and the structural unit [E] represented by the general formula [7] if necessary, and further represented by the general formula [22] as necessary. Structural unit [F]
Are obtained by polymerizing a cyclic olefin monomer corresponding to each of the above with a ring-opening metathesis catalyst and hydrogenating it under a hydrogenation catalyst.

The cyclic olefin monomer corresponding to the structural unit [A] represented by the general formula [1] is represented by the following general formula [9]
And a cyclic olefin monomer corresponding to the structural unit [B] represented by the general formula [3] is a cyclic olefin monomer having a structure represented by the following general formula [10]. The cyclic olefin monomer which is a monomer and corresponds to the structural unit [C] represented by the general formula [4] is a cyclic olefin monomer having a structure of the following general formula [11], The cyclic olefin monomer corresponding to the structural unit [E] represented by [7] is a cyclic olefin monomer having a structure represented by the following general formula [12] and represented by the general formula [2]
The cyclic olefin monomer corresponding to the structural unit [F] represented by 2] is a cyclic olefin monomer having a structure represented by the following general formula [23].

[0064]

Embedded image (Wherein, R ^{1 to} R ⁷⁵ , X ^{1 to} X ⁶ , Y ¹ , Y ² , j,
m, n, r and v are the same as defined above. )

The hydrogenated product of the ring-opening metathesis copolymer used in the present invention is prepared by subjecting the above cyclic olefin monomer to a solvent using a living ring-opening metathesis catalyst, preferably in the presence of a chain transfer agent such as an olefin or a diene. After polymerization in a medium or without a solvent, it is obtained by hydrogenating in a solvent under a hydrogen pressure using a hydrogenation catalyst.

Further, in the hydrogenated product of the ring-opening metathesis copolymer obtained by polymerization and hydrogenation, the tertiary ester group of the cyclic alkyl in the general formula [2] and / or the ester group in the general formula [8] By converting at least a part thereof into a carboxylic acid, the structural unit [A] represented by the general formula [1] and the structural unit [B] represented by the general formula [3] and / or the general formula [3] 3] a structural unit [C], a structural unit [D] represented by a general formula [5], and a structural unit [E] represented by a general formula [7] as necessary.
Further, if necessary, X ^{1 of the} structural unit [A] composed of the structural unit [F] represented by the general formula [22] and represented by the general formula [3] At least one of X ² of the structural unit [B] and X ³ of the structural unit [C] represented by the general formula [4] is —O—, and the constituent molar ratio [A] / ([ B] and [C]) are 20/8
It is possible to produce a hydrogenated product of a ring-opening metathesis polymer having a weight-average molecular weight Mw and a number-average molecular weight Mn of 1.0 to 2.0 (Mw / Mn) in the range of 0 to 99/1. it can.

As a method for decomposing at least a part of the tertiary ester group of the cyclic alkyl in the general formula [2] and / or the ester group in the general formula [8] to convert it into a carboxylic acid, a usual method can be applied. Specific examples include hydrolysis under basic conditions, hydrolysis under acidic conditions, hydrolysis under neutral conditions, and acid decomposition, but are not limited thereto.

Further, by converting the carboxylic acid functional group of the hydrogenated product of the ring-opening metathesis polymer having a carboxylic acid functional group obtained by the above method into an ester, the structure represented by the general formula [1] is obtained. The unit [A] and the structural unit [B] represented by the general formula [3] and / or the structural unit [C] represented by the general formula [3], and if necessary, represented by the general formula [5] It is composed of a structural unit [D], if necessary, a structural unit [E] represented by a general formula [7], and further optionally a structural unit [F] represented by a general formula [22]. And X ¹ of the structural unit [A] represented by the general formula [1], X ² of the structural unit [B] represented by the general formula [3], and the structure represented by the general formula [4] At least one of X ^{3 in} the unit [C] is —O—, and its constituent molar ratio [A] /
([B] and [C]) are 20/80 to 99/1,
And the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (M
(w / Mn) of 1.0 to 2.0 can be produced as a hydrogenated product of a ring-opening metathesis polymer.

As a method for converting a carboxylic acid functional group into an ester, a usual method can be applied.
Esterification by dehydration-condensation reaction with an ester, an esterification by an ortho-alkylating agent, an esterification by addition of an olefin in the presence of an acid, a condensation reaction with a halide using an organic basic compound Esterification, alkoxyalkyl esterification by addition of alkyl vinyl ethers, a method of converting a carboxylic acid to an acid halide with thionyl chloride or the like, followed by contact with an alcohol to perform esterification, and a method of preparing a metal salt of a carboxylic acid. A method of contacting with a halide for esterification can be exemplified, but the method is not limited thereto.

The resist material containing a hydrogenated product of the ring-opening metathesis polymer having a specific structure according to the present invention as a base resin is suitable as a positive resist material, particularly a chemically amplified positive resist material. In addition to the above hydrogenated product of the ring-opening metathesis polymer, a compound which generates an acid in response to a high energy beam or an electron beam (hereinafter, an acid generator) and an organic solvent are included.

The acid generator used in the present invention includes: i. An onium salt of the following general formula (P1a-1), (P1a-2) or (P1b); ii. A diazomethane derivative represented by the following general formula (P2), iii. A glyoxime derivative of the following general formula (P3), iv. A bissulfone derivative represented by the following general formula (P4); A sulfonic acid ester of an N-hydroxyimide compound represented by the following general formula (P5), vi. β-ketosulfonic acid derivatives, vii. Disulfone derivatives, viii. A nitrobenzylsulfonate derivative, ix. And sulfonic acid ester derivatives.

[0072]

Embedded image (Wherein, R ^101a , R ^101b , and R ^101c each represent a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 12 carbon atoms, and aryl having 6 to 20 carbon atoms. Group or 7 to carbon atoms
12 represents an aralkyl group or an aryloxoalkyl group, and a part or all of the hydrogen atoms of these groups may be substituted with an alkoxy group or the like. Also, R ^101b
And may be the ^{R 101 c} to form a ring, when they form a ^ring, R ^{101b, R 101c} are each 1 to carbon atoms
6 represents an alkylene group. K ^- is a non-nucleophilic counter ion. )

The above R ^101a , R ^101b , R ^101c
May be the same or different from each other, and specifically, as an alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group , Hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group,
Examples include a 4-methylcyclohexyl group, a cyclohexylmethyl group, a norbornyl group, and an adamantyl group.
Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and the like. A 2-oxopropyl group, a 2-cyclopentyl-2-oxoethyl group, a 2-cyclohexyl-2-oxoethyl group, a 2- (4 -Methylcyclohexyl) -2-
An oxoethyl group and the like can be mentioned. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group ,
Alkylnaphthyl groups such as methylnaphthyl group and ethylnaphthyl group, alkoxynaphthyl groups such as methoxynaphthyl group and ethoxynaphthyl group, dialkylnaphthyl groups such as dimethylnaphthyl group and diethylnaphthyl group, dimethoxynaphthyl groups and diethoxynaphthyl groups such as diethoxynaphthyl groups And alkoxynaphthyl groups. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group.
As the aryloxoalkyl group, 2-phenyl-2
And 2-aryl-2-oxoethyl groups such as -oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group and 2- (2-naphthyl) -2-oxoethyl group. K ^- a non-nucleophilic counter as the ionic chloride ions,
Halide ion such as bromide ion, triflate, 1,
Fluoroalkylsulfonates such as 1,1-trifluoroethanesulfonate and nonafluorobutanesulfonate; arylsulfonates such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, 1,2,3,4,5-pentafluorobenzenesulfonate, and mesylate And alkyl sulfonates such as butane sulfonate.

[0074]

Embedded image (Wherein, R ^102a and R ^102b each have 1 to 1 carbon atoms.
8 represents a linear, branched or cyclic alkyl group. R
¹⁰³ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. R ^104a and R ^104b each represent a 2-oxoalkyl group having 3 to 7 carbon atoms. K ^- is a non-nucleophilic counter ion. )

Specific examples of R ^102a and R ^102b include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, and heptyl. Octyl group, cyclopentyl group, cyclohexyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group and the like. R ¹⁰³ includes methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, 1,4-cyclohexylene,
-Cyclohexylene group, 1,3-cyclopentylene group,
Examples thereof include a 1,4-cyclooctylene group and a 1,4-cyclohexanedimethylene group. R ^104a , R ^104b
Examples thereof include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group. K ^- is the formula (P1a-
Examples similar to those described in 1) and (P1a-2) can be given.

[0076]

Embedded image (Wherein, R ¹⁰⁵ and R ¹⁰⁶ are a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 20 carbon atoms, or And 7 to 12 aralkyl groups.)

The alkyl group for R ¹⁰⁵ and R ¹⁰⁶ includes methyl, ethyl, propyl, isopropyl, n
-Butyl group, sec-butyl group, tert-butyl group,
Pentyl, hexyl, heptyl, octyl, amyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, adamantyl and the like. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group,
Examples thereof include a 1-trichloroethyl group and a nonafluorobutyl group. Examples of the aryl group include an alkoxyphenyl group such as a phenyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and a m-tert-butoxyphenyl group. 2-methylphenyl group, 3-
Examples thereof include alkylphenyl groups such as a methylphenyl group, a 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, and a dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, 1,2,3,4,5
-Pentafluorophenyl group and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0078]

Embedded image (Wherein, R ¹⁰⁷ , R ¹⁰⁸ and R ^{109 each} have 1 to 1 carbon atoms.
2 represents a linear, branched or cyclic alkyl group or halogenated alkyl group, an aryl group or halogenated aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. R ^{108, R 109} may be bonded to each other to form a cyclic structure, when they form a ^{ring, R 108,}
R ¹⁰⁹ represents a linear or branched alkylene group having 1 to 6 carbon atoms. )

The alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group represented by R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are R ¹⁰⁵ , R ¹⁰⁶
And the same groups as described in the above. Note that R
^As the alkylene group for ¹⁰⁸ and R ^109, a methylene group,
Examples include an ethylene group, a propylene group, a butylene group, and a hexylene group.

[0080]

Embedded image (In the formula, R ^101a and R ^101b are the same as described above.)

[0081]

Embedded image (In the formula, R ¹¹⁰ represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms or an alkenylene group having 2 to 6 carbon atoms, and a part or all of the hydrogen atoms of these groups further have carbon atoms. R ¹¹¹ may be substituted with a linear or branched alkyl or alkoxy group, a nitro group, an acetyl group, or a phenyl group having from 1 to 4. R ¹¹¹ has 1 to 8 carbon atoms. Or a substituted alkyl group, alkenyl group or alkoxyalkyl group, phenyl group or naphthyl group, and a part or all of the hydrogen atoms of these groups are further an alkyl group or alkoxy group having 1 to 4 carbon atoms; ~ 4
A phenyl group optionally substituted by an alkyl group, an alkoxy group, a nitro group or an acetyl group; a heteroaromatic group having 3 to 5 carbon atoms; or a chlorine atom or a fluorine atom. )

Here, the arylene group of R ¹¹⁰ is 1,2-phenylene group, 1,8-naphthylene group or the like, and the alkylene group is methylene group, 1,2-ethylene group, 1,3-propylene group. Group, 1,4-butylene group,
1-phenyl-1,2-ethylene group, norbornane-
When the 2,3-diyl group or the like is an alkenylene group,
2-vinylene group, 1-phenyl-1,2-vinylene group,
5-norbornene-2,3-diyl group and the like.
As the alkyl group for R ¹¹¹ , R ^{101a to} R ^{10
The same} alkenyl groups as those described in ^{1c except} that they are vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3
-Butenyl group, isoprenyl group, 1-pentenyl group, 3
-Pentenyl group, 4-pentenyl group, dimethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7-octenyl group and the like, Examples of the alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl group,
Propoxymethyl group, butoxymethyl group, pentoxylmethyl group, hexyloxymethyl group, heptyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, pentoxyloxy group,
Hexyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, methoxypentyl group, ethoxypentyl group,
Examples include a methoxyhexyl group and a methoxyheptyl group.

In addition, carbon atom 1 which may be further substituted
Examples of the alkyl group having 1 to 4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. Group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, etc., which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a nitro group or an acetyl group. A phenyl group, a tolyl group, a p-tert-butoxyphenyl group, a p-acetylphenyl group, a p-nitrophenyl group, etc.
Examples of the heteroaromatic group 5 include a pyridyl group and a furyl group.

Specifically, for example, diphenyliodonium trifluoromethanesulfonate, phenyliodonium trifluoromethanesulfonate (p-tert-butoxyphenyl), diphenyliodonium p-toluenesulfonate, p-toluenesulfonic acid (p-tert-
(Butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris trifluoromethanesulfonate (P-tert-butoxyphenyl) sulfonium,
triphenylsulfonium p-toluenesulfonate, p
-(P-tert-butoxyphenyl) diphenylsulfonium toluenesulfonate, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (p-tert-toluenesulfonate)
(t-butoxyphenyl) sulfonium, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) Sulfonium, cyclohexylmethyl p-toluenesulfonate (2-oxocyclohexyl) sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate , Trifluoromethane sulfone Trinaphthylsulfonium, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, (2-norbonyl) methyl (2-oxocyclohexyl) sulfonium, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate Onium salts such as 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) Diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutyl) Ruhoniru)
Diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) Diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-
Diazomethane derivatives such as amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane, bis-O- (p-
Toluenesulfonyl) -α-dimethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluenesulfonyl)
-Α-dicyclohexylglyoxime, bis-O- (p
-Toluenesulfonyl) -2,3-pentanedione glyoxime, bis-O- (p-toluenesulfonyl) -2
-Methyl-3,4-pentanedione glyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (N-butanesulfonyl) -α-dicyclohexylglyoxime, bis-O
-(N-butanesulfonyl) -2,3-pentanedione glyoxime, bis-O- (n-butanesulfonyl)-
2-methyl-3,4-pentanedione glyoxime, bis-O- (methanesulfonyl) -α-dimethylglyoxime, bis-O- (trifluoromethanesulfonyl)-
α-dimethylglyoxime, bis-O- (1,1,1-
Trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-O- (tert-butanesulfonyl)-
α-dimethylglyoxime, bis-O- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-O- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-O- (benzenesulfonyl) -α
-Dimethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-tert-butylbenzenesulfonyl)-
glyoxime derivatives such as α-dimethylglyoxime, bis-O- (xylenesulfonyl) -α-dimethylglyoxime, bis-O- (camphorsulfonyl) -α-dimethylglyoxime, bisnaphthylsulfonylmethane,
Bissulfone derivatives such as bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane;
-Cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl-2-
Β-ketosulfone derivatives such as (p-toluenesulfonyl) propane, disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone, nitros such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate Benzylsulfonate derivatives, 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene and the like Sulfonic acid ester derivatives, N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide ethanesulfonic acid ester, N-
Hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfone Acid ester, N-
Hydroxysuccinimide p-methoxybenzenesulfonate, N-hydroxysuccinimide 2-chloroethanesulfonate, N-hydroxysuccinimidebenzenesulfonate, N-hydroxysuccinimide-2,4,6-trimethylbenzenesulfonate, N-hydroxy Succinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N-hydroxy-2-phenylsuccinimide methanesulfonic acid ester, N-hydroxymaleimide methanesulfonic acid ester, N-hydroxymaleimidoethanesulfonic acid ester, N-hydroxy-2-phenylmaleimide methanesulfonic acid ester, N-hydroxyglutarimide methanesulfonic acid ester Ether, N- hydroxy glutarimide benzenesulfonate ester, N- hydroxyphthalimide methanesulfonate ester, N- hydroxyphthalimide benzenesulfonate ester, N- hydroxyphthalimide trifluoromethanesulfonate ester,
N-hydroxyphthalimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimidebenzenesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboximide methanesulfonic acid ester N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboximide p-toluenesulfonic acid ester, etc.
Sulfonic acid ester derivatives of a hydroxyimide compound, such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, and tris (pt) trifluoromethanesulfonate;
tert-butoxyphenyl) sulfonium, triphenylsulfonium p-toluenesulfonate, diphenylsulfonium p-toluenesulfonate (p-tert-butoxyphenyl), tris (p-toluenesulfonate)
-Tert-butoxyphenyl) sulfonium, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2
Onium salts such as -oxocyclohexyl) sulfonium, (2-norbonyl) methyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, Bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane,
Bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, etc. Diazomethane derivative of bis-O-
Glyoxime derivatives such as (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bissulfone derivatives such as bisnaphthylsulfonylmethane, N-hydroxysuccinimide methanesulfonic acid Ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2
-Propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester,
Sulfonate derivatives of N-hydroxyimide compounds such as N-hydroxynaphthalimide methanesulfonate and N-hydroxynaphthalimidobenzenesulfonate are preferably used. In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. Onium salts are excellent in the effect of improving rectangularity, and diazomethane derivatives and glyoxime derivatives are excellent in the effect of reducing standing waves. Therefore, fine adjustment of the profile can be performed by combining the two.

The acid generator is preferably added in an amount of 0.1 to 15 parts by weight based on 100 parts (parts by weight, hereinafter the same) of the base resin.
Parts, more preferably 0.5 to 8 parts. If the amount is less than 0.1 part, the sensitivity may be poor. If the amount is more than 15 parts, the transparency may be lowered, and the resolution of the resist material may be reduced.

The organic solvent used in the present invention may be any organic solvent capable of dissolving the base resin, acid generator, other additives and the like. Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol,
-Methyl-3-methoxybutanol, 1-methoxy-2
Alcohols such as -propanol, 1-ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethers such as ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monoter
Esters such as t-butyl ether acetate and the like can be mentioned, and one of these can be used alone or a mixture of two or more thereof, but is not limited thereto. In the present invention, among these organic solvents, in addition to diethylene glycol dimethyl ether and 1-ethoxy-2-propanol in which the solubility of the acid generator in the resist component is the most excellent, propylene glycol monomethyl ether acetate as a safe solvent and a mixture thereof Solvents are preferably used.

The amount of the organic solvent to be used is preferably 200 to 1,000 parts, more preferably 400 to 800 parts per 100 parts of the base resin.

The resist composition of the present invention may contain a polymer compound other than the hydrogenated product of the ring-opening metathesis polymer.

As a specific example of the polymer compound, a weight average molecular weight represented by the following formula (R1) and / or (R2) is from 1,000 to 500,000, preferably 5,
000 to 100,000, but are not limited thereto.

[0090]

Embedded image (Wherein, R ⁰⁰¹ is a hydrogen atom, a methyl group or CH ₂ CO
₂ R ⁰⁰³ is shown. R ^{0 02} represents a hydrogen atom, a methyl group or _CO 2 ^{R 003.} R ⁰⁰³ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. R ⁰⁰⁴ represents a hydrogen atom or a monovalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms. R ^{0 05} ~R
^{008 represents} a monovalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms, and the rest are each independently a hydrogen atom or a linear, branched or cyclic group having 1 to 15 carbon atoms. Represents an alkyl group. R ^{005 to} R
⁰⁰⁸ may form a ring with each other, in which case at least one of R ^{005 to} R ⁰⁰⁸ has 1 to 15 carbon atoms.
A carboxy group or a divalent hydrocarbon group containing a hydroxyl group, and the rest are each independently a single bond or a carbon number of 1 to 1.
5 represents a linear, branched or cyclic alkylene group. R
⁰⁰⁹ represents a monovalent hydrocarbon group having a —CO ₂ — partial structure having 3 to 15 carbon atoms. At least one of R ^{010 to} R ^{013 represents} a monovalent hydrocarbon group having a —CO ₂ — partial structure having 2 to 15 carbon atoms, and the rest are each independently a hydrogen atom or a straight chain having 1 to 15 carbon atoms. A branched, branched or cyclic alkyl group. R ⁰¹⁰ to R ^013, taken together, may form a ring, in which case ^{R 0} 10 ^{to R 013}
At least one is -CO 2 C 1 -C 15 _- moiety represents a divalent hydrocarbon group containing, while the remaining are independently a single bond or a C15 straight, branched or Shows a cyclic alkylene group. R ⁰¹⁴ has 7 to 15 carbon atoms
Or a polycyclic hydrocarbon group or an alkyl group containing a polycyclic hydrocarbon group. R ⁰¹⁵ represents an acid labile group. R
⁰¹⁶ represents a hydrogen atom or a methyl group. R ⁰¹⁷ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. X represents CH ₂ or an oxygen atom. k ′ is 0 or 1. x ′, y ′, z ′ are integers from 0 to 3, and x ′ +
It is a number that satisfies y ′ + z ′ ≦ 5 and 1 ≦ y ′ + z ′.
a1 ', a2', a3 ', b1', b2 ', b3', c
1 ', c2', c3 ', d1', d2 ', d3', e '
Is a number from 0 to less than 1, and a1 ′ + a2 ′ + a3 ′ +
b1 '+ b2' + b3 '+ c1' + c2 '+ c3' + d
1 ′ + d2 ′ + d3 ′ + e ′ = 1 is satisfied. f ',
g ′, h ′, i ′, j ′ are numbers from 0 to less than 1,
f ′ + g ′ + h ′ + i ′ + j ′ = 1 is satisfied. )

Here, R ⁰⁰³ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-
Butyl group, sec-butyl group, tert-butyl group, t
ert-amyl group, n-pentyl group, n-hexyl group,
Examples thereof include a cyclopentyl group, a cyclohexyl group, an ethylcyclopentyl group, a butylcyclopentyl group, an ethylcyclohexyl group, a butylcyclohexyl group, an adamantyl group, an ethyladamantyl group, and a butyladamantyl group. R ⁰⁰⁴ represents a hydrogen atom or a monovalent hydrocarbon group containing a carboxy group or a hydroxyl group having 1 to 15 carbon atoms,
Specific examples include carboxyethyl, carboxybutyl, carboxycyclopentyl, carboxycyclohexyl, carboxynorbornyl, carboxyadamantyl, hydroxyethyl, hydroxybutyl, hydroxycyclopentyl, hydroxycyclohexyl, hydroxynorbornyl, hydroxyadamantyl and the like. R
^At least one of ^{005 to} R ⁰⁰⁸ represents a carboxy group having 1 to 15 carbon atoms or a monovalent hydrocarbon group having a hydroxyl group, and the rest are each independently a hydrogen atom or 1 to 1 carbon atom.
5 represents a linear, branched or cyclic alkyl group. Specific examples of the monovalent hydrocarbon group containing a carboxy group or a hydroxyl group having 1 to 15 carbon atoms include carboxy, carboxymethyl, carboxyethyl, carboxybutyl, hydroxymethyl, hydroxyethyl, hydroxybutyl,
2-carboxyethoxycarbonyl, 4-carboxybutoxycarbonyl, 2-hydroxyethoxycarbonyl, 4-hydroxybutoxycarbonyl, carboxycyclopentyloxycarbonyl, carboxycyclohexyloxycarbonyl, carboxynorbornyloxycarbonyl, carboxyadamantyloxycarbonyl, hydroxycyclopentyloxycarbonyl , Hydroxycyclohexyloxycarbonyl, hydroxynorbornyloxycarbonyl, hydroxyadamantyloxycarbonyl and the like. Examples of the straight, branched, the alkyl group of cyclic, specifically exemplified the same ones as exemplified for R ^003. R
^{005 to} R ⁰⁰⁸ may form a ring with each other, in which case at least one of R ^{005 to} R ^{008 represents} a divalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms. And the rest each independently represent a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms. Specific examples of the divalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms include one hydrogen atom from those exemplified as the monovalent hydrocarbon group having a carboxy group or a hydroxyl group. Excluded ones can be exemplified. Specific examples of the linear, branched, or cyclic alkylene group having 1 to 15 carbon atoms include those exemplified for R ⁰⁰³ with one hydrogen atom removed.

R ⁰⁰⁹ represents a monovalent hydrocarbon group having a —CO ₂ — partial structure having 3 to 15 carbon atoms, and specifically, 2-oxooxolan-3-yl and 4,4-dimethyl-
2-oxooxolan-3-yl, 4-methyl-2-oxooxan-4-yl, 2-oxo-1,3-dioxolan-4-ylmethyl, 5-methyl-2-oxooxolan-5-yl and the like Can be exemplified. R ^{010 to} R ⁰¹³
At least one is -CO 2 of 2 to 15 carbon atoms _- a monovalent hydrocarbon group containing a partial structure, while the remaining R's are independently hydrogen or C15 straight, branched or Shows a cyclic alkyl group. -CO ₂ having 2 to 15 carbon atoms
-Specific examples of the monovalent hydrocarbon group having a partial structure include 2-oxooxolan-3-yloxycarbonyl, 4,4-dimethyl-2-oxooxolan-3-yloxycarbonyl, -Methyl-2-oxooxan-4-yloxycarbonyl, 2-oxo-1,3-dioxolan-4-ylmethyloxycarbonyl, 5-methyl-2-oxooxolan-5-yloxycarbonyl and the like can be exemplified. C1-C15 linear, branched,
The cyclic alkyl group, specifically exemplified the same ones as exemplified for R ^003. R ^{010 to} R
⁰¹³ may form a ring with each other, in which case at least one of R ^{010 to} R ⁰¹³ has 1 to 15 carbon atoms.
Represents a divalent hydrocarbon group having a —CO ₂ — partial structure, and the rest each independently represent a single bond or a linear, branched, or cyclic alkylene group having 1 to 15 carbon atoms. Carbon number 1
15 of -CO ₂ - Examples of the divalent hydrocarbon group containing a partial structure include 1-oxo-2-oxa-1,3-diyl, 1,3-dioxo-2-oxa-propane 1,3-diyl, 1-oxo-2-Okisabutan-1,4-diyl, other like 1,3-dioxo-2-Okisabutan-1,4-diyl, the -CO ₂ - containing partial structure Examples thereof include those obtained by removing one hydrogen atom from those exemplified for the monovalent hydrocarbon group. Specific examples of the linear, branched, or cyclic alkylene group having 1 to 15 carbon atoms include those exemplified for R ⁰⁰³ with one hydrogen atom removed.

R ⁰¹⁴ represents a polycyclic hydrocarbon group having 7 to 15 carbon atoms or an alkyl group containing a polycyclic hydrocarbon group, and specifically, norbornyl, bicyclo [3.3.1]
Nonyl, tricyclo [5.2.1.0 ^2,6 ] decyl,
Adamantyl, ethyl adamantyl, butyl adamantyl, norbornylmethyl, adamantylmethyl and the like can be exemplified. R ⁰¹⁵ represents an acid labile group. R ⁰¹⁶ represents a hydrogen atom or a methyl group. R ⁰¹⁷ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, specifically, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl , N-pentyl, n-hexyl, cyclopentyl,
Examples include cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl and the like.

As the acid labile group for R ⁰¹⁵ , various ^ones can be selected, and specifically, the following general formula (L1)
A group represented by (L4), having 4 to 20 carbon atoms, preferably 4 carbon atoms;
Examples thereof include a tertiary alkyl group having 1 to 15 carbon atoms, a trialkylsilyl group in which each alkyl group has 1 to 6 carbon atoms, and an oxoalkyl group having 4 to 20 carbon atoms.

[0095]

Embedded image

In the formula, R ^L01 and R ^{L02 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. , Propyl group, isopropyl group, n-butyl group,
sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-
An octyl group can be exemplified. R ^L03 has 1 to 1 carbon atoms
8, preferably a monovalent hydrocarbon group which may have 1 to 10 hetero atoms such as an oxygen atom, and is a linear, branched or cyclic alkyl group, and a part of these hydrogen atoms is a hydroxyl group , An alkoxy group, an oxo group, an amino group, an alkylamino group or the like, and specific examples thereof include the following substituted alkyl groups.

[0097]

Embedded image

R ^L01 and R ^L02 , R ^L01 and R ^L03 , and R ^L02 and R ^L03 may form a ring, and when a ring is formed, R ^L01 , R ^L02 , R
^L03 has 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms.
Represents a linear or branched alkylene group.

R ^L04 has 4 to 20 carbon atoms, preferably 4 carbon atoms.
A tertiary alkyl group having 1 to 15 carbon atoms, each alkyl group being a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms or a group represented by the above formula (L1); Specific examples of the group include a tert-butyl group, a tert-amyl group, a 1,1-diethylpropyl group, a 1-ethylcyclopentyl group, a 1-butylcyclopentyl group, a 1-ethylcyclohexyl group, a 1-butylcyclohexyl group, -Ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2-methyl-2-adamantyl group, and the like. Specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and dimethyl. -Tert-butylsilyl group and the like, and specific examples of the oxoalkyl group include 3-oxocyclohexyl. Group, 4-methyl-2-oxooxan-4-yl group, 5-methyl-5-oxo-dioxolane -
4-yl group and the like. y is an integer of 0-6.

R ^L05 represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group,
Propyl group, isopropyl group, n-butyl group, sec-
Butyl group, tert-butyl group, tert-amyl group,
n-pentyl group, n-hexyl group, cyclopentyl group,
Examples thereof include a cyclohexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group. Group, pyrenyl group and the like. m is 0 or 1, n is 0, 1,
It is either 2 or 3, which is 2m + n = 2 or 3.

R^L06Is a linear or branched C1-C8
Or a cyclic alkyl group or substituted with 6 to 20 carbon atoms
Represents an optionally substituted aryl group, specifically R^L05Same as
Can be exemplified. R^L07~ R^L16Are each
Independently contains a hydrogen atom or a heteroatom having 1 to 15 carbon atoms
A monovalent hydrocarbon group which may be a methyl group, an ethyl group
Group, propyl group, isopropyl group, n-butyl group, se
c-butyl group, tert-butyl group, tert-amyl
Group, n-pentyl group, n-hexyl group, n-octyl
Group, n-nonyl group, n-decyl group, cyclopentyl group,
Cyclohexyl, cyclopentylmethyl, cyclope
Ethyl group, cyclopentylbutyl group, cyclohexyl
Silmethyl group, cyclohexylethyl group, cyclohexyl
A linear, branched or cyclic alkyl group such as a rubutyl group,
Some of these hydrogen atoms are hydroxyl, alkoxy,
Boxy group, alkoxycarbonyl group, oxo group, amino
Group, alkylamino group, cyano group, mercapto group,
Examples include those substituted with a thio group, a sulfo group, or the like.
You. R^L07~ R^L16May form a ring with each other
(For example, R^L07And R^L08, R^L07When
R^L09, R^L08And R^L10, R ^L09And R^L10,
R^L11And R^L12, R^L13And R^L14Etc.), on the spot
Divalent optionally containing a heteroatom having 1 to 15 carbon atoms
And a hydrocarbon group represented by the above-mentioned monovalent hydrocarbon group.
Examples thereof include those in which one hydrogen atom has been removed therefrom. Ma
R^L07~ R^L16Is bonded to adjacent carbon
May bond to each other without any intervention to form a double bond
(For example, R^L07And R^L09, R^L09And R ^L15,
R^L13And R^L15etc).

Specific examples of the linear or branched acid labile groups represented by the formula (L1) include the following groups.

[0103]

Embedded image

The cyclic group of the acid labile group represented by the above formula (L1) is specifically a tetrahydrofuran-2-yl group, a 2-methyltetrahydrofuran-2-yl group, a tetrahydropyran-2-yl group. And 2-methyltetrahydropyran-2-yl group.

Specific examples of the acid labile group of the above formula (L2) include a tert-butoxycarbonyl group and a tert-butoxycarbonyl group.
Butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1,1-diethylpropyloxycarbonyl group,
1,1-diethylpropyloxycarbonylmethyl group,
1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-
Examples thereof include an ethyl-2-cyclopentenyloxycarbonylmethyl group, a 1-ethoxyethoxycarbonylmethyl group, a 2-tetrahydropyranyloxycarbonylmethyl group, and a 2-tetrahydrofuranyloxycarbonylmethyl group.

Specific examples of the acid labile group of the above formula (L3) include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, -Sec-butylcyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopenten-3-yl, 3-methyl-1-cyclohexene-3- Yl, 3-ethyl-1-cyclohexene-3
-Il and the like.

Specific examples of the acid labile group of the formula (L4) include the following groups.

[0108]

[Of 60]

Examples of the tertiary alkyl group, trialkylsilyl group and oxoalkyl group of the acid labile group represented by R ⁰¹⁵ include those exemplified above.

The acid labile group of R ⁰¹⁵ can be used alone or in combination of two or more.
By using a plurality of types of acid labile groups, fine adjustment of the pattern profile can be performed.

The mixing ratio of the hydrogenated product of the ring-opening metathesis polymer to another polymer compound is 100: 0 to 10:
It is preferably in the range of 90, especially 100: 0 to 20:80 by weight. If the compounding ratio of the hydrogenated product of the ring-opening metathesis polymer is less than this, favorable performance as a resist material may not be obtained. The performance of the resist material can be adjusted by appropriately changing the above mixing ratio.

The above-mentioned another polymer compound is not limited to one kind, and two or more kinds can be added. By using a plurality of types of polymer compounds, the performance of the resist material can be adjusted.

The resist composition of the present invention may further contain a dissolution controlling agent. The dissolution controlling agent has an average molecular weight of 100 to 1,000, preferably 150 to 80.
0 and a compound having two or more phenolic hydroxyl groups in the molecule, wherein a hydrogen atom of the phenolic hydroxyl group is substituted with an acid labile group at an average rate of 0 to 100 mol% or a carboxy group in the molecule. And a compound in which the hydrogen atom of the carboxy group of the compound having the formula (1) is substituted with an acid labile group at an average ratio of 50 to 100 mol% as a whole.

Incidentally, the substitution rate of the hydrogen atom of the phenolic hydroxyl group by the acid labile group is 0 mol% or more, preferably 30 mol% or more of the whole phenolic hydroxyl group on average.
The upper limit is 100 mol%, more preferably 80 mol%. The substitution rate of the hydrogen atom of the carboxy group by the acid labile group is 50 mol% or more, preferably 70 mol% or more of the entire carboxy group on average, and the upper limit is 100 mol%.
It is.

In this case, the phenolic hydroxyl group is
As the compound having one or more compounds or the compound having a carboxy group, compounds represented by the following formulas (D1) to (D14) are preferable.

[0116]

Embedded image(Where R²⁰¹, R²⁰²Is a hydrogen atom,
Or a linear or branched alkyl group having 1 to 8 carbon atoms or
Shows an alkenyl group. R²⁰³Is a hydrogen atom or carbon number
1-8 linear or branched alkyl or alkenyl
Group or-(R ²⁰⁷)_hIndicates COOH. R²⁰⁴
Is-(CH₂)_i-(I = 2 to 10), carbon number 6 to 10
Arylene, carbonyl, sulfonyl, oxygen
Represents a hydrogen atom or a sulfur atom. R²⁰⁵Is a group having 1 to 10 carbon atoms.
Alkylene group, arylene group having 6 to 10 carbon atoms, carbonyl
A sulfonyl group, an oxygen atom or a sulfur atom. R
^{20 6}Is a hydrogen atom, a linear or branched C1-8
Substituted with alkyl group, alkenyl group or each hydroxyl group
Phenyl group or naphthyl group. R²⁰⁷Is charcoal
Represents a linear or branched alkylene group having a prime number of 1 to 10
You. R²⁰⁸Represents a hydrogen atom or a hydroxyl group. j is 0-5
Is an integer. u and h are 0 or 1. s, t,
s ′, t ′, s ″, and t ″ are each s + t = 8,
s ′ + t ′ = 5, s ″ + t ″ = 4, and
To have at least one hydroxyl group in the phenyl skeleton
It is a number. α is a molecule of the compound of formulas (D8) and (D9)
It is a number that makes the amount 100 to 1,000. )

In the above formula, R ²⁰¹ and R ²⁰² are, for example, hydrogen atom, methyl group, ethyl group, butyl group, propyl group, ethynyl group, cyclohexyl group, and R ²⁰³ are, for example, the same as R ²⁰¹ and R ^202. Thing, or-
_COOH, as the -CH 2 ^{COOH, R 204,} an ethylene group, a phenylene group, a carbonyl group, a sulfonyl group, an oxygen atom, a sulfur atom, ^etc., as the ^{R 205,} for example a methylene group, or ones similar to ^{R 204,} R ²⁰⁶
Examples thereof include a hydrogen atom, a methyl group, an ethyl group, a butyl group, a propyl group, an ethynyl group, a cyclohexyl group, a phenyl group each substituted with a hydroxyl group, and a naphthyl group.

Here, the acid labile group of the dissolution controlling agent includes groups represented by the following formulas (L1) to (L4), tertiary alkyl groups having 4 to 20 carbon atoms, and carbon atoms of each alkyl group. 1 to 6 trialkylsilyl groups, 4 to 2 carbon atoms
And an oxoalkyl group of 0.

[0119]

Embedded image(Where R^L01, R^L02Is a hydrogen atom or carbon number 1
It represents 18 linear, branched or cyclic alkyl groups. R
^L03Has a heteroatom such as an oxygen atom having 1 to 18 carbon atoms.
And a monovalent hydrocarbon group which may be used. R^L01And R
^L02, R^L01And R ^L03, R^L02And R^L03What is
A ring may be formed, and when a ring is formed, R ^L01,
R^L02, R^L03Is a linear group having 1 to 18 carbon atoms
Or a branched alkylene group. R^L04Is carbon number 4
-20 tertiary alkyl groups, each alkyl group being carbon
A trialkylsilyl group having 1 to 6 carbon atoms,
A xoalkyl group or a group represented by the above general formula (L1)
Show. R^L05Is a linear, branched or cyclic C1-8
Alkyl group or substituted with 6 to 20 carbon atoms
Shows good aryl groups. R^L06Is a linear chain having 1 to 8 carbon atoms
, Branched or cyclic alkyl groups or C6-C20
It shows the aryl group which may be substituted. R^L07~ R
^L16Are each independently a hydrogen atom or a group having 1 to 15 carbon atoms.
It represents a monovalent hydrocarbon group which may contain a hetero atom. R
^L07~ R^L16May form a ring with each other,
May contain a heteroatom having 1 to 15 carbon atoms
Shows a divalent hydrocarbon group. Also, R^L07~ R^L16Is
Bonds between adjacent carbons without any intervention
Then, a double bond may be formed. y is an integer from 0 to 6
You. m is 0 or 1, and n is 0, 1, 2, or 3.
2m + n = 2 or 3. )

The amount of the above-mentioned dissolution controlling agent was determined based on the amount of the base resin 1
It is 0 to 50 parts, preferably 5 to 50 parts, more preferably 10 to 30 parts with respect to 00 parts, and can be used alone or in combination of two or more. If the amount is less than 5 parts, the resolution may not be improved. If the amount is more than 50 parts, the pattern may be reduced in film thickness and the resolution may be reduced.

The dissolution controlling agent as described above is used for a compound having a phenolic hydroxyl group or a carboxy group.
It is synthesized by introducing an acid labile group using an organic chemical formulation.

The resist composition of the present invention may further contain a basic compound. As the basic compound, a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. By compounding a basic compound, the diffusion rate of acid in the resist film is suppressed and the resolution is improved. Etc. can be improved.

Such basic compounds include primary, secondary and tertiary aliphatic amines, hybrid amines, and the like.
Aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group,
Examples include a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, and an imide derivative.

Specifically, as primary aliphatic amines, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tertiary amine
t-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine,
Nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like are exemplified. As secondary aliphatic amines, dimethylamine, diethylamine, di-n
-Propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine,
Dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N
-Dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine, and the like. Examples of the tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, and triisopropylamine. , Tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine,
Triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetra Examples include methylethylenediamine, N, N, N ', N'-tetramethyltetraethylenepentamine and the like.

Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine and benzyldimethylamine. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (for example, aniline,
N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline , 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-
Dimethyl toluidine), diphenyl (p-tolyl) amine, methyl diphenylamine, triphenylamine,
Phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole,
2,5-dimethylpyrrole, N-methylpyrrole, etc.),
Oxazole derivatives (eg, oxazole, isoxazole, etc.), thiazole derivatives (eg, thiazole, isothiazole, etc.), imidazole derivatives (eg, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, Pyrroline derivatives (eg, pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (eg, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg, pyridine, methyl) Pyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridyl , 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-pyrrolidinopyridine, 1-methyl- 4-phenylpyridine, 2- (1-ethylpropyl) pyridine,
Aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indone derivatives, Quinoline derivatives (for example, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1 , 1
Examples thereof include 0-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

Further, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (eg, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine,
Histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine, etc.), and 3-pyridinesulfonic acid as a nitrogen-containing compound having a sulfonyl group. , Pyridinium p-toluenesulfonate, and the like. Examples of the nitrogen-containing compound having a hydroxyl group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, and 2,4-quinolinediol. , 3-indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine,
2,2′-iminodiethanol, 2-aminoethanol
3-amino-1-propanol, 4-amino-1-
Butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2
-Hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine,
1- (2-hydroxyethyl) -2-pyrrolidinone, 3
-Piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyurolidine, 3-quinuclidinol, 3-tropanol,
Examples thereof include 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, and N- (2-hydroxyethyl) isonicotinamide. Examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamido, N-methylacetamido,
Examples include N-dimethylacetamide, propionamide, benzamide and the like. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

Further, one or more selected from basic compounds represented by the following general formula (B1) may be blended.

[0128]

Embedded image (In the formula, n = 1, 2, or 3. Each Y independently represents a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and may include a hydroxy group or an ether. X each independently represents a group represented by the following formulas (X1) to (X3), and two or three Xs may be bonded to form a ring)

[0129]

Embedded image (Wherein ^{R 300, R 302, R 305} is a straight or branched alkylene group of 1 to 4 carbon atoms ^{.R 301,} R
^{Reference numeral 304} denotes a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, which may contain one or more hydroxy groups, ethers, esters or lactone rings. R ³⁰³ represents a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms. )

Specific examples of the compound represented by formula (B1) include tris (2-methoxymethoxyethyl)
Amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- ( 1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2- {2-
(2-hydroxyethoxy) ethoxydiethyl] amine, 4,7,13,16,21,24-hexaoxa-
1,10-diazabicyclo [8.8.8] hexacosan, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosan, 1,4,1
0,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-
6, tris (2-formyloxyethyl) amine, tris (2-formyloxyethyl) amine, tris (2
-Acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, Tris (2-pivaloyloxyxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-te
rt-butoxycarbonyloxyethyl) amine, tris [2- (2-oxopropoxy) ethyl] amine, tris [2- (methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] Amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl]
Amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine,
N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2 -(Ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2
-Methoxyethoxycarbonyl) ethylamine, N, N
-Bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-
(Hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2
-[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-
[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2-
(2-oxopropoxycarbonyl) ethylamine,
N, N-bis (2-acetoxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis ( 2
-Acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N,
N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2
-(4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(2-formyloxyethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N -(2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2 -(Ethoxycarbonyl) ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl)
Ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2-
(Methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl]
Amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine,
N-methylbis (2-pivaloyloxyxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert
-Butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, β- (diethylamino) -Δ-valerolactone and the like.

The compounding amount of the above-mentioned basic compound depends on the amount of the acid generator 1
0.001 to 10 parts, preferably 0.01 to 10 parts by weight
One copy. If the amount is less than 0.001 part, the effect as an additive may not be sufficiently obtained, and if it exceeds 10 parts, the resolution and sensitivity may be reduced.

Further, a compound having a group represented by ΔC-COOH in the molecule can be blended with the resist composition of the present invention.

As the compound having a group represented by ≡C-COOH in the molecule, for example, one or more compounds selected from the following groups I and II can be used, but are not limited thereto. Not something. By blending this component, the PED stability of the resist is improved, and the edge roughness on the nitride film substrate is improved. [Group I] Part or all of the hydrogen atoms of the phenolic hydroxyl group of the compounds represented by the following general formulas (A1) to (A10) is -R ⁴⁰¹ -COOH (R ⁴⁰¹ is a linear or Substituted by a branched alkylene group),
And a phenolic hydroxyl group (C) in the molecule and ΔC-COO
The molar ratio with the group (D) represented by H is C / (C + D) =
A compound which is 0.1 to 1.0. [Group II] Compounds represented by the following general formulas (A11) to (A15).

[0134]

Embedded image(Where R⁴⁰⁸Represents a hydrogen atom or a methyl group.
R⁴⁰², R⁴⁰³Is a hydrogen atom or carbon number 1
8 linear or branched alkyl or alkenyl groups
Show. R⁴⁰⁴Is a hydrogen atom or a straight chain having 1 to 8 carbon atoms or
Is a branched alkyl or alkenyl group, or-(R
⁴⁰⁹)_h-COOR 'group (R' is a hydrogen atom or -R
⁴⁰⁹-COOH). R⁴⁰⁵Is-(CH₂)_i
-(I = 2 to 10), an arylene group having 6 to 10 carbon atoms,
A carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom
Show. R⁴⁰⁶Is an alkylene group having 1 to 10 carbon atoms,
Arylene group, carbonyl group, sulfonyl of the number 6 to 10
Represents a group, an oxygen atom or a sulfur atom. R⁴⁰⁷Is a hydrogen atom
Or a linear or branched alkyl group having 1 to 8 carbon atoms,
A alkenyl group, a phenyl group each substituted with a hydroxyl group or
Represents a naphthyl group. R ⁴⁰⁹Is a linear chain having 1 to 10 carbon atoms
It represents a branched or branched alkylene group. R⁴¹⁰Is hydrogen field
A linear or branched alkyl group having 1 to 8 carbon atoms or
Is an alkenyl group or -R⁴¹¹-COOH group is shown. R
⁴¹¹Is a linear or branched alkylene having 1 to 10 carbon atoms
Shows a substituent group. j is an integer of 0-5. u and h are 0 or
It is one. s1, t1, s2, t2, s3, t3, s
4 and t4 are respectively s1 + t1 = 8, s2 + t2 = 5,
s3 + t3 = 4, s4 + t4 = 6, and
A number having at least one hydroxyl group in the phenyl skeleton
It is. κ represents the compound of the formula (A6) having a weight average molecular weight of 1,
The number is 000 to 5,000. λ is the value of equation (A7)
The compound has a weight average molecular weight of 1,000 to 10,000.
Number. )

[0135]

Embedded image (R ⁴⁰² , R ⁴⁰³ and R ⁴¹¹ have the same meaning as described above. R ⁴¹² represents a hydrogen atom or a hydroxyl group. S5, t
5 is a number that s5 ≧ 0 and t5 ≧ 0, and s5 + t5 = 5. h ′ is 0 or 1. )

As the component, specifically, the following general formula AI
Compounds represented by -1 to 14 and AII-1 to 10 can be exemplified, but are not limited thereto.

[0137]

Embedded image (R ″ represents a hydrogen atom or a CH ₂ COOH group, and in each compound, 10 to 100 mol% of R ″ is CH ₂ CO
OH group. α and κ have the same meanings as described above. )

[0138]

Embedded image

The compounds having a group represented by ≡C—COOH in the molecule can be used alone or in combination of two or more.

The amount of the compound having a group represented by .DELTA.C-COOH in the molecule is 0 to 5 parts, preferably 0.1 to 5 parts, more preferably 0.1 to 5 parts with respect to 100 parts of the base resin. To 3 parts, more preferably 0.1 to 2 parts. 5
If the number is more than the number, the resolution of the resist material may be reduced.

Further, an acetylene alcohol derivative can be added to the resist composition of the present invention as an additive, whereby the storage stability can be improved.

As the acetylene alcohol derivative, those represented by the following general formulas (S1) and (S2) can be suitably used.

[0143]

Embedded image (Wherein R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ , R
⁵⁰⁵ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and X and Y each represent 0 or a positive number, and satisfy the following values. 0 ≦ X ≦ 30, 0 ≦
Y ≦ 30 and 0 ≦ X + Y ≦ 40. )

As acetylene alcohol derivatives, Surfynol 61, Surfynol 82, Surfynol 104, Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol TG, Surfynol PC, Surfynol 44
0, Surfynol 465, Surfynol 485 (A
ir Products and Chemicals
Inc. And Surfynol E1004 (manufactured by Nissin Chemical Industry Co., Ltd.).

The acetylene alcohol derivative is added in an amount of 0.01 to 2% by weight, more preferably 0.02 to 1% by weight, based on 100% by weight of the resist composition. 0.0
If the amount is less than 1% by weight, the effect of improving coating properties and storage stability may not be sufficiently obtained.

The resist composition of the present invention may contain, as an optional component, a surfactant which is commonly used for improving coating properties, in addition to the above components. In addition, the addition amount of the optional component can be a normal amount as long as the effect of the present invention is not impaired.

Here, the surfactant is preferably a nonionic surfactant, and is preferably a perfluoroalkylpolyoxyethylene ethanol, a fluorinated alkyl ester, a perfluoroalkylamine oxide, a perfluoroalkylEO adduct, or a fluorine-containing organosiloxane-based surfactant. And the like. For example, Florad “FC-430”, “F
C-431 "(all manufactured by Sumitomo 3M Limited), Surflon" S-141 "," S-145 "(all manufactured by Asahi Glass Co., Ltd.), Unidyne" DS-401 "," DS
-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), Megafac" F-8151 "(manufactured by Dainippon Ink Industries, Ltd.)," X-70-092 "," X-7 "
0-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Preferably, Florad “FC-4”
30 "(manufactured by Sumitomo 3M Limited)," X-70-09 "
3 "(manufactured by Shin-Etsu Chemical Co., Ltd.).

A pattern can be formed using the resist material of the present invention by a known lithography technique. For example, a film having a thickness of 0 is formed on a substrate such as a silicon wafer by a method such as spin coating. 0.3-2.0μ
m on a hot plate.
１５０150 ° C., 1 to 10 minutes, preferably 80 to 130
Pre-bake at 1 ° C for 1 to 5 minutes. Next, a mask for forming a target pattern is held over the above resist film, and a high energy ray such as far ultraviolet ray, excimer laser, or X-ray or an electron beam is exposed at a dose of about 1 to 200 mJ / cm ² , preferably about 10 to 10 mJ / cm ^2. After irradiating so as to be about 100 mJ / cm ² , on a hot plate at 60 to 150 ° C.
Perform post-exposure bake (PEB) for 1 to 5 minutes, preferably 80 to 130 ° C. for 1 to 3 minutes. In addition, 0.
Using a developer of an aqueous alkali solution such as 1-5%, preferably 2-3% tetramethylammonium hydroxide (TMAH), for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, a dip method A target pattern is formed on the substrate by developing using a conventional method such as a paddle method or a spray method. In addition, the material of the present invention is 248 to 193, especially among high energy rays.
It is most suitable for fine patterning by deep ultraviolet light of nm or excimer laser, X-ray and electron beam. In addition, when the above range is out of the upper limit and the lower limit, a desired pattern may not be obtained.

[0149]

The hydrogenated product of the ring-opening metathesis polymer used in the present invention is suitable for a photoresist for semiconductor microfabrication using ultraviolet rays or far ultraviolet rays having excellent heat resistance, heat decomposition resistance, light transmittance and the like. It is a polymer and is extremely valuable industrially. The resist material of the present invention using this as a base resin is sensitive to high energy rays and is excellent in sensitivity, resolution, and etching resistance, and thus is useful for fine processing by an electron beam or far ultraviolet rays. In particular, since the absorption at the exposure wavelength of an ArF excimer laser or a KrF excimer laser is small, a fine pattern perpendicular to the substrate can be easily formed.

[0150]

EXAMPLES The present invention will be specifically described below with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Examples. [Synthesis Example] A hydrogenated product of the ring-opening metathesis polymer used in the examples was synthesized by the following procedure. The physical properties of the polymer obtained here were measured by the following methods. Average molecular weight: GPC was used to dissolve the obtained cyclic olefin-based ring-opening metathesis polymer and the hydrogenated polymer in tetrahydrofuran, and used as a detector was JASCO 830
-RI and 875-UV, Shodexk as column
Using -805, 804, 803, 802.5, the molecular weight was calibrated by polystyrene standards at room temperature with a flow rate of 1.0 ml / min.

Hydrogenation rate: The powder of the hydrogenated cyclic olefin-based ring-opening metathesis polymer was dissolved in deuterated chloroform, and δ = 4 using 270 MHz- ¹ H-NMR.
The magnitude at which the peak attributed to the carbon-carbon double bond in the main chain at 0 to 6.5 ppm was reduced by the hydrogenation reaction was calculated. Ratio of carboxylic acid contained in the polymer: Measured by neutralization titration using bromothymol blue as an indicator.

[Synthesis Example 1] Synthesis of Polymer 1 In a 300 ml Schlenk flask under nitrogen, 4,10-dioxatricyclo [5.2.1.0 ^2,6 ] dec-8-ene-3 was used as a cyclic olefin monomer. -One (2.43 g, 16 mmol) and 8- (1′-ethylcyclopentoxycarbonyl) tetracyclo [4.4.
0.1 ^2,5 . ^{17, 10} ] -3-dodecene (7.21
g, 24 mmol) in tetrahydrofuran (hereinafter THF)
Dissolved). This _W as the ring-opening metathesis polymerization Sawacho _{(N-2,6-Me 2 C} 6 H 3) (CHCHCM
e ₂ ) (OC (CF ₃ ) ₂ Me) ₂ (PMe ₃ ) (46
2 mg, 0.57 mmol) and reacted at room temperature for 1 hour. Then, butyraldehyde (205 mg, 2.8
5 mmol) and stirred for 30 minutes to terminate the reaction.

This ring-opening metathesis polymer solution was added to methanol to precipitate a ring-opening metathesis polymer, which was then filtered.
After washing with methanol and vacuum drying, 9.46 g of a ring-opening metathesis polymer powder was obtained.

Thereafter, 9.0 g of this ring-opening metathesis polymer powder was placed in a 200 ml autoclave of THF (100 ml).
of dichlorotetrakis (triphenylphosphine) ruthenium (27 mg, 0.022 mmol) and triethylamine (11.3 mg, 0.108 mmol) prepared in advance as a hydrogenation catalyst in THF (2 mL).
0 ml) solution, and a hydrogenation reaction was performed at a hydrogen pressure of 8.1 MPa and 165 ° C. for 5 hours. Then, the temperature was returned to room temperature and hydrogen gas was released. This ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opening metathesis polymer hydrogenated product, and the precipitate was separated by filtration and vacuum-dried to obtain a white powdered ring-opened metathesis polymer hydrogenated product. 8.
0 g was obtained. Of the resulting hydrogenated ring-opening metathesis polymer
^As for the hydrogenation rate calculated from ¹ H-NMR, no peak attributed to protons of the olefin in the main chain was observed, the hydrogenation rate was 100%, and the number average molecular weight Mn in terms of polystyrene standard measured by GPC was 37 , 60
0 and Mw / Mn were 1.10. The composition ratio of the structural units [A] / [B] of the obtained polymer was 60/40.

[Synthesis Example 2] Synthesis of Polymer 2 In Synthesis Example 1, the cyclic olefin monomer was changed to bicyclo [2.2.1] hept-2-ene-5-spiro-3'-
Oxolan-2-one (1.31 g, 8 mmol),
4,10-dioxatricyclo [5.2.1.
0 ^2,6 ] dec-8-en-3-one (1.82 g, 1
2 mmol) and 8- (1′-ethylcyclopentoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-dodecene (6.01 g, 20 mmol
Ring-opening metathesis polymerization was carried out in the same manner as in Synthesis Example 1 except that l) was replaced, to obtain 9.10 g of a ring-opening metathesis polymer.

Further, 9.0 g of the obtained ring-opening metathesis polymer powder was treated in the same manner as in Synthesis Example 1 under a hydrogen pressure of 8.1 MPa and a pressure of 16 MPa.
A hydrogenation reaction was performed at 5 ° C for 5 hours to obtain 8.4 g of a hydrogenated ring-opening metathesis polymer in the form of a white powder. The hydrogenation rate calculated from ¹ H-NMR of the obtained hydrogenated ring-opening metathesis polymer did not show a peak attributed to protons of olefins in the main chain, and the hydrogenation rate was 100%. The measured number average molecular weight Mn in terms of polystyrene standard was 35,600, and Mw / Mn was 1.2.
It was 0. Further, the structural unit [A] /
The composition ratio of [B] / [C] was 50/30/20.

[Synthesis Example 3] Synthesis of Polymer 3 In Synthesis Example 1, the ring-opening metathesis polymer butterfly was replaced with Mo (N-
2,6-iPr ₂ C ₆ H ₃ ) (CHCMe ₃ ) (OC
(CF ₃ ) ₂ Me) ₂ (198 mg, 0.286 mmol)
Ring-opening metathesis polymerization was carried out in the same manner as in Synthesis Example 1 except that l) was replaced, to obtain 9.25 g of a ring-opening metathesis polymer.

Thereafter, 9.0 g of the ring-opening metathesis polymer powder was added to a 200 ml autoclave in THF (100 ml).
chlorohydridocarbonyltris (triphenylphosphine) ruthenium (27 mg, 0.022 mmol) and triethylamine (11.3 mg, 0.108 mmol) previously prepared as hydrogenation catalysts.
Of THF (20 ml) was added, and the hydrogen pressure was set to 8.1MP.
a) After performing a hydrogenation reaction at 165 ° C. for 5 hours, the temperature was returned to room temperature, and hydrogen gas was released. This ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opening metathesis polymer hydrogenated product, and the precipitate was separated by filtration and vacuum-dried to obtain a white powdered ring-opened metathesis polymer hydrogenated product. 8.1 g were obtained. The hydrogenation rate calculated from ¹ H-NMR of the obtained hydrogenated ring-opening metathesis polymer did not show a peak attributed to protons of olefins in the main chain, and the hydrogenation rate was 100%. Measured number average molecular weight Mn in terms of polystyrene standard
Was 75,200 and Mw / Mn was 1.15. The composition ratio of the structural units [A] / [B] of the obtained polymer was 60/40.

[Synthesis Example 4] Synthesis of Polymer 4 In Synthesis Example 2, the ring-opening metathesis polymer butterfly was replaced with Ru (P
(C ₆ H ₁₁ ) ₃ ) ₂ (CHPh) Cl ₂ (470 m
g, 0.57 mmol), except that ring-opening metathesis polymerization was carried out in the same manner as in Synthesis Example 2 to obtain 9.0 g of a ring-opening metathesis polymer.

Further, 9.0 g of the obtained ring-opening metathesis polymer powder was treated in the same manner as in Synthesis Example 2 under a hydrogen pressure of 8.1 MPa and a pressure of 16 MPa.
A hydrogenation reaction was carried out at 5 ° C. for 5 hours to obtain 8.6 g of a hydrogenated ring-opening metathesis polymer as a white powder. The hydrogenation rate calculated from ¹ H-NMR of the obtained hydrogenated ring-opening metathesis polymer did not show a peak attributed to protons of olefins in the main chain, and the hydrogenation rate was 100%. The measured number average molecular weight Mn in terms of polystyrene standard was 33,100, and Mw / Mn was 1.3.
It was 7. Further, the structural unit [A] /
The composition ratio of [B] / [C] was 50/30/20.

[Synthesis Example 5] Synthesis of Polymer 5 Under nitrogen, 1,000 ml of an air was equipped with a magnetic stirrer.
4,10-
Dioxatricyclo [5.2.1.0^2,6] Deca-8
-En-3-one (17.0 g, 111.7 mmol)
And 8- (1'-ethylcyclopentoxycarbonyl)
Toracyclo [4.4.0.1^2,5. 1 ^7,10] -3
-Dodecene (33.57 g, 111.7 mmol)
Dissolved in trahydrofuran (550 ml). To this
1,5-hexadiene (1.5 ml, 1
2.3 mmol) and M as ring-opening metathesis polymer butterfly
o (N-2,6-iPr₂C₆H₃) (CHCMe₃)
(OC (CF₃)₂Me) ₂(786 mg, 1.12 m
mol) was added and reacted at room temperature for 2 hours with stirring. That
Then, butyraldehyde (404 mg, 5.60 mmol
l) was added and the mixture was stirred for 30 minutes to stop the reaction.

The ring-opening metathesis polymer solution was added to methanol to precipitate a ring-opening metathesis polymer, which was then filtered.
After washing with methanol and vacuum drying, 42.5 g of a ring-opening metathesis polymer powder was obtained.

Thereafter, 40.0 g of the ring-opening metathesis polymer powder was added to a 1,000 ml autoclave in THF.
(400 ml), and chlorohydridocarbonyltris (triphenylphosphine) ruthenium (20 mg, 0.02 mmol) previously prepared as a hydrogenation catalyst was prepared.
l) in THF (40 ml) was added and a hydrogen pressure of 6.0 M was added.
After performing a hydrogenation reaction at Pa and 100 ° C. for 20 hours, the temperature was returned to room temperature, and hydrogen gas was released. This ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opening metathesis polymer hydrogenated product, and the precipitate was separated by filtration and vacuum-dried to obtain a white powdered ring-opened metathesis polymer hydrogenated product. 38.5 g were obtained. The hydrogenation rate of the obtained hydrogenated product of the ring-opening metathesis polymer, which was calculated from ¹ H-NMR, showed no peak attributed to protons of olefins in the main chain, and the hydrogenation rate was 100%.
The number average molecular weight Mn in terms of polystyrene standard measured in was 8,260, and Mw / Mn was 1.32.
The composition ratio of the structural units [A] / [B] of the obtained polymer was 50/50.

[Synthesis Example 6] Synthesis of Polymer 6 In a 1,000 ml autoclave equipped with a magnetic stirrer under nitrogen, 5,5-dimethyl-4,10-dioxatricyclo [5.2.1] was used as a cyclic olefin monomer. .
0 ^2,6 ] dec-8-en-3-one (11.41 g,
75.0 mmol) and 8- (2′-ethyl-2′-norbornyloxycarbonyl) tetracyclo [4.4.
0.1 ^2,5 . ^{17, 10} ] -3-dodecene (36.7
3g, 112.5mmol) in tetrahydrofuran (5
00 ml). 1,6 as a chain transfer agent
-Heptadiene (3.17 ml, 23.41 mmol)
And W (N-2,6-i) as ring-opening metathesis polymer butterfly
Pr ₂ C ₆ H ₃ ) (CHCMe ₃ ) (OC (CF ₃ ) ₂
Me) ₂ (740 mg, 0.935 mmol) was added and reacted at room temperature for 3 hours. Then, butyraldehyde (3
60 mg, 5.00 mmol) and stirred for 30 minutes.
The reaction was stopped.

The ring-opening metathesis polymer solution was added to methanol to precipitate a ring-opening metathesis polymer, which was then filtered.
After washing with methanol and vacuum drying, 48.9 g of a ring-opening metathesis polymer powder was obtained.

Thereafter, 40.0 g of this ring-opening metathesis polymer powder, 5% palladium carbon (5.0 g, 2.35 mmol as palladium) as a hydrogenation catalyst and THF (300 as a solvent) were placed in a 500 ml autoclave.
ml), and a hydrogenation reaction was performed at a hydrogen pressure of 8.0 MPa and 120 ° C. for 24 hours. Then, the temperature was returned to room temperature, and hydrogen gas was released. After removing the palladium carbon used as a catalyst by filtration, this ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate a ring-opened metathesis polymer hydrogenated product, and then separated by filtration and vacuum-dried. 39.1 g of a hydrogenated ring-opening metathesis polymer in the form of a white powder was obtained. The hydrogenation rate of the obtained hydrogenated product of the ring-opening metathesis polymer was 99%, as calculated from ¹ H-NMR. The number average molecular weight Mn of the polystyrene standard measured by GPC was 4,690, and Mw / Mn was 1%. .3
It was 8. Further, the structural unit [A] /
The composition ratio of [B] was 60/40.

[Synthesis Example 7] Synthesis of Polymer 7 In a 1,000 ml autoclave equipped with a magnetic stirrer under nitrogen, 5-methyl-4,10-dioxatricyclo [5.2.1.0] was used as a cyclic olefin monomer.
^2,6 ] dec-8-en-3-one (19.94, 12
0.0 mmol) and 8- (2'-methyl-2'-adamantyloxycarbonyl) tetracyclo [4.4.0.
^12,5 . ^{17, 10} ] -3-dodecene (28.20
g, 80.0 mmol) were dissolved in 600 ml of toluene. To this, 1-octene (10.3 m
l (65.0 mmol) and Re (CBu ^t ) (CHBu ^t ) (OC (CF ₃ )
_{2 Me) 2 (687.6mg, 1.00mmol} ) was reacted for 6 hours at 50 ° C. added. Thereafter, butyraldehyde (360 mg, 5.00 mmol) was added and the mixture was stirred for 30 minutes to stop the reaction.

The ring-opening metathesis polymer solution was added to methanol to precipitate a ring-opening metathesis polymer, which was then filtered.
After washing with methanol and vacuum drying, 46.3 g of a ring-opening metathesis polymer powder was obtained.

Thereafter, 40.0 g of this ring-opening metathesis polymer powder was placed in a 1,000 ml autoclave, and dihydridotetrakis (triphenylphosphine) ruthenium (12.0 mg, 0.013 mmol) was used as a hydrogenation catalyst.
l), triethylamine (4.05 mg, 0.04 mm)
ol) and toluene (600 ml) as a solvent were added, and a hydrogenation reaction was carried out at a hydrogen pressure of 8.0 MPa and 100 ° C. for 24 hours. Then, the temperature was returned to room temperature and hydrogen gas was released. This ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opening metathesis polymer hydrogenated product, and the precipitate was separated by filtration and vacuum-dried to obtain a white powdered ring-opened metathesis polymer hydrogenated product. 38.8 g were obtained. The hydrogenation rate of the obtained hydrogenated ring-opening metathesis polymer was calculated from ¹ H-NMR, which was 100%. .42. The composition ratio of the structural units [A] / [B] of the obtained polymer was 40.
/ 60.

[Synthesis Example 8] Synthesis of Polymer 8 20.0 g of hydrogenated ring-opening metathesis polymer obtained in Synthesis Example 5 was added to a 1,000 ml solution of 5.0 ml of trifluoroacetic acid in 1,000 ml of toluene in a 2000 ml eggplant-shaped flask. The mixture was stirred at 70 ° C. for 3 hours.
It was dissolved in HF, added to methanol, precipitated, filtered, and dried under vacuum to obtain 17.8 g of a hydrogenated ring-opening metathesis polymer partially esterified as a white powder. The composition ratio of the constituent units [A] / [B] / [D] of the obtained polymer was 30/50/20, the number average molecular weight Mn measured by GPC was 8,150, and Mw / Mn was 1. 33.

[Synthesis Example 9] Synthesis of Polymer 9 15.0 g of the hydrogenated ring-opening metathesis polymer obtained in Synthesis Example 6 was added to a solution of 5.0 ml of trifluoroacetic acid in 1,000 ml of benzene in a 2000 ml eggplant-shaped flask. The mixture was stirred at 70 ° C. for 2 hours.
It was dissolved in HF, added to methanol, precipitated, filtered, and dried under vacuum to obtain 13.1 g of a hydrogenated ring-opening metathesis polymer partially decomposed as a white powder. The composition ratio of the structural units [A] / [B] / [D] of the obtained polymer was 40/40/20, the number average molecular weight Mn measured by GPC was 4,490, and Mw / Mn was 1. 35.

[Synthesis Example 10] Synthesis of Polymer 10 15.0 g of the hydrogenated ring-opening metathesis polymer obtained in Synthesis Example 7 was added to a 1,000 ml solution of 10.0 ml of concentrated hydrochloric acid in 1,000 ml of THF in a 2000 ml eggplant-shaped flask.
The mixture was stirred at 0 ° C. for 6 hours, added to methanol, precipitated, filtered and dried under vacuum to obtain 13.0 g of a hydrogenated ring-opening metathesis polymer partially decomposed as a white powder.
The composition ratio of the constituent units [A] / [B] / [D] of the obtained polymer was 25/60/15, the number average molecular weight Mn measured by GPC was 2,810, and Mw / Mn was 1. 39.

[Synthesis Example 11] Synthesis of Polymer 11 In a 500 ml autoclave equipped with a magnetic stirrer under nitrogen, 4,10-dioxatricyclo [5.2.1.0 ^2,6 ] deca was used as a cyclic olefin monomer. 8-en-3-one (9.89 g, 65.0 mmol), 8-
(1′-ethylcyclopentoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^{7,1 0]} -3- dodecene (11.72 g, 39.0 mmol) and 8-te
rt-butoxycarbonyltetracyclo [4.4.0.
^12,5 . 1 ^7,10 ] -3-dodecene (6.77 g,
26.0 mmol) were dissolved in 300 ml of tetrahydrofuran. To this, 1,5-hexadiene (0.75 ml, 6.5 mmol) as a chain transfer agent and Mo (N-2,6-iPr ₂ C) as a ring-opening metathesis polymer butterfly were added.
_{6 H 3) (CHCMe 2 Ph} ) (OC (CF 3) 2 M
e) ₂ (536 mg, 0.70 mmol) was added and reacted at room temperature for 2 hours. Then, butyraldehyde (250
mg, 3.47 mmol), and the mixture was stirred for 30 minutes to stop the reaction.

The ring-opening metathesis polymer solution was added to methanol to precipitate a ring-opening metathesis polymer, which was then filtered.
After washing with methanol and vacuum drying, 26.6 g of a ring-opening metathesis polymer powder was obtained.

Thereafter, the mixture was placed in a 500 ml autoclave.
20.0 g of the ring-opening metathesis polymer powder of
0 ml) and previously prepared as a hydrogenation catalyst
Dichlorotris (triphenylphosphine) osmium
(30.0 mg, 0.029 mmol) and triethyl alcohol
Min (11.74 mg, 0.116 mmol) in THF
(20 ml) solution, hydrogen pressure 6.0 MPa, 100 MPa
After performing the hydrogenation reaction at 20 ° C for 20 hours,
Back hydrogen gas was released. This ring-opening metathesis polymer water
Ring-opening metathesis polymerization by adding an additive solution to methanol
Precipitate the hydrogenated product, separate by filtration, and perform vacuum drying.
-Opened ring-opening metathesis polymer hydrogenated product
Was obtained 18.8 g. The resulting ring-opening metathesis polymer hydrogen
Additive ¹The hydrogenation rate calculated from H-NMR was 100.
% And the polystyrene standard measured by GPC
The converted number average molecular weight Mn is 9,110, and Mw / Mn is
1.43. Also, the structural unit of the obtained polymer
The composition ratio of [A] / [B] / [E] is 30/50/20.
there were.

[Synthesis Example 12] Synthesis of Polymer 12 In a 500 ml autoclave equipped with a magnetic stirrer under nitrogen, 4,10-dioxatricyclo [5.2.1.0 ^2,6 ] deca was used as a cyclic olefin monomer. 8-en-3-one (9.13 g, 60.0 mmol), 8-
(1′-ethylcyclopentoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^{7,1 0]} -3- dodecene (14.42 g, 48.0 mmol) and 8-methoxycarbonyltetracyclo [4.4.0.1 ^{2, 5.}
1 ^7,10] -3-dodecene (2.62 g, 12.0m
mol) was dissolved in 350 ml of toluene. To this, 1,5-hexadiene (0.70 ml,
6.0 mmol) and W as ring-opening metathesis polymerized butterfly
_{(N-2,6-Me 2 C} 6 H 3) (CHCHCMe 2)
(OC (CF ₃ ) ₂ Me) ₂ (440 mg, 0.60 m
mol) was added and reacted at room temperature for 5 hours. Then, butyraldehyde (216 mg, 3.0 mmol) was added and 3
The reaction was stopped by stirring for 0 minutes.

The ring-opening metathesis polymer solution was added to methanol to precipitate a ring-opening metathesis polymer, which was then filtered.
After washing with methanol and vacuum drying, 24.7 g of a ring-opening metathesis polymer powder was obtained.

Thereafter, 20.0 g of this ring-opening metathesis polymer powder was placed in a 500 ml autoclave and treated with toluene (3
50 ml) and dichlorobis (triphenylphosphine) palladium (66.0 m) as a hydrogenation catalyst.
g, 0.094 mmol) in toluene (30 ml), and a hydrogenation reaction was carried out at a hydrogen pressure of 6.0 MPa and 100 ° C. for 20 hours. Then, the temperature was returned to room temperature and hydrogen gas was released. This ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opening metathesis polymer hydrogenated product, and the precipitate was separated by filtration and vacuum-dried to obtain a white powdered ring-opened metathesis polymer hydrogenated product. 17.9 g were obtained. The resulting hydrogenated ring-opening metathesis polymer ¹ H-
The hydrogenation rate calculated from NMR was 100%, and GP
The number average molecular weight Mn in terms of polystyrene measured in C was 8,810, and Mw / Mn was 1.24. In addition, the structural units [A] / [B] /
The composition ratio of [E] was 40/50/10.

[Synthesis Example 13] Synthesis of Polymer 13 9.0 g of the hydrogenated ring-opening metathesis polymer obtained in Synthesis Example 12 was added to 400 ml of a 5% aqueous solution of potassium hydroxide / methanol in a 1,000 ml flask.
Stir at 3 ° C for 3 hours, and then add
The mixture was neutralized, precipitated, filtered, washed with water, and dried under vacuum to obtain 8.4 g of a hydrogenated ring-opening metathesis polymer partially hydrolyzed as a white powder. The composition ratio of the structural units [A] / [B] / [D] of the obtained polymer was 40/50.
/ 10, and the number average molecular weight Mn measured by GPC was 8,730 and Mw / Mn was 1.25.

[Synthesis Example 14] Synthesis of Polymer 14 In a 500 ml autoclave equipped with a magnetic stirrer under nitrogen, 4,10-dioxatricyclo [5.2.1.0 ^2,6 ] deca was used as a cyclic olefin monomer. 8-en-3-one (9.13 g, 60.0 mmol), 8-
(1′-ethylcyclopentoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^{7,1 0]} -3- dodecene (9.01 g, 30.0 mmol) and 8- (tetrahydropyran-2'-yl) oxycarbonyl tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-dodecene (8.65 g, 30.0 mmol) in THF 32
Dissolved in 0 ml. This as a chain transfer agent 1,5-hexadiene (0.70 ml, 6.0 mmol) and ring-opening metathesis polymerization Sawacho as _{W (N-2,6-Me 2} C 6
H ₃ ) (CHCHCMe ₂ ) (OBu ^t ) ₂ (PM
e ₃ ) (356 mg, 0.60 mmol) was added and reacted at room temperature for 5 hours. Then, butyraldehyde (216
mg, 3.0 mmol), and the mixture was stirred for 30 minutes to stop the reaction.

This ring-opening metathesis polymer solution was added to methanol to precipitate a ring-opening metathesis polymer, which was filtered,
After washing with methanol and vacuum drying, 24.3 g of a ring-opening metathesis polymer powder was obtained.

Thereafter, 20.0 g of this ring-opening metathesis polymer powder was added to a 500 ml autoclave in THF (30 ml).
0 ml), and chlorotris (triphenylphosphine) rhodium (91.0 mg,
0.10 mmol) in THF (30 ml)
After performing a hydrogenation reaction at a hydrogen pressure of 6.0 MPa and 100 ° C. for 20 hours, the temperature was returned to room temperature, and hydrogen gas was released.
This ring-opening metathesis polymer hydrogenate solution was added to methanol to precipitate a ring-opening metathesis polymer hydrogenate,
After filtration and separation, vacuum drying was performed to obtain 17.1 g of a hydrogenated ring-opening metathesis polymer as a white powder. The hydrogenation rate of the obtained ring-opening metathesis polymer hydrogenated product calculated from ¹ H-NMR was 100%, the number average molecular weight Mn in terms of polystyrene standard measured by GPC was 9,620, and Mw / Mn was 1 .19. The composition ratio of the structural units [A] / [B] / [E] of the obtained polymer was 25/50/25.

[Synthesis Example 15] Synthesis of Polymer 15 8.0 g of the hydrogenated ring-opening metathesis polymer obtained in Synthesis Example 14 was added to a 500 ml solution of 3.0 ml of trifluoroacetic acid in a 1,000 ml eggplant-shaped flask. And stirred at 30 ° C. for 1 hour.
It was dissolved in F, added to methanol, precipitated, filtered, and dried under vacuum to obtain 6.8 g of a white powder. As a result of NMR analysis,
It was a hydrogenated ring-opening metathesis polymer in which only the tetrahydropyranyl group was esterified. The composition ratio of the structural units [A] / [B] / [D] of the obtained polymer was 25/50.
/ 25, the number average molecular weight Mn measured by GPC was 9,060, and Mw / Mn was 1.21.

[Synthesis Example 16] Synthesis of Polymer 16 Partially esterified ring-opening obtained in Synthesis Example 8 in a 500-ml three-necked eggplant-shaped flask equipped with a 100-ml dropping funnel, a stirrer and a three-way cock under a nitrogen stream. 8.0 g of hydrogenated metathesis polymer was added to a solution of 80 mg of p-toluenesulfonic acid / pyridine salt in 200 ml of toluene, and a solution of 5,6-dihydropyran (10 g) in 70 ml of toluene was stirred for about 1 hour at 25 ° C. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours. After the solvent was distilled off, the residue was further dissolved in THF, added to methanol, precipitated, filtered, and dried under vacuum to obtain 6.6 g of a partially powdered hydrogenated ring-opening metathesis polymer in the form of a white powder. Constituent units [A] / [B] / [D] of the obtained polymer
/ [E] is 30/50/5/15, and GP
C: 8,200, Mw / M
n was 1.33.

[Synthesis Example 17] Synthesis of Polymer 17 In a 500 ml autoclave equipped with a magnetic stirrer under nitrogen, 4-oxatricyclo [5.2.1.0 ^2,6 ] dec-8-ene was used as a cyclic olefin monomer. -3-
ON (4.51 g, 30.0 mmol), 8- (1′-
Ethylcyclopentoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 17, ¹⁰ ] -3-dodecene (12.02 g, 40.0 mmol) and 5- (1'-
Ethylcyclopentoxycarbonyl) -6-methoxycarbonyl-7-oxabicyclo [2.2.1] hept-
2-ene (8.83 g, 30.0 mmol) was added to THF3
Dissolved in 50 ml. 1-hexene (0.42 ml, 3.5 mmol) as a chain transfer agent and W (N-2,6-iPr ₂ C) as a ring-opening metathesis polymer butterfly
^{_{6 H 3) (CHCMe 3)}} (OBu t) 2 (288m
g, 0.50 mmol) and reacted at room temperature for 5 hours. Then, butyraldehyde (180 mg, 2.5 m
mol) was added and the mixture was stirred for 30 minutes to stop the reaction.

The ring-opening metathesis polymer solution was added to methanol to precipitate a ring-opening metathesis polymer, which was then filtered,
After washing with methanol and vacuum drying, 23.3 g of a ring-opening metathesis polymer powder was obtained.

Thereafter, 20.0 g of the ring-opening metathesis polymer powder was placed in a 1,000 ml autoclave in THF.
(500 ml) and dichlorobis (tetrahydrofuran) bis (triphenylphosphine) ruthenium (4.0 mg, 0.0 mg) prepared in advance as a hydrogenation catalyst.
048 mmol) and triethylamine (4.86 mg,
(0.048 mmol) in THF (100 ml) was added, and a hydrogenation reaction was carried out at a hydrogen pressure of 6.0 MPa and 100 ° C. for 20 hours. Then, the temperature was returned to room temperature and hydrogen gas was released. This ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opening metathesis polymer hydrogenated product, and the precipitate was separated by filtration and vacuum-dried to obtain a white powdered ring-opened metathesis polymer hydrogenated product. 18.1 g were obtained. ¹ H-NMR of the hydrogenated ring-opening metathesis polymer obtained
Is 100%, and the number average molecular weight M in terms of polystyrene standard measured by GPC.
n was 12,600 and Mw / Mn was 1.39. Further, the structural unit [A] / [A] ′ /
The composition ratio of [B] was 40/30/30.

[Synthesis Example 18] Synthesis of Polymer 18 In a 500 ml autoclave equipped with a magnetic stirrer under nitrogen, 6-oxapentacyclo [9.2.1.1 ^3,9 . 0 ^2,10 . 0
^4,8 ] -pentadec-12-en-5-one (10.
81 g, 50.0 mmol) and 5- (1′-ethylcyclopentoxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene (11.82 g, 5
0.0 mmol) was dissolved in 250 ml of THF. 1-heptene (0.64 ml, 6.
5 mmol) and W (N
_{-2,6-Me 2 C 6 H 3} ) (CHCHCMePh)
(OBu ^t ) ₂ (PMe ₃ ) (328 mg, 0.50 m
mol) was added and reacted at room temperature for 5 hours. Thereafter, pentylaldehyde (258 mg, 3.0 mmol) was added, and the mixture was stirred for 30 minutes to stop the reaction.

The ring-opening metathesis polymer solution was added to methanol to precipitate a ring-opening metathesis polymer, which was then filtered.
After washing with methanol and vacuum drying, 20.8 g of a ring-opening metathesis polymer powder was obtained.

Thereafter, 15.0 g of the ring-opening metathesis polymer powder was added to a 500 ml autoclave in THF (30 ml).
0 ml), and chlorohydridocarbonyltris (triphenylphosphine) ruthenium (9.5 mg, 0.01 mmol) and triphenylamine (4.9 mg, 0.02 mmol) previously prepared as hydrogenation catalysts.
Of THF (30 ml) was added, and the hydrogen pressure was set to 10.0MP.
a) After performing a hydrogenation reaction at 80 ° C. for 42 hours, the temperature was returned to room temperature, and hydrogen gas was released. This ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opening metathesis polymer hydrogenated product, and the precipitate was separated by filtration and vacuum-dried to obtain a white powdered ring-opened metathesis polymer hydrogenated product. 12.3 g were obtained. The hydrogenation rate of the obtained hydrogenated product of the ring-opening metathesis polymer was 100%, as calculated from ¹ H-NMR, and the number average molecular weight Mn in terms of polystyrene measured by GPC was 8,450, Mw /
Mn was 1.29. The composition ratio of the structural units [A] / [B] of the obtained polymer was 50/50.

[Synthesis Example 19] Synthesis of Polymer 19 In a 500 ml autoclave equipped with a magnetic stirrer under nitrogen, 4,10-dioxatricyclo [5.2.1.0 ^2,6 ] deca was used as a cyclic olefin monomer. 8-en-3-one (11.41 g, 75.0 mmol), 8
-(1'-ethylcyclopentoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] -3-dodecene (7.51 g, 25.0 mmol) and 8-
(2'-ethyl-2'-norbornyl butyloxycarbonyl) tetracyclo [4.4.0.1 ^2, 5.
1 ^7,10 ] -3-dodecene (8.16 g, 25.0 m
mol) was dissolved in 300 ml of THF. To this, 1,5-hexadiene (1.04 ml, 9.
0 mmol) and W (N
−2,6-iPr ₂ C ₆ H ₃ ) (CHCMe ₃ ) (OB
_{^{u t) 2 (PMe 3)}} (652mg, 1.00mmo
l) was added and reacted at room temperature for 5 hours. Thereafter, butyraldehyde (432 mg, 6.0 mmol) was added and the mixture was stirred for 30 minutes to stop the reaction.

This ring-opening metathesis polymer solution was added to methanol to precipitate a ring-opening metathesis polymer, which was filtered,
After washing with methanol and vacuum drying, 25.1 g of a ring-opening metathesis polymer powder was obtained.

Thereafter, 10.0 g of this ring-opening metathesis polymer powder was placed in a 1,000 ml autoclave in THF.
(350 ml), and THF of dichlorotris (trimethylphosphite) ruthenium (44.8 mg, 0.10 mmol) and triethylamine (15.2 mg, 0.15 mmol) previously prepared as a hydrogenation catalyst were dissolved.
(200 ml) solution, hydrogen pressure 10.0 MPa, 7
After performing a hydrogenation reaction at 0 ° C. for 20 hours, the temperature was returned to room temperature, and hydrogen gas was released. This ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opening metathesis polymer hydrogenated product, and the precipitate was separated by filtration and vacuum-dried to obtain a white powdered ring-opened metathesis polymer hydrogenated product. 8.8 g were obtained. The hydrogenation rate calculated from ¹ H-NMR of the obtained hydrogenated ring-opening metathesis polymer was 100.
%, The number average molecular weight Mn in terms of polystyrene standard measured by GPC was 8,330, and Mw / Mn was 1.44. The composition ratio of the structural units [A] / [A] ′ / [B] of the obtained polymer was 20/20/60.
Met.

[Synthesis Example 20] Synthesis of Polymer 20 In a 500 ml Schlenk flask under nitrogen, 4,10-dioxatricyclo [5.2.1.0 ^2,6 ] dec-8-ene-3 was used as a cyclic olefin monomer. -One (2.43 g, 16 mmol) and 8- (1′-ethylcyclopentoxycarbonyl) -8-methyltetracyclo [4.4.0.1 ^2,5 . 17, ¹⁰ ] -3-dodecene (7.55 g, 24 mmol) in tetrahydrofuran 2
Dissolved in 00 ml. To this, W (N-2,6-iPr ₂ C ₆ H ₃ ) (CHCHC) was used as a ring-opening metathesis polymer butterfly.
Me ₂ ) (OC (CF ₃ ) ₂ Me) ₂ (PMe ₃ ) (6
(0.6 mg, 0.70 mmol) and reacted at room temperature for 30 minutes. Then, butyraldehyde (202 mg,
(2.80 mmol) was added and the mixture was stirred for 1 hour to stop the reaction.

The ring-opening metathesis polymer solution was added to methanol to precipitate a ring-opening metathesis polymer, which was then filtered.
After washing with methanol and vacuum drying, 9.13 g of a ring-opening metathesis polymer powder was obtained.

Thereafter, 9.0 g of this ring-opening metathesis polymer powder was placed in a 500 ml autoclave of THF (250 ml).
ml), and dichlorotetrakis (triphenylphosphine) ruthenium (27 mg, 0.022 mmol) and triethylamine (11.3 mg, 0.108 mmol) previously prepared as hydrogenation catalysts in THF (5 mg) were dissolved.
0 ml) solution, and a hydrogenation reaction was performed at a hydrogen pressure of 9.0 MPa and 120 ° C. for 16 hours. Then, the temperature was returned to room temperature and hydrogen gas was released. This ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opening metathesis polymer hydrogenated product, and the precipitate was separated by filtration and vacuum-dried to obtain a white powdered ring-opened metathesis polymer hydrogenated product. 7.4 g were obtained. The hydrogenation rate of the obtained hydrogenated product of the ring-opening metathesis polymer was 100%, as calculated from ¹ H-NMR, the number average molecular weight Mn was 28,600 in terms of polystyrene standard measured by GPC, and .
07. Also, the structural unit [A] of the obtained polymer
The composition ratio of / [B] was 60/40.

[Synthesis Example 21] Synthesis of Polymer 21 A cyclic olefin was placed in a 500 ml Schlenk flask under nitrogen.
4,10-dioxatricyclo as the monomer
[5.2.1.0^2,6] Dec-8-en-3-one
(4.56 g, 30.0 mmol) and 8- (1'-ethyl)
Rucyclopentoxycarbonylmethyl) tetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene
(6.29 g, 20.0 mmol) in tetrahydrofura
Dissolved in 200 ml. This is followed by ring-opening metathesis polymerization
W (N-2,6-iPr) as a butterfly₂C₆H ₃) (CHC
HCMe₂) (OC (CF₃)₂Me)₂(PMe₃)
(606 mg, 0.70 mmol) for 30 minutes at room temperature
Reaction. Then, butyraldehyde (202m
g, 2.80 mmol) and stirred for 1 hour to stop the reaction.
Stopped.

This ring-opening metathesis polymer solution was added to methanol to precipitate a ring-opening metathesis polymer, which was then filtered.
After washing with methanol and vacuum drying, 9.98 g of a ring-opening metathesis polymer powder was obtained.

Thereafter, 9.0 g of this ring-opening metathesis polymer powder was placed in a 500 ml autoclave of THF (250 ml).
ml), and dichlorotetrakis (triphenylphosphine) ruthenium (61 mg, 0.05 mmol) and triethylamine (10.1 mg, 0.10 mmol) prepared in advance as a hydrogenation catalyst in THF (50 m2).
1) The solution was added, and a hydrogenation reaction was performed at 90 ° C. and a hydrogen pressure of 9.0 MPa for 16 hours. Then, the temperature was returned to room temperature and hydrogen gas was released. This ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opening metathesis polymer hydrogenated product, and the precipitate was separated by filtration and vacuum-dried to obtain a white powdered ring-opened metathesis polymer hydrogenated product. 8.0g
Obtained. ¹ H of the resulting hydrogenated ring-opening metathesis polymer
-The hydrogenation rate calculated from NMR was 100%,
The number average molecular weight Mn of the polystyrene standard measured by PC was 34,100, and Mw / Mn was 1.09. Also, the structural units [A] / [B] of the obtained polymer
Was 40/60.

[Synthesis Example 22] Synthesis of Polymer 22 In a 500 ml Schlenk flask under nitrogen, 5,5-dimethyl-4,10-dioxatricyclo [5.2.1.0 ^2,6 ] deca was used as a cyclic olefin monomer. -8-en-3-one (1.08 g, 6.0 mmol) and 8.9
-Di (1'-ethylcyclopentoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . ^{17 , 10} ] -3-
Dodecene (6.17 g, 14.0 mmol) was dissolved in 200 ml of tetrahydrofuran. Mo (N-2,6-iPr ₂ C) was used as a ring-opening metathesis polymer butterfly.
_{6 H 3) (CHCHCMe 2)} (OC (CF 3) 2 M
e) ₂ (206 mg, 0.35 mmol) was added and reacted at room temperature for 30 minutes. Then, butyraldehyde (10
(8 mg, 1.50 mmol) and stirred for 1 hour to stop the reaction.

This ring-opening metathesis polymer solution was added to methanol to precipitate a ring-opening metathesis polymer, which was then filtered.
After washing with methanol and vacuum drying, 6.66 g of a ring-opening metathesis polymer powder was obtained.

Thereafter, 6.0 g of this ring-opening metathesis polymer powder was placed in a 500 ml autoclave in THF (250 ml).
ml), and dichlorotetrakis (triphenylphosphine) ruthenium (36.6 mg, 0.03 mmol) and triethylamine (10.1 mg, 0.10 mmol) prepared in advance as a hydrogenation catalyst in THF (5 mL).
0 ml) solution, and a hydrogenation reaction was performed at a hydrogen pressure of 9.0 MPa and 100 ° C. for 16 hours. Then, the temperature was returned to room temperature and hydrogen gas was released. This ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opening metathesis polymer hydrogenated product, and the precipitate was separated by filtration and vacuum-dried to obtain a white powdered ring-opened metathesis polymer hydrogenated product. 5.4 g were obtained. The hydrogenation rate of the obtained hydrogenated product of the ring-opening metathesis polymer calculated from ¹ H-NMR was 100%, the number average molecular weight Mn in terms of polystyrene standard measured by GPC was 26,900, and Mw / Mn was 1 .
06. Also, the structural unit [A] of the obtained polymer
The composition ratio of / [B] was 30/70.

[0203]

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[0204]

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[0205]

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[0206]

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[0207]

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[0208]

[Of 75]

Example I The resist composition of the present invention was evaluated for its resolution in KrF excimer laser exposure. [Examples I-1 to 12] Evaluation of resist resolution The polymer (Polymer 1, 2) represented by the above formula was used as a base resin, and an acid generator (PAG) represented by the following formula was used.
1, 2), a dissolution controlling agent represented by the following formula (DRR1
4), a basic compound, ΔC- in the molecule represented by the following formula:
Compound having a group represented by COOH (ACC1, 2)
And the solvent were mixed in the composition shown in Table 1. Next, filter them with a Teflon (registered trademark) filter (pore size 0.2 μm).
To obtain a resist material.

[0210]

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[0211]

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[0212]

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The resist solution was coated with an antireflection film (D manufactured by Nissan Chemical Industries, Ltd.).
(UV 30 nm, 55 nm) was spin-coated on the silicon wafer, and heat-treated at 130 ° C. for 90 seconds to form a 485 nm-thick resist film. A KrF excimer laser stepper (manufactured by Nikon Corporation, NA = 0.
Exposure was performed using 5), heat treatment was performed at 110 ° C. for 90 seconds, and paddle development was performed using a 2.38% aqueous solution of tetramethylammonium hydroxide for 60 seconds.
One line and space pattern was formed. The cross section of the developed wafer is observed by a cross-sectional SEM (scanning electron microscope), and an exposure amount for resolving a 0.30 μm line and space at 1: 1 (optimum exposure amount = Eop, mJ /
The minimum line width (μm) of the separated lines and spaces in cm ² ) was taken as the resolution of the evaluation resist. In addition, the shape of the pattern at that time is classified into any one of a rectangle, a round head, a T-top, a forward taper, and a reverse taper.

Table 1 shows the composition and evaluation results of each resist. In Table 1, the solvent and the basic compound are as follows. All solvents used contained 0.05% by weight of FC-430 (manufactured by Sumitomo 3M Limited). CyHO: cyclohexanone TBA: tributylamine TEA: triethanolamine TMMEA: trismethoxymethoxyethylamine TMMEA: trismethoxyethoxymethoxyethylamine

[0215]

[Table 1]

From the results shown in Table 1, it was confirmed that the resist material of the present invention had high sensitivity and high resolution in KrF excimer laser exposure.

Example II The resist composition of the present invention was evaluated for resolution in ArF excimer laser exposure. [Examples II-1 to 22] Evaluation of resolution of resist In the same manner as described above, resist materials having the compositions shown in Table 2 were prepared.

A resist solution was applied to an antireflection film (A manufactured by Nissan Chemical Industries, Ltd.).
(RC25, 77 nm) was applied on a silicon wafer, and heat-treated at 130 ° C. for 90 seconds to form a resist film having a thickness of 375 nm. This is an ArF excimer laser stepper (Nikon Corporation, NA = 0.5
Exposure was performed using 5), heat treatment was performed at 110 ° C. for 90 seconds, and paddle development was performed using a 2.38% aqueous solution of tetramethylammonium hydroxide for 60 seconds.
One line and space pattern was formed. The developed wafer is cut and observed with a cross-sectional SEM (scanning electron microscope), and an exposure amount (optimum exposure amount = Eop, mJ /
The minimum line width (μm) of the separated lines and spaces in cm ² ) was taken as the resolution of the evaluation resist. In addition, the shape of the pattern at that time is classified into any one of a rectangle, a round head, a T-top, a forward taper, and a reverse taper.

Table 2 shows the composition of each resist and the evaluation results. In Table 2, the solvent and the basic compound are as follows. In addition, all solvents used contained 0.01% by weight of FC-430 (manufactured by Sumitomo 3M Limited). CyHO: cyclohexanone TMMEA: trismethoxymethoxyethylamine

[0220]

[Table 2]

From the results shown in Table 2, it was confirmed that the resist material of the present invention had high sensitivity and high resolution in ArF excimer laser exposure.

[Brief description of the drawings]

FIG. 1 shows a ¹ H-NMR spectrum of a hydrogenated product of the ring-opening metathesis polymer obtained in Synthesis Example 1.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Shigehiro Nakura 28-1 Nishifukushima, Nishi-Jukumura, Nakakubijo-gun, Niigata Prefecture Within Synthetic Research Laboratory, Shin-Etsu Chemical Co., Ltd. 28-1 Oishi Nishifukushima Shin-Etsu Chemical Industry Co., Ltd. Synthetic Technology Laboratory (72) Inventor Satoshi Watanabe 28-1 Nishi-Fukushima Oaza, Nakakushiro-gun, Niigata Prefecture Shin-Etsu Chemical Industry Co., Ltd. Synthetic Technology Laboratory F-term (reference) AA01 AA02 AA09 AB16 AC04 AC06 AC08 AD03 BE00 BE10 BG00 CB08 CB41 CB55 CB56 FA17 4J032 BA07 CA32 CA34

Claims (9)

[Claims] 1. At least the following general formula [1](Where R¹~ R⁴At least one of the following general
Formula [2](In the formula, a chain line indicates a bond. R⁵Is hydrogen atom, carbon number
1-10 linear, branched or cyclic alkyl groups, carbon
Linear, branched or cyclic alkoxyal having 2 to 10
A kill group, or a linear, branched or cyclic C1-C10 group
Represents an acyl group. R⁶Is a straight chain having 1 to 10 carbon atoms,
Shows a branched or cyclic alkyl group. W¹Is a single bond or charcoal
And a k + 2 divalent hydrocarbon group having a prime number of 1 to 10. Z is carbon
A divalent hydrocarbon group represented by the following formulas 2 to 15;
Forms a single or bridged ring with the k is 0 or 1
It is. ) Represents a tertiary ester group of the cyclic alkyl
The other are each independently a hydrogen atom
, Linear, branched or cyclic alkyl having 1 to 20 carbon atoms
Group, halogen atom, C1-C20 linear or branched
Or a cyclic halogenated alkyl group having 1 to 20 carbon atoms
Chain, branched or cyclic alkoxy group, having 2 to 20 carbon atoms
Linear, branched or cyclic alkoxyalkyl group, charcoal
Linear, branched or cyclic alkyl carboxy having a prime number of 2 to 20
Bonyloxy group, arylcarbonyl having 6 to 20 carbon atoms
Oxy group, linear, branched or cyclic having 1 to 20 carbon atoms
Alkylsulfonyloxy group, aryl having 6 to 20 carbon atoms
Rusulfonyloxy group, C2-C20 linear, branched
Or cyclic alkoxycarbonyl group, or having 3 to 3 carbon atoms
20 linear, branched or cyclic alkoxycarbonyl
X selected from alkyl groups¹Is -O- or -CR⁷ ₂−
(R⁷Is a hydrogen atom or a straight or branched chain having 1 to 10 carbon atoms
Represents an alkyl group), which may be the same or different
No. j represents 0 or an integer of 1 to 3; )
The unit [A] is represented by the following general formula [3]:(Where R⁸~ R¹¹Are each independently a hydrogen atom or
Is a linear, branched or cyclic alkyl having 1 to 10 carbons
X²Is -O- or -CR¹² ₂− (R ¹²Is
A hydrogen atom or a linear or branched alkyl having 1 to 10 carbon atoms
Represents a kill group), and may be the same or different. m is
Represents an integer of 0 or 1 to 3. ) Structural unit
[B] and / or the following general formula [4]:(Where R¹³~ R¹⁶Is independently a hydrogen atom
Or a linear, branched or cyclic alkyl having 1 to 10 carbon atoms
And X³Is -O- or -CR¹⁷ ₂− (R¹⁷
Is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.
Represents an alkyl group) and may be the same or different. Y
¹And Y²Is that one is-(C = O)-and the other is
-CR¹⁸ ₂− (R¹⁸Is a hydrogen atom or 1 to 10 carbon atoms
Represents a linear or branched alkyl group). n is
Represents an integer of 0 or 1 to 3. ) Structural unit
[C] and represented by the general formula [1].
X of unit [A]¹, A structural unit represented by the general formula [3]
X of [B]²And a structural unit represented by general formula [4]
X of [C]³At least one of which is -O-,
Has a molar ratio [A] / ([B] + [C]) of 20/80
９９99/1, and the weight average molecular weight Mw and the number average
The ratio (Mw / Mn) to the molecular weight Mn is 1.0 to 2.0.
Using hydrogenated ring-opening metathesis polymer as base resin
A resist material characterized by containing. 2. The functional group having a cyclic alkyl tertiary ester group represented by the general formula [2] selected as at least one of R ^{1 to} R ^{4 in} the general formula [1] is 1-alkylcyclopentyl The resist material according to claim 1, which is an ester, 2-alkyl-2-norbornyl ester or 2-alkyl-2-adamantyl ester. 3. The hydrogenated product of the ring-opening metathesis polymer,
Further, the following general formula [5] (Wherein at least one of R ^{19 to} R ²² is represented by the following general formula [6]: (In the formula, a chain line represents a bond. R ²³ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms. Represents an alkoxyalkyl group or a linear, branched or cyclic acyl group having 1 to 10 carbon atoms, and W ² is a single bond or 1 to 10 carbon atoms.
Represents a k + divalent hydrocarbon group. q is 0 or 1. ) Is a functional group having a carboxylic acid group represented by
Others are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a halogen atom,
C1-C20 linear, branched or cyclic halogenated alkyl group, C1-C20 linear, branched or cyclic alkoxy group, C2-C20 linear or branched Or a cyclic alkoxyalkyl group, a linear, branched or cyclic alkylcarbonyloxy group having 2 to 20 carbon atoms, an arylcarbonyloxy group having 6 to 20 carbon atoms,
-20 linear, branched or cyclic alkylsulfonyloxy group, a C6-C20 arylsulfonyloxy group, a C2-C20 linear, branched or cyclic alkoxycarbonyl group, or 3-20 linear, selected from alkoxycarbonyl alkyl group branched or cyclic, ^{X 4} is -O- or ^{-CR ₂₄} 2 - ^(R ₂₄ represents a linear hydrogen atom or a C1-10 or Represents a branched alkyl group), and may be the same or different. p represents 0 or an integer of 1 to 3. 3. The resist material according to claim 1, which comprises a structural unit [D] represented by the formula: 4. In a hydrogenated product of a ring-opening metathesis polymer contained as a base resin, a structural unit [A] represented by the general formula [1] and a structural unit [B] represented by the general formula [3] And the structural molar ratio of the structural unit [D] represented by the general formula [5] to the structural unit [C] represented by the general formula [4] ([A] + [B] + [C]) / [D ] Is 100/0
The resist material according to claim 3, which is 20/80. 5. The hydrogenated product of the ring-opening metathesis polymer,
Furthermore, the general formula [7](Where R²⁵~ R²⁸At least one of the following
General formula [8](In the formula, a chain line indicates a bond. R²⁹Is a hydrogen atom, carbon
A linear, branched or cyclic alkyl group of the formulas 1 to 10;
Linear, branched or cyclic alkoxya having a prime number of 2 to 10
Alkyl group, or linear, branched or cyclic C 1-10
Represents an acyl group. R³⁰Is a linear chain having 1 to 10 carbon atoms
, Branched or cyclic alkyl groups having 2 to 10 carbon atoms
Chain, branched or cyclic alkoxyalkyl group, or charcoal
A linear, branched or cyclic halogenated amine having a prime number of 1 to 20;
Represents a alkyl group. W³Is a single bond or k having 1 to 10 carbon atoms
+ Represents a divalent hydrocarbon group. s is 0 or 1. )so
It is a functional group having a carboxylic acid ester group represented,
Others are each independently a hydrogen atom, having 1 to 20 carbon atoms.
Linear, branched or cyclic alkyl group, halogen atom,
Linear, branched or cyclic halogenation having 1 to 20 carbon atoms
Alkyl group, C1-C20 linear, branched or cyclic
An alkoxy group, having 2 to 20 carbon atoms, linear, branched or
Cyclic alkoxyalkyl group, straight chain having 2 to 20 carbon atoms
, Branched or cyclic alkylcarbonyloxy group, charcoal
An arylcarbonyloxy group having a prime number of 6 to 20, having 1 carbon atom
-20 linear, branched or cyclic alkylsulfonyl
Oxy group, arylsulfonyloxy having 6 to 20 carbon atoms
Group, a linear, branched or cyclic alcohol having 2 to 20 carbon atoms
Xycarbonyl group or C3-C20 linear, branched
Selected from linear or cyclic alkoxycarbonylalkyl groups
X⁵Is -O- or CR³¹ ₂− (R³¹Is a hydrogen atom
Or a linear or branched alkyl group having 1 to 10 carbon atoms
) And may be the same or different. r is 0 or 1
Represents an integer of 1 to 3. ) Contains the structural unit [E]
The resist material according to claim 1. 6. A hydrogenated product of a ring-opening metathesis polymer contained as a base resin, wherein a structural unit [A] represented by the general formula [1] and a structural unit [B] represented by the general formula [3] And the structural molar ratio of the structural unit [E] represented by the general formula [7] to the structural unit [C] represented by the general formula [4] ([A] + [B] + [C]) / [E] ] Is 100/0
The resist material according to claim 5, wherein the ratio is 40/60. 7. The hydrogenated product of a ring-opening metathesis polymer contained as a base resin, wherein the number average molecular weight Mn in terms of polystyrene measured by GPC is from 500 to 200,000. The resist material according to claim 1. 8. The polystyrene-equivalent number average molecular weight Mn of the hydrogenated product of the ring-opening metathesis polymer contained as a base resin measured by GPC is from 3,000 to 20,000. The resist material as described. 9. A step of applying the resist material according to claim 1 on a substrate, and a step of exposing the substrate to a high energy beam or an electron beam via a photomask after the heat treatment. And subjecting it to a heat treatment in accordance with the formula (1), and then developing using a developer.