JP2003330193A - Radiation-sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition having high transparency for radiation and an excellent balance in the characteristics as a resist such as sensitivity, resolution, dry etching durability, pattern profile, mask pattern dependence, exposure allowance or the like. <P>SOLUTION: The radiation-sensitive resin composition contains (A) a resin which is changed into alkali-soluble by the effect of an acid and is represented by a resin having a repeating unit derived from a compound expressed by formula (i-1) or (ii-2) and (B) a radiation-sensitive acid generating agent. In each formula, R represents a hydrogen atom or a methyl group. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a radiation-sensitive resin composition, and more specifically, to far-ultraviolet rays such as KrF excimer laser or ArF excimer laser, charged particle rays such as electron beam, X-ray such as synchrotron radiation and the like. The present invention relates to a radiation-sensitive resin composition which can be suitably used as a chemically amplified resist useful for fine processing using various kinds of radiation such as rays.

[0002]

2. Description of the Related Art In the field of microfabrication represented by the manufacture of integrated circuit devices, recently, in order to obtain a higher degree of integration, a lithography technique capable of microfabrication at a level of 0.20 μm or less is required. Has been done. In the conventional lithography process, near-ultraviolet rays such as i-rays are generally used as radiation, and it is said that with this near-ultraviolet rays, fine processing at the subquarter micron level is extremely difficult. Therefore, in order to enable fine processing at a level of 0.20 μm or less, use of radiation having a shorter wavelength is being studied. Examples of such short-wavelength radiation include bright line spectra of mercury lamps, far-ultraviolet rays typified by excimer lasers, X-rays, electron beams, and the like. Of these, KrF excimer lasers (wavelength 248 nm) are particularly preferable. ) Or an ArF excimer laser (wavelength 193 nm) is drawing attention. As a radiation-sensitive resin composition suitable for such an excimer laser, a component having an acid-dissociable functional group and a component that generates an acid upon irradiation with radiation (hereinafter referred to as “exposure”) (hereinafter, referred to as “radiation-sensitive”). Many compositions (hereinafter referred to as "chemically amplified radiation-sensitive compositions") utilizing the chemical amplification effect of "acid generator") have been proposed. Examples of the chemically amplified radiation-sensitive composition include Japanese Patent Publication No. 2-2
Japanese Patent No. 7660 proposes a composition containing a polymer having a carboxylic acid t-butyl ester group or a phenol t-butyl carbonate group and a radiation-sensitive acid generator. In this composition, the acid generated by exposure dissociates the t-butyl ester group or t-butyl carbonate group present in the polymer, and the polymer has an acidity of carboxyl group or phenolic hydroxyl group. This is due to the fact that it has a group, and as a result, the exposed region of the resist film becomes easily soluble in an alkali developing solution.

By the way, most of the conventional chemically amplified radiation-sensitive compositions are based on a phenolic resin. However, in the case of such a resin, if deep ultraviolet rays are used as radiation, the fragrance in the resin will be improved. Since the deep UV rays are absorbed due to the group ring, there is a drawback that the exposed deep UV rays cannot reach the lower layer portion of the resist film sufficiently. There is a problem in that the pattern shape after development becomes a trapezoidal shape in which the upper part is thin and the lower part is thicker, and sufficient resolution cannot be obtained. In addition, when the pattern shape after development becomes a trapezoidal shape, the desired dimensional accuracy cannot be achieved in the next step, that is, during etching or ion implantation, which is a problem. In addition, if the shape of the upper portion of the resist pattern is not rectangular, the rate of disappearance of the resist due to dry etching will be high, which makes it difficult to control the etching conditions. On the other hand, the shape of the resist pattern can be improved by increasing the radiation transmittance of the resist film. For example, a (meth) acrylate resin represented by polymethylmethacrylate is a highly preferable resin from the viewpoint of radiation transmittance because it has high transparency to deep ultraviolet rays and is disclosed in, for example, JP-A-4-226461. Has proposed a chemically amplified radiation-sensitive composition using a methacrylate resin. However, although this composition is excellent in terms of microfabrication performance, it does not have an aromatic ring and thus has a drawback of low dry etching resistance. In this case also, it is difficult to perform highly accurate etching processing. However, it cannot be said that it has both transparency to radiation and dry etching resistance.

Further, regarding a resist comprising a chemically amplified radiation-sensitive composition, as one of measures for improving dry etching resistance without impairing transparency to radiation, an aromatic ring is used as a resin component in the composition. There is known a method of introducing an aliphatic ring in place of, for example, JP-A-7-23.
4511 discloses a chemically amplified radiation-sensitive composition using an (meth) acrylate resin having an aliphatic ring. However, in this composition, as the acid dissociable functional group of the resin component, a group that is relatively easily dissociated by a conventional acid (for example, an acetal-based functional group such as a tetrahydropyranyl group) or an acid is relatively difficult to dissociate by an acid. Group (for example, t-butyl functional group such as t-butyl ester group and t-butyl carbonate group) is used, and in the case of the former resin component having an acid dissociable functional group, basic physical properties of the resist, particularly Although the sensitivity and pattern shape are good, there is a problem in storage stability as a composition, and the latter resin component having an acid-dissociable functional group, on the contrary, has good storage stability. There is a drawback that the physical properties, particularly the sensitivity and the pattern shape are impaired. Furthermore, since an aliphatic ring is introduced into the resin component in this composition, the hydrophobicity of the resin itself becomes very high, and there is a problem in terms of adhesiveness to the substrate.

Furthermore, the applicant has already used a resin having a repeating unit derived from a compound in which the carboxyl group of (meth) acrylic acid is protected by a t-butyl group substituted with an alicyclic group or an aromatic group. A chemically amplified radiation-sensitive composition has been proposed (see JP 2001-33970 A). This composition has little change in the line width of the resist pattern due to fluctuations in the exposure time (PED) from exposure to post-exposure heat treatment, and does not generate standing waves even on a substrate with high reflectance. Although it has excellent sensitivity and resolution, it is a chemically amplified radiation-sensitive composition that is adaptable to short-wave radiation represented by far-ultraviolet rays from the viewpoint of technological development that can respond to the progress of miniaturization in semiconductor devices. However, the development of a new resin component that is highly transparent to radiation and has an excellent property balance as a resist including dry etching resistance, pattern shape, mask pattern dependence, exposure margin, etc. remains an important issue. Has become.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to have a high radiation transparency, and to balance the characteristics of a resist including sensitivity, resolution, dry etching resistance, pattern shape, mask pattern dependence, exposure margin, etc. Another object of the present invention is to provide an excellent radiation-sensitive resin composition.

[0007]

According to the present invention, the above-mentioned problems are selected from the group consisting of (A) a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II). A radiation-sensitive resin composition comprising at least one alkali-insoluble or sparingly alkali-soluble resin, which becomes alkali-soluble by the action of an acid, and (B) a radiation-sensitive acid generator. Achieved by things.

[0008]

[Chemical 3]

[In the general formula (I), each R ¹ independently of ^one another is a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxyl group having 1 to 6 carbon atoms. , A linear or branched alkoxycarbonyl group having 2 to 6 carbon atoms, or 4 to 4 carbon atoms having an alicyclic structure
20 monovalent hydrocarbon groups or their derivatives,
² represents a linear or branched alkyl group having 1 to 20 carbon atoms, or a monovalent hydrocarbon group having 4 to 20 carbon atoms having an alicyclic structure or a derivative thereof, and X ¹ represents a methylene group or a carbon atom. A linear or branched alkylene group having a number of 2 to 9 or a divalent hydrocarbon group having a carbon number of 4 to 20 having an alicyclic structure or a derivative thereof is shown, and n is an integer of 0 to 2.

In the general formula (II), each R ³ independently of one another is a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxyl group having 1 to 6 carbon atoms, A straight-chain or branched alkoxycarbonyl group having 2 to 6 carbon atoms, or 4 to 4 carbon atoms having an alicyclic structure
20 monovalent hydrocarbon groups or their derivatives,
⁴ represents a linear or branched alkyl group having 1 to 20 carbon atoms, or a monovalent hydrocarbon group having 4 to 20 carbon atoms having an alicyclic structure or a derivative thereof, and X ² represents a methylene group or a carbon atom. A linear or branched alkylene group having a number of 2 to 9 or a divalent hydrocarbon group having a cycloaliphatic structure and having a carbon number of 4 to 20 or a derivative thereof, and R ⁵ represents a hydrogen atom, a methyl group, or a carbon atom. A linear or branched hydroxyalkyl group having 1 to 4 carbon atoms or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms is shown. ]

The present invention will be described in detail below. Component (A) The component (A) in the present invention is a repeating unit represented by the general formula (I) (hereinafter referred to as “repeating unit (I)”) and a repeating unit represented by the general formula (II). A resin which is at least one selected from the group of units (hereinafter, referred to as “repeating unit (II)”) and which is alkali-insoluble or sparingly soluble in alkali and which becomes alkali-soluble by the action of an acid (hereinafter, “resin”). (A) ”). The term "alkali-insoluble or alkali-insoluble" as used herein means that under the alkaline developing conditions adopted when forming a resist pattern from a resist coating formed from a radiation-sensitive resin composition containing a resin (A), This means the property that when a film using only the resin (A) instead of the resist film is developed, 50% or more of the initial film thickness of the film remains after development.

In the repeating unit (I) and the repeating unit (II) in the resin (A), the monovalent hydrocarbon group having an alicyclic structure of R ¹ , R ² , R ³ and R ⁴ is a bridged carbon. It can have a hydrogen skeleton. Therefore, the position numbers of carbon atoms in the main bridged hydrocarbon skeleton are shown below.

[0013]

[Chemical 4]

Here, (a) is bicyclo [2.2.1].
Heptane, (b) is tetracyclo [6.2.1.1]
^3,6 . 0 ^2,7 ] dodecane, (ha) is tricyclo [5.
2.1.0 ^2,6 ] decane, (d) is tricyclo [4.
2.1.0 ^3,7 ] Nonane. The nomenclature of the bridged hydrocarbon skeleton in the following shall follow these (a) to (d).

In the general formula (I) and the general formula (II), examples of the linear or branched alkyl group having 1 to 6 carbon atoms of R ¹ and R ³ include, for example, methyl group, ethyl group and n- Propyl group, i-propyl group, n-butyl group,
1-methylpropyl group, 2-methylpropyl group, t-butyl group, n-pentyl group, n-hexyl group and the like can be mentioned.

Examples of the linear or branched alkoxyl group having 1 to 6 carbon atoms for R ¹ and R ³ include, for example, methoxy group, ethoxy group, n-propoxy group, i-
Examples thereof include propoxy group, n-butoxy group, 1-methylpropoxy group, 2-methylpropoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group and the like.

Examples of the linear or branched alkoxycarbonyl group having 2 to 6 carbon atoms for R ¹ and R ³ include, for example, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group. Group, n-butoxycarbonyl group, 1-methylpropoxycarbonyl group, 2-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group and the like.

The C 4-20 monovalent hydrocarbon group having an alicyclic structure represented by R ¹ and R ³ or a derivative thereof is, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, A cycloalkyl group such as a cyclooctyl group; an adamantane-1-yl group, a bicyclo [2.2.1] heptan-2-yl group, a tetracyclo [[6.2.1.1 ^3,6 . Bridged hydrocarbon groups such as 0 ^2,7 ] dodecan-4-yl group and tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group; these cycloalkyl groups or bridged carbonization Hydrogen group is methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t
A group substituted with at least one or a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms such as a butyl group; an alicyclic hydrocarbon optionally substituted with these alkyl groups Examples thereof include a group in which one or more groups such as a hydroxyl group, a carboxyl group, a nitro group, a cyano group, and an amino group are substituted or one or more groups are substituted.

R ¹ in the general formula (I) and R ³ in the general formula (II) are a methyl group, an ethyl group, an n-propyl group, a methoxy group, an ethoxy group and an n-group, respectively.
A propoxy group, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, a cyclopentyl group, a cyclohexyl group, an adamantane-1-yl group, a bicyclo [2.2.1] heptan-2-yl group and the like are preferable.

In the general formula (I) and the general formula (II), the linear or branched alkyl group having 1 to 20 carbon atoms represented by R ² and R ⁴ is, for example, a methyl group, an ethyl group or n-. Propyl group, i-propyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, t
-Butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group and the like can be mentioned.

Examples of the monovalent hydrocarbon group having 4 to 20 carbon atoms having an alicyclic structure of R ² and R ⁴ or a derivative thereof include, for example, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, A cycloalkyl group such as a cyclooctyl group; an adamantane-1-yl group, a bicyclo [2.2.1] heptan-2-yl group, a tetracyclo [[6.2.1.1 ^3,6 . Bridged hydrocarbon groups such as 0 ^2,7 ] dodecan-4-yl group and tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group; these cycloalkyl groups or bridged carbonization Hydrogen group is methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t
A group substituted with at least one or a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms such as a butyl group; a cycloalkyl group which may be substituted with these alkyl groups or Examples thereof include a group obtained by substituting a bridged hydrocarbon group with one or more groups such as a hydroxyl group, a carboxyl group, a nitro group, a cyano group, and an amino group, and the like.

R in the general formula (I)² And the general formula
R in (II)^Four Respectively as cyclopentyl
Group, cyclohexyl group, adamantane-1-yl group, bi-group
Cyclo [2.2.1] heptan-2-yl group, tetracy
Black [6.2.1.1^3,6 ． 0 ^2,7 ] Dodecane-4-a
Group, tricyclo [5.2.1.0^2,6 ] Decane-8-
Ileyl group and the like are preferable.

In the general formula (I) and the general formula (II), examples of the linear or branched alkylene group of X ¹ and X ² having 2 to 9 carbon atoms include, for example, ethylene group, propylene group and trimethylene group. , Tetramethylene group, 2-
Examples thereof include methyltrimethylene group, hexamethylene group, octamethylene group and the like.

Examples of the divalent hydrocarbon group having 4 to 20 carbon atoms having an alicyclic structure of X ¹ and X ² or a derivative thereof include cyclobutane, cyclopentane,
Groups derived from cycloalkanes such as cyclohexane, cycloheptane, cyclooctane; adamantane, bicyclo [2.2.1] heptane, tetracyclo [6.2.
1.1 ^3,6 . 0 ^2,7 ] dodecane, tricyclo [5.2.
1.0 ^2,6 ] Group derived from bridged hydrocarbons such as decane: a group derived from these cycloalkanes or bridged hydrocarbons is a methyl group, an ethyl group, an n-propyl group,
1 carbon atom such as i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group
To 4 groups substituted with one or more linear or branched or cyclic alkyl groups or one or more; derived from cycloalkanes or bridged hydrocarbons that may be substituted with these alkyl groups Examples thereof include a group in which one or more groups such as a hydroxyl group, a carboxyl group, a nitro group, a cyano group, and an amino group are substituted or one or more groups are substituted.

Each of X ¹ in the general formula (I) and X ² in the general formula (II) is preferably a methylene group, an ethylene group, a trimethylene group or the like.

In the general formula (II), the carbon number of R ⁵ is 1 to
Examples of the linear or branched hydroxyalkyl group of 4 include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, and a 3-hydroxypropyl group. , 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.

Examples of the linear or branched fluorinated alkyl group having 1 to 4 carbon atoms represented by R ⁵ include, for example, monofluoromethyl group, difluoromethyl group, trifluoromethyl group, 1-fluoroethyl group, 1,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 1,
Examples include 1,2,2-tetrafluoroethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, nonafluoro-n-butyl group and the like.

R ⁵ in the general formula (II) is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a trifluoromethyl group or the like.

The monomer giving the repeating unit (I) is
For example, it can be synthesized by the following method. 1) 1-Methylcarbonylmethyl adamantane was replaced with C
Reduction with a Grineer reagent such as H ₃ MgBr gives 1- (2,2-dimethyl-2-hydroxyethyl) adamantane. 2) By dehydrochlorinating the compound obtained in 1) with (meth) acrylic acid chloride in the presence of a base such as sodium hydroxide, (meth) acrylic acid 1-
Methyl-1-[(adamantan-1-yl) methyl] ethyl is obtained. 3) The compound obtained in 2) and cyclopentadiene are subjected to a Diels-Alder reaction to give 5- [1-methyl-1-represented by the formula (i-1) described later.
This gives {(adamantan-1-yl) methyl} ethyl] bicyclo [2.2.1] hept-2-ene.

Further, the monomer giving the repeating unit (II) is represented by the formula (ii-1) described later by, for example, the method of 1) and 2) in the process of synthesizing the monomer giving the repeating unit (I). 1-Methyl-1-[(adamantan-1-yl) methyl] ethyl (meth) acrylate is obtained.

In the present invention, the monomer giving the particularly preferred repeating unit (I) is represented by the following formula (i-1):
Examples of the monomer that gives the particularly preferable repeating unit (II) include compounds represented by (i-3), and the following formulas (ii-1) to (ii-3) (in each formula, R Represents a hydrogen atom or a methyl group) and the like.

[0032]

[Chemical 5]

[0033]

[Chemical 6]

The resin (A) may have at least one repeating unit other than the repeating unit (I) and the repeating unit (II) (hereinafter referred to as "other repeating unit"). Preferred other repeating units include, for example, a repeating unit represented by the following general formula (III) (hereinafter referred to as "repeating unit (III)"), a repeating unit represented by the following general formula (IV) (hereinafter , “Repeating unit (IV)”) and the like.

[0035]

[Chemical 7] [In the general formula (III), Z ¹ represents a hydrogen atom or a monovalent organic group, and m is an integer of 0 to 2. General formula (IV)
In, Z ² represents a hydrogen atom or a monovalent organic group,
R ⁶ is a hydrogen atom, a methyl group, a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms
4 represents a linear or branched fluorinated alkyl group. ]

In the general formulas (III) and (IV), examples of the monovalent organic group represented by Z ¹ and Z ² include, for example,
A linear or branched alkyl group having 1 to 12 carbon atoms,
A monovalent organic group having 4 to 20 carbon atoms having an alicyclic structure, a monovalent organic group having a cyclic ether structure, a monovalent organic group having an optionally substituted lactone skeleton, the following formula (1-1 )
And a group represented by the following formula (1-2).

[0037]

[Chemical 8]

[In the formula (1-1), Y ¹ represents a linear or branched divalent organic group or a divalent organic group having an alicyclic structure, and R ⁷ represents a hydrogen atom or 1 A valent functional group is shown.

In the formula (1-2), each R ⁸ is independently a straight-chain or branched alkyl group having 1 to 4 carbon atoms,
It represents a linear or branched oxoalkyl group having 2 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or any two R ⁸ are bonded to each other. To form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the carbon atoms to which they are bonded, and the remaining R ⁸ is a straight chain having 1 to 4 carbon atoms or Branched alkyl group, linear or branched oxoalkyl group having 2 to 4 carbon atoms, or 4 to 2 carbon atoms
The monovalent alicyclic hydrocarbon group of 0 or its derivative is shown. ]

In the general formulas (III) and (IV), examples of the linear or branched alkyl group having 1 to 12 carbon atoms of Z ¹ and Z ² include, for example, methyl group, ethyl group and n- Propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t
-Butyl group, n-pentyl group, n-hexyl group and the like can be mentioned. Of these alkyl groups, methyl group, ethyl group and the like are preferable.

Examples of the monovalent organic group having 4 to 20 carbon atoms and having an alicyclic structure of Z ¹ and Z ² include cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like. Groups derived from alkanes; adamantane, bicyclo [2.2.
1] heptane, tetracyclo [6.2.1.1 ^3,6 . 0
Groups derived from bridged hydrocarbons such as ^2,7 ] dodecane and tricyclo [5.2.1.0 ^2,6 ] decane; groups derived from these cycloalkanes or bridged hydrocarbons A straight chain having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group,
A group substituted with one or more or one or more branched or cyclic alkyl groups; a group derived from cycloalkanes or bridged hydrocarbons which may be substituted with these alkyl groups is a hydroxyl group, a carboxyl group, Nitro group, cyano group,
There may be mentioned one or more groups such as amino groups, or groups substituted with one or more groups. Of these monovalent organic groups,
Cyclopentane, cyclohexane, cycloheptane, cyclooctane, adamantane, bicyclo [2.2.1]
A group derived from heptane, tricyclo [5.2.1.0 ^2,6 ] decane or the like is preferable.

The monovalent organic group having a cyclic ether structure of Z ¹ and Z ² is, for example, a tetrahydrofuran-2-yl group or a tetrahydropyran-2-yl group, or a methyl group or an ethyl group. Group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, etc., having a straight chain, branched or cyclic group having 1 to 4 carbon atoms. The group etc. which were couple | bonded with the alkyl group can be mentioned. Also, Z ¹ and Z ²
Examples of the monovalent organic group having an optionally substituted lactone skeleton are represented by the following formula (2-1), formula (2-2), formula (2-3) or formula (2-4) And the like.

[0043]

[Chemical 9]

[In the formulas (2-1) and (2-2),
Each R ⁹ independently of one another is a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkoxyl group having 1 to 5 carbon atoms, or an alkyl group having 2 to 5 carbon atoms. It represents a linear or branched alkoxycarbonyl group, and Y ² represents a methylene group, a dimethylmethylene group, an oxygen atom or a sulfur atom. In formula (2-3), R ¹⁰ is a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkoxyl group having 1 to 5 carbon atoms, or 2 carbon atoms. 5 represents a linear or branched alkoxycarbonyl group. In formula (2-4),
R ¹¹ is a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkoxyl group having 1 to 5 carbon atoms, or a linear or branched chain having 2 to 5 carbon atoms. A plurality of R ^{11 s} may be the same or different, a is an integer of 0 to 4, and Y ³ represents a single bond or a methylene group. ]

In the formulas (2-1) to (2-4), R ⁹ ,
Examples of the linear or branched alkyl group having 1 to 5 carbon atoms of R ¹⁰ and R ¹¹ include a methyl group, an ethyl group,
n-propyl group, i-propyl group, n-butyl group, 1-
Examples thereof include methylpropyl group, 2-methylpropyl group, t-butyl group, n-pentyl group and the like. Also, R
Examples of the linear or branched alkoxyl group having carbon atoms of 1 to 5 of ⁹ , R ¹⁰ and R ¹¹ include, for example, a methoxy group,
Ethoxy group, n-propoxy group, i-propoxy group, n
Examples thereof include -butoxy group, 1-methylpropoxy group, 2-methylpropoxy group, t-butoxy group and n-pentyloxy group. Examples of the linear or branched alkoxycarbonyl group having 2 to 5 carbon atoms represented by R ⁹ , R ¹⁰ and R ¹¹ include, for example, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i.
-Propoxycarbonyl group, n-butoxycarbonyl group, 1-methylpropoxycarbonyl group, 2-methylpropoxycarbonyl group, t-butoxycarbonyl group and the like can be mentioned.

Z ¹ in the general formula (III) and Z ² in the general formula (IV) are a straight-chain or branched alkyl group having 1 to 12 carbon atoms, or 4 to ² carbon atoms having an alicyclic structure.
Preferred examples of the monovalent organic group of 0, the monovalent organic group having a cyclic ether structure and the monovalent organic group having an optionally substituted lactone skeleton include, for example, a methyl group,
Linear or branched alkyl groups such as ethyl group and n-propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; adamantane-1-yl group, bicyclo [2.2.1] heptan-2-yl group Group, 7,7-dimethylbicyclo [2.2.1] heptan-1-yl group, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecane-
Groups derived from bridged hydrocarbons such as 4-yl group and tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group; cyclic ethers such as (tetrahydrofuran-2-yl) methyl group Organic group having a structure; 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl group, 9-
Methoxycarbonyl-5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl group, 7-oxo-6-oxabicyclo [3.2.1] octane-4
-Yl group, 2-methoxycarbonyl-7-oxo-6-
Oxa-bicyclo [3.2.1] octane-4-yl group, 2-oxotetrahydropyran-4-yl group, 4-
A methyl-2-oxotetrahydropyran-4-yl group,
4-ethyl-2-oxotetrahydropyran-4-yl group, 4-n-propyl-2-oxotetrahydropyran-4-yl group, 5-oxotetrahydrofuran-3-yl group, 2,2-dimethyl-5- Oxotetrahydrofuran-3-yl group, 4,4-dimethyl-5-oxotetrahydrofuran-3-yl group, 2-oxotetrahydrofuran-3-yl group, 4,4-dimethyl-2-oxotetrahydrofuran-3-yl group, 5,5-dimethyl-2-
Oxotetrahydrofuran-3-yl group, 2-oxotetrahydrofuran-3-yl group, (5-oxotetrahydrofuran-2-yl) methyl group, (3,3-dimethyl-5-oxotetrahydrofuran-2-yl) methyl group, Examples thereof include an organic group having an optionally substituted lactone skeleton such as (4,4-dimethyl-5-oxotetrahydrofuran-2-yl) methyl group.

In the formula (1-1), the linear or branched divalent organic group for Y ¹ is a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group or a 2-methyltrimethyl group. Methylene group, hexamethylene group,
Examples thereof include alkylene groups having 2 to 12 carbon atoms such as octamethylene group. The divalent organic group having an alicyclic structure of Y ¹ is, for example, a group derived from a cycloalkane having 4 to 20 carbon atoms such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane; adamantane. , Bicyclo [2.2.1] heptane, tetracyclo [6.2.1.1 ^3,6 . And groups derived from bridged hydrocarbons having 4 to 20 carbon atoms such as 0 ^2,7 ] dodecane.

Y ¹ in the formula (1-1) is a methylene group, an ethylene group, a divalent group derived from adamantane,
A divalent group derived from bicyclo [2.2.1] heptane and the like are preferable.

In the formula (1-1), examples of the monovalent functional group for R ⁷ include a hydroxyl group, a carboxyl group, a nitro group, a cyano group and an amino group. R ⁷ in the formula (1-1) is preferably a hydrogen atom, a hydroxyl group, a carboxyl group, a cyano group or the like.

Preferred groups represented by the formula (1-1) include, for example, hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 3-hydroxyadamantan-1-yl group and 5-hydroxybicyclo group. [2.
2.1] heptan-2-yl group, 6-hydroxybicyclo [2.2.1] heptan-2-yl group, 9-hydroxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 10-hydroxytetracyclo [6.
2.1.1 ^3,6 . 0 ^2,7 ] dodecane-4-yl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 3-carboxyadamantan-1-yl group, 5-carboxybicyclo [2.2.1] heptane -2-yl group, 6-carboxybicyclo [2.2.1]
Heptan-2-yl group, 9-carboxytetracyclo [
6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group,
10-carboxytetracyclo [6.2.1.1 ^3,6 .
0 ^2,7 ] dodecan-4-yl group, cyanomethyl group, 2-
Cyanoethyl group, 3-cyanopropyl group, 3-cyanoadamantan-1-yl group, 5-cyanobicyclo [2.
2.1] heptan-2-yl group, 6-cyanobicyclo [2.2.1] heptan-2-yl group, 9-cyanotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecane-4
-Yl group, 10-cyanotetracyclo [6.2.1.1
^3,6 . [0 ^2,7 ] dodecan-4-yl group and the like can be mentioned.

In the formula (1-2), R ⁸ has 4 to 2 carbon atoms.
A monovalent alicyclic hydrocarbon group having 0 and a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, which is formed together with carbon atoms to which any two R ⁸ are bonded to each other. Examples of such compounds include cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane, adamantane, and bicyclo [2.2.1].
Heptane, tetracyclo [6.2.1.1 ^3,6 . 0
Groups derived from bridged hydrocarbons such as ^2,7 ] dodecane and tricyclo [5.2.1.0 ^2,6 ] decane; groups derived from these cycloalkanes or bridged hydrocarbons A straight chain having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group,
Examples thereof include groups substituted with one or more branched or cyclic alkyl groups, or one or more.

Examples of the derivative of the monovalent or divalent alicyclic hydrocarbon group include a hydroxyl group; a carboxyl group; an oxy group (ie, = 0 group); a hydroxymethyl group,
1-hydroxyethyl group, 2-hydroxyethyl group, 1
-Hydroxypropyl group, 2-hydroxypropyl group,
3-hydroxypropyl group, 2-hydroxybutyl group,
A hydroxyalkyl group having 1 to 4 carbon atoms such as 3-hydroxybutyl group, 4-hydroxybutyl group; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-
Butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group and other alkoxy groups having 1 to 4 carbon atoms; cyano group; cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 4-cyanobutyl Examples thereof include groups having one or more substituents such as cyanoalkyl groups having 2 to 5 carbon atoms such as groups, or groups having one or more substituents. Of these substituents, a hydroxyl group, a carboxyl group, a hydroxymethyl group, a cyano group, a cyanomethyl group and the like are preferable.

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms of R ⁸ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n
-Butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like can be mentioned. Also, R
The ⁸ linear or branched oxoalkyl group having 2 to 4 carbon atoms, for example, oxoethyl, 1-oxopropyl group, and a 1-oxo -n- butyl group.

Preferred groups represented by the formula (1-2) are, for example, t-butyl group, 2-methyl-2-butyl group, 2-ethyl-2-butyl group and 3-ethyl-3-butyl group. Group, 1,1-dimethyl-2-oxopropyl group, 1,
1-dimethyl-2-oxo-n-butyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-
Methylcyclohexyl group, 1-ethylcyclohexyl group, 2-methyladamantan-2-yl group, 2-ethyladamantan-2-yl group, 2-methyl-3-hydroxyadamantan-2-yl group, 2-methylbicyclo [2 2.1] heptan-2-yl group, 2-ethylbicyclo [2.2.1] heptan-2-yl group, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodecan-4-yl group, 4-ethyltetracyclo [6.2.1.
1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 8-methyltricyclo [5.2.1.0 ^2,6 ] decan-8-yl group,
8-Ethyltricyclo [5.2.1.0 ^2,6 ] decane-
8-yl group,

1-methyl-1-cyclopentylethyl group, 1-methyl-1- (2-hydroxycyclopentyl) ethyl group, 1-methyl-1- (3-hydroxycyclopentyl) ethyl group, 1-methyl-1-cyclohexyl Ethyl group, 1-methyl-1- (3-hydroxycyclohexyl) ethyl group, 1-methyl-1- (4-hydroxycyclohexyl) ethyl group, 1-methyl-1-cycloheptylethyl group, 1-methyl-1- (3-Hydroxycycloheptyl) ethyl group, 1-methyl-1- (4-hydroxycycloheptyl) ethyl group, 1-methyl-1-
(Adamantan-1-yl) ethyl group, 1-methyl-1
-(3-Hydroxyadamantan-1-yl) ethyl group, 1-methyl-1- (bicyclo [2.2.1] heptan-2-yl) ethyl group, 1-methyl-1- (tetracyclo [6.2] .1.1 ^3,6 .0 ^2,7] dodecane-4-yl) ethyl group, 1-methyl-1- (tricyclo [5.
2.1.0 ^2,6 ] Decan-8-yl) ethyl group, 1,1
-Dicyclopentylethyl group, 1,1-dicyclohexylethyl group, 1,1-di (adamantan-1-yl) ethyl group, 1,1-di (bicyclo [2.2.1] heptan-2-yl) ethyl Group, 1,1-di (tetracyclo [
6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) ethyl group, 1,1-di (tricyclo [5.2.1.0]
^2,6 ] decane-8-yl) ethyl group and the like can be mentioned. Further, as Z ¹ in the general formula (III) and Z ² in the general formula (IV), a hydrogen atom is also preferable.

Examples of the monomer giving the repeating unit (III) include bicyclo [2.2.1] hept-2-ene-5-carboxylic acid and bicyclo [2.2.1] hept-2.
(3-hydroxyadamantan-1-yl) ester of -ene-5-carboxylic acid, bicyclo [2.2.1] hept-2-ene-5-carboxylic acid (5-hydroxybicyclo [2.2.1]). ] Heptan-2-yl) ester, bicyclo [2.2.1] hept-2-ene-5-carboxylic acid (6-hydroxybicyclo [2.2.1] heptan-2-yl) ester, bicyclo [ 2.2.1] Hept-2-ene-5-carboxylic acid (9-hydroxytetracyclo [6.2.1.1 ^3,6 0.0 ^2,7 ] dodecane-4-
Yl) ester, bicyclo [2.2.1] hept-2-
(10-Hydroxytetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecan-4-yl) ester of ene-5-carboxylic acid,

Methyl bicyclo [2.2.1] hept-2-ene-5-carboxylate, ethyl bicyclo [2.2.1] hept-2-ene-5-carboxylate, bicyclo [2.
2.1] n-propyl hept-2-ene-5-carboxylate, t-butyl bicyclo [2.2.1] hept-2-ene-5-carboxylate, bicyclo [2.2.1] hept-
2-Methyl-2-butyl 2-ene-5-carboxylate, bicyclo [2.2.1] 2-ethyl-2-butyl hept-2-ene-5-carboxylate, bicyclo [2.2.1]. 3-Ethyl-3-butyl hept-2-ene-5-carboxylate, bicyclo [2.2.1] cyclopentyl hept-2-ene-5-carboxylate, bicyclo [2.2.1] hept-2- Cyclohexene-5-carboxylate, bicyclo [2.2.1] (adamantan-1-yl) ester of hept-2-ene-5-carboxylic acid, bicyclo [2.
2.1] (bicyclo [2.2.1] heptan-2-yl) ester of hept-2-ene-5-carboxylic acid, bicyclo [2.2.1] hept-2-ene-5-carboxylic acid (7,7-Dimethylbicyclo [2.2.1] heptan-1-yl) ester of, and bicyclo [2.2.1] hept-2-ene-5-carboxylic acid (tetracyclo [6.
2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) ester, (tricyclo [5.2.1.0 ^2,6 ] decane-8- of bicyclo [2.2.1] hept-2-ene-5-carboxylic acid Ill) ester,

Bicyclo [2.2.1] hept-2-ene-5-carboxylic acid 1-methylcyclopentyl, bicyclo [2.2.1] hept-2-ene-5-carboxylic acid 1-
Ethylcyclopentyl, bicyclo [2.2.1] hept-2-ene-5-carboxylic acid 1-methylcyclohexyl, bicyclo [2.2.1] hept-2-ene-5-carboxylic acid 1-ethylcyclohexyl, bicyclo [2.
2.1] Hept-2-ene-5-carboxylic acid (2-methyladamantan-2-yl) ester, bicyclo [2.2.1] hept-2-ene-5-carboxylic acid (2-methyl -3-Hydroxyadamantan-2-yl) ester, bicyclo [2.2.1] hept-2-ene-5-carboxylic acid (2-ethyladamantan-2-
Yl) ester, bicyclo [2.2.1] hept-2-
The ene-5-carboxylic acid (2-methylbicyclo [2.
2.1] heptan-2-yl) ester, (2-ethylbicyclo [2.2.1] heptan-2-yl) ester of bicyclo [2.2.1] hept-2-ene-5-carboxylic acid , Bicyclo [2.2.1] hept-2-ene-5-carboxylic acid (4-methyltetracyclo [
6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) ester, bicyclo [2.2.1] hept-2-ene-5
Of the carboxylic acid (4-ethyltetracyclo [6.2.
1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) ester,
Bicyclo [2.2.1] hept-2-ene-5-carboxylic acid (8-methyltricyclo [5.2.1.0 ^2,6 ]
Decan-8-yl) ester, bicyclo [2.2.1]
(8-Ethyltricyclo [5.2.1.0 ^2,6 ] decan-8-yl) ester of hept-2-ene-5-carboxylic acid,

Bicyclo [2.2.1] hept-2-ene-5-carboxylic acid 1-methyl-1-cyclopentylethyl, bicyclo [2.2.1] hept-2-ene-5-carboxylic acid 1- Methyl-1-cyclohexylethyl, [1-methyl-1- (adamantan-1-yl) ethyl] ester of bicyclo [2.2.1] hept-2-ene-5-carboxylic acid, bicyclo [2.2. 1] Hept-2-ene-5-carboxylic acid [1-methyl-1- (bicyclo [2.2.1] heptan-2-yl) ethyl] ester, bicyclo [2.2.1] hept-2 -Ene-5-carboxylic acid [1-methyl-1- (tetracyclo [6.
2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) ethyl] ester, bicyclo [2.2.1] hept-2-ene-5-carboxylic acid [1-methyl-1- (tricyclo
[5.2.1.0 ^2,6 ] Decan-8-yl) ethyl] ester, bicyclo [2.2.1] hept-2-ene-5
1-methyl-1- (2-hydroxycyclopentyl) ethyl carboxylate, bicyclo [2.2.1] hept-2
1-Methyl-1- (3-hydroxycyclopentyl) ethyl-ene-5-carboxylate, bicyclo [2.2.1]
Hept-2-ene-5-carboxylic acid 1-methyl-1-
(3-Hydroxycyclohexyl) ethyl, bicyclo [2.2.1] hept-2-ene-5-carboxylic acid 1-
Methyl-1- (4-hydroxycyclohexyl) ethyl, bicyclo [2.2.1] hept-2-ene-5-carboxylate 1-methyl-1- (3-hydroxycycloheptyl) ethyl, bicyclo [2. 2.1] Hept-2-ene-5-carboxylic acid 1-methyl-1- (4-hydroxycycloheptyl) ethyl, bicyclo [2.2.1] hept-2-ene-5-carboxylic acid [ 1-methyl-1-
(3-hydroxyadamantan-1-yl) ethyl] ester,

Bicyclo [2.2.1] hept-2-ene-5-carboxylic acid 1,1-dicyclopentylethyl, bicyclo [2.2.1] hept-2-ene-5-carboxylic acid 1,1 -Dicyclohexylethyl, bicyclo [2.
2.1] [1,1 of hept-2-ene-5-carboxylic acid
-Di (adamantan-1-yl) ethyl] ester, bicyclo [2.2.1] hept-2-ene-5-carboxylic acid [1,1-di (bicyclo [2.2.1] heptane-
2-yl) ethyl] ester, bicyclo [2.2.1]
Hept-2-ene-5-carboxylic acid [1,1-di (tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecane-
4-yl) ethyl] ester, bicyclo [2.2.1]
[1,1-Di (tricyclo [5.2.1.0 ^2,6 ] decan-8-yl) ethyl] ester of hept-2-ene-5-carboxylic acid, bicyclo [2.2.1] hept -2-
Ene-5-carboxylic acid (tetrahydrofuran-2-yl) methyl, bicyclo [2.2.1] hept-2-ene-5-carboxylic acid 1,1-dimethyl-2-oxopropyl,

Bicyclo [2.2.1] hept-2-ene-5-carboxylic acid (5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl) The ester, bicyclo [2.2.1] hept-2-ene-5-carboxylic acid (9-methoxycarbonyl-5-oxo-4
-Oxatricyclo [4.2.1.0 ^3,7 ] nonane-2
-Yl) ester, bicyclo [2.2.1] hept-2
(7-oxo-6-oxabicyclo [3.2.1] octane-4-yl) ester of -ene-5-carboxylic acid,
Bicyclo [2.2.1] hept-2-ene-5-carboxylic acid (2-methoxycarbonyl-7-oxo-6-oxabicyclo [3.2.1] octane-4-yl) ester, bicyclo [ 2.2.1] Hept-2-ene-5-
Carboxylic acid (2-oxotetrahydropyran-4-yl) ester, bicyclo [2.2.1] hept-2-en-5-carboxylic acid (4-methyl-2-oxotetrahydropyran-4-yl) Ester, bicyclo [2.
2.1] Hept-2-ene-5-carboxylic acid (4-ethyl-2-oxotetrahydropyran-4-yl) ester, bicyclo [2.2.1] hept-2-ene-5-
(4-n-Propyl-2-oxotetrahydropyran-4-yl) ester of carboxylic acid, bicyclo [2.2.
1] (5-oxotetrahydrofuran-3-yl) ester of hept-2-ene-5-carboxylic acid, (2,2-dimethyl of bicyclo [2.2.1] hept-2-ene-5-carboxylic acid -5-oxotetrahydrofuran-
3-yl) ester, bicyclo [2.2.1] hept-
2-ene-5-carboxylic acid (4,4-dimethyl-5-
Oxotetrahydrofuran-3-yl) ester, bicyclo [2.2.1] hept-2-ene-5-carboxylic acid (2-oxotetrahydrofuran-3-yl) ester, bicyclo [2.2.1] hept- (4,4-Dimethyl-2-oxotetrahydrofuran-3-yl) ester of 2-ene-5-carboxylic acid, bicyclo [2.2.
1] Hept-2-ene-5-carboxylic acid (5,5-dimethyl-2-oxotetrahydrofuran-3-yl) ester, bicyclo [2.2.1] hept-2-ene-5
Of the carboxylic acid (2-oxotetrahydrofuran-3-
Yl) ester, bicyclo [2.2.1] hept-2-
[(5-Oxotetrahydrofuran-2-yl) methyl] ester of ene-5-carboxylic acid, bicyclo [2.
2.1] of hept-2-ene-5-carboxylic acid [(3,
3-dimethyl-5-oxotetrahydrofuran-2-yl) methyl] ester, bicyclo [2.2.1] hept-2-ene-5-carboxylic acid [(4,4-dimethyl-
5-oxotetrahydrofuran-2-yl) methyl] ester,

Tetracyclo [6.2.1.1 ^3,6 . 0
^2,7 ] Dodeca-4-ene-9-carboxylic acid, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-en-
The 9-carboxylic acid (3-hydroxyadamantane-1-
Yl) ester, tetracyclo [6.2.1.1 ^3,6 .
0 ^2,7 ] Dodeca-4-en-9-carboxylic acid (5-hydroxybicyclo [2.2.1] heptan-2-yl)
Ester, tetracyclo [6.2.1.1 ^3,6 . 0
^2,6- ] Dodeca-4-en-9-carboxylic acid (6-hydroxybicyclo [2.2.1] heptan-2-yl) ester, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ]
Dodecapeptide-4-ene-9-carboxylic acid (9-hydroxy tetracyclo [6.2.1.1 ^3,6 .0 ^2,7] dodecane-4-yl) ester, tetracyclo [6.2.1. 1
^3,6 . 0 ^2,7 ] dodeca-4-en-9-carboxylic acid (10-hydroxytetracyclo [6.2.1.1]
^3,6 . 0 ^2,7 ] dodecan-4-yl) ester,

Tetracyclo [6.2.1.1 ^3,6 . 0
^2,7 ] Methyl dodeca-4-ene-9-carboxylate, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-
Ethyl ene-9-carboxylate, tetracyclo [6.2.
1.1 ^3,6 . 0 ^2,7 ] n-propyl dodeca-4-en-9-carboxylate, tetracyclo [6.2.1.1 ^3,6 .
^0,7 ] t-butyl dodeca-4-ene-9-carboxylate, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] 2-Methyl-2-butyl dodeca-4-ene-9-carboxylate, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] ² -dec-2-butyl dodeca-4-ene-9-carboxylate, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] 3-dec-3-butyl dodeca-4-ene-9-carboxylate, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Cyclodecyl dodeca-4-ene-9-carboxylate, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] cyclohexyl dodeca-4-ene-9-carboxylate, tetracyclo [
6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-ene-9-
Carboxylic acid (adamantan-1-yl) ester, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4
-Ene-9-carboxylic acid (bicyclo [2.2.1] heptan-2-yl) ester, tetracyclo [6.2.
1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-en-9-carboxylic acid (7,7-dimethylbicyclo [2.2.1] heptan-1-yl) ester, tetracyclo [6.2.1.
1 ^3,6 . 0 ^2,7] dodecapeptide-4-ene-9-carboxylic acid (tetracyclo [6.2.1.1 ^{3, 6} .0 ^2,7] dodecane-4-yl) ester, tetracyclo [6.2.1 ．
1 ^3,6 . (Tricyclo [5.2.1.0 ^2,6 ] decan-8-yl) ester of 0 ^2,7 ] dodeca-4-en-9-carboxylic acid,

Tetracyclo [6.2.1.1 ^3,6 . 0
^2,7 ] 1-Methylcyclopentyl dodeca-4-en-9-carboxylic acid, tetracyclo [6.2.1.1 ^3,6 . 0
^2,7 ] Dodeca-4-ene-9-carboxylic acid 1-ethylcyclopentyl, tetracyclo [6.2.1.1 ^3,6 . 0
^2,7 ] Dodeca-4-ene-9-carboxylic acid 1-methylcyclohexyl, tetracyclo [6.2.1.1 ^3,6 . 0
^2,7 ] Dodeca-4-ene-9-carboxylate 1-ethylcyclohexyl, tetracyclo [6.2.1.1 ^3,6 . 0
^2,7 ] Dodeca-4-en-9-carboxylic acid (2-methyladamantan-2-yl) ester, tetracyclo [
6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-ene-9-
(2-Methyl-3-hydroxyadamantan-2-yl) ester of carboxylic acid, tetracyclo [6.2.1.
1 ^3,6 . ^0,7 ] Dodeca-4-en-9-carboxylic acid (2-ethyladamantan-2-yl) ester, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-
The ene-9-carboxylic acid (2-methylbicyclo [2.
2.1] heptan-2-yl) ester, tetracyclo
[6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-en-9
-(2-Ethylbicyclo [2.2.1] heptan-2-yl) ester of carboxylic acid, tetracyclo [6.2.
1.1 ^3,6 . 0 ^2,7 ] dodeca-4-en-9-carboxylic acid (4-methyltetracyclo [6.2.1.1 ^3,6 .
0 ^2,7 ] dodecan-4-yl) ester, tetracyclo
[6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-en-9
Of the carboxylic acid (4-ethyltetracyclo [6.2.
1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) ester,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca
4-ene-9-carboxylic acid (8-methyltricyclo [
5.2.1.0 ^2,6 ] Decan-8-yl) ester, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4
-Ene-9-carboxylic acid (8-ethyltricyclo [
5.2.1.0 ^2,6 ] decane-8-yl) ester,

Tetracyclo [6.2.1.1 ^3,6 . 0
^2,7 ] Dodeca-4-ene-9-carboxylic acid 1-methyl-
1-cyclopentylethyl, tetracyclo [6.2.
1.1 ^3,6 . 0 ^2,7 ] 1-methyl-1-cyclohexylethyl dodeca-4-ene-9-carboxylic acid, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-en-
9-carboxylic acid [1-methyl-1- (adamantane-
1-yl) ethyl] ester, tetracyclo [6.2.
1.1 ^3,6 . [2-methyl-1- (bicyclo [2.2.1] heptan-2-yl) ethyl] ester of 0 ^2,7 ] dodec-4-ene-9-carboxylic acid, tetracyclo [
6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-ene-9-
Carboxylic acid [1-methyl-1- (tetracyclo [6.
2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) ethyl] ester, tetracyclo [6.2.1.1 ^3,6 . 0
^2,1- ] dodec-4-ene-9-carboxylic acid [1-methyl-1- (tricyclo [5.2.1.0 ^2,6 ] decane-
8-yl) ethyl] ester, tetracyclo [6.2.
1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-ene-9-carboxylic acid 1-methyl-1- (2-hydroxycyclopentyl)
Ethyl, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ]
Dodeca-4-ene-9-carboxylic acid 1-methyl-1-
(3-Hydroxycyclopentyl) ethyl, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-en-
1-Methyl-1- (3-hydroxycyclohexyl) ethyl 9-carboxylate, tetracyclo [6.2.1.1]
^3,6 . 0 ^2,7 ] dodeca-4-ene-9-carboxylic acid 1-
Methyl-1- (4-hydroxycyclohexyl) ethyl, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene-9-carboxylic acid 1-methyl-1- (3-
Hydroxycycloheptyl) ethyl, tetracyclo [
6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-ene-9-
1-Methyl-1- (4-hydroxycycloheptyl) ethyl carboxylate, tetracyclo [6.2.1.1 ^3,6 .
0 ^2,7 ] 1-methyl-1- (3-hydroxyadamantan-1-yl) ethyl dodeca-4-en-9-carboxylate,

Tetracyclo [6.2.1.1 ^3,6 . 0
^2,7 ] Dodeca-4-ene-9-carboxylic acid 1,1-dicyclopentylethyl, tetracyclo [6.2.1.1]
^3,6 . 0 ^2,7 ] dodeca-4-ene-9-carboxylic acid 1,
1-dicyclohexylethyl, tetracyclo [6.2.
1.1 ^3,6 . [ ^2,7 ] Dodeca-4-ene-9-carboxylic acid [1,1-di (adamantan-1-yl) ethyl]
Ester, tetracyclo [6.2.1.1 ^3,6 . 0
^2,7 ] dodeca-4-ene-9-carboxylic acid [1,1-
Di (bicyclo [2.2.1] heptan-2-yl) ethyl] ester, tetracyclo [6.2.1.1 ^3,6 . 0
^2,7 ] dodeca-4-ene-9-carboxylic acid [1,1-
Di (tetracyclo [6.2.1.1 ^3,6 0.0 ^2,7 ] dodecan-4-yl) ethyl] ester, tetracyclo [
6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-ene-9-
The carboxylic acid [1,1-di (tricyclo [5.2.1.
0 ^2,6 ] Decan-8-yl) ethyl] ester, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-en-9-carboxylic acid (tetrahydrofuran-2-yl)
Methyl, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ]
Dodeca-4-ene-9-carboxylic acid 1,1-dimethyl-
2-oxopropyl,

Tetracyclo [6.2.1.1 ^3,6 . 0
^2,7] dodecapeptide-4-ene-9-carboxylic acid (5-oxo-4-oxatricyclo [4.2.1.0 ^3,7] nonan-2-yl) ester, tetracyclo [6.2 1.
1 ^3,6 . (9-Methoxycarbonyl-5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl) ester of 0 ^2,7 ] dodeca-4-en-9-carboxylic acid , Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ]
Dodeca-4-ene-9-carboxylic acid (7-oxo-6
-Oxabicyclo [3.2.1] octan-4-yl)
Ester, tetracyclo [6.2.1.1 ^3,6 . 0
(2-Methoxycarbonyl-7-oxo-6-oxabicyclo [3.2.1] octane-4-yl) ester of ^2,7 ] dodec-4-ene-9-carboxylic acid, tetracyclo [6.2. 1.1 ^3,6 . (2-oxotetrahydropyran-4-yl) ester of 0 ^2,7 ] dodeca-4-en-9-carboxylic acid, tetracyclo [6.2.1.1]
^3,6 . ^0,7 ] Dodeca-4-en-9-carboxylic acid (4-methyl-2-oxotetrahydropyran-4-yl) ester, tetracyclo [6.2.1.1 ^3,6 . 0
^2,7 ] Dodeca-4-en-9-carboxylic acid (4-ethyl-2-oxotetrahydropyran-4-yl) ester, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-ene-9-carboxylic acid (4-n-propyl-
2-oxotetrahydropyran-4-yl) ester,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca
(5-Oxotetrahydrofuran-3-yl) ester of 4-ene-9-carboxylic acid, tetracyclo [6.2.
1.1 ^3,6 . (2,2-Dimethyl-5-oxotetrahydrofuran-3-yl) ester of 0 ^2,7 ] dodec-4-en-9-carboxylic acid, tetracyclo [6.2.1.
1 ^3,6 . 0 ^2,7 ] Dodeca-4-ene-9-carboxylic acid (4,4-dimethyl-5-oxotetrahydrofuran-
3-yl) ester, tetracyclo [6.2.1.1]
^3,6 . ^0,7 ] Dodeca-4-en-9-carboxylic acid (2-oxotetrahydrofuran-3-yl) ester, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-ene-9-carboxylic acid (4,4-dimethyl-
2-oxotetrahydrofuran-3-yl) ester,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca
4-ene-9-carboxylic acid (5,5-dimethyl-2-
Oxotetrahydrofuran- ³ -yl) ester, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-
(2-Oxotetrahydrofuran-3-yl) ester of ene-9-carboxylic acid, tetracyclo [6.2.1.
1 ^3,6 . [ ^2,7 ] dodeca-4-en-9-carboxylic acid [(5-oxotetrahydrofuran-2-yl) methyl] ester, tetracyclo [6.2.1.1 ^3,6 . 0
^2,7 ] dodec-4-ene-9-carboxylic acid [(3,3
-Dimethyl-5-oxotetrahydrofuran-2-yl) methyl] ester, tetracyclo [6.2.1.1]
^3,6 . [(4,4-dimethyl-5-oxotetrahydrofuran-2-yl) methyl] ester of 0 ^2,7 ] dodec-4-ene-9-carboxylic acid and the like can be mentioned.

Examples of the monomer giving the repeating unit (IV) include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylate. ) (Fluoro) (hydroxy) methyl acrylate, (difluoro) (hydroxy) methyl (meth) acrylate, 1,2-difluoro-2-hydroxyethyl (meth) acrylate, 1,2,1 (meth) acrylic acid , 2-tetrafluoro-2-hydroxyethyl, (meth) acrylic acid 2-
Trifluoromethyl-2-hydroxyethyl, (meth)
2,2-Di (trifluoromethyl) -2-hydroxyethyl acrylate, 3-hydroxyadamantan-1-yl (meth) acrylate, 5-hydroxybicyclo [2.2.1] heptane- (meth) acrylate 2-yl, (meth) acrylic acid 6-hydroxybicyclo [2.2.1]
Heptane-2-yl, (meth) acrylic acid 9-hydroxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl, 10-hydroxytetracyclo [meth] acrylate [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecane-
4-yl,

(Meth) acrylic acid, carboxymethyl (meth) acrylic acid, (meth) acrylic acid 2-carboxyethyl ester, (meth) acrylic acid 3-carboxypropyl, (meth) acrylic acid 3-carboxyadamantane-1- Yl, (meth) acrylic acid 5-carboxybicyclo [2.2.1] heptan-2-yl, (meth) acrylic acid 6-carboxybicyclo [2.2.1] heptan-2-yl, (meth) acrylic Acid 9-carboxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-yl, (meth) acrylic acid 10-carboxytetracyclo
[6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-yl,
Cyanomethyl (meth) acrylate, 2-cyanoethyl 1- (meth) acrylate, 3-cyanopropyl (meth) acrylate, 3-cyanoadamantan-1-yl (meth) acrylate, 5-cyano (meth) acrylate Bicyclo [2.2.1] heptan-2-yl, 6-cyanobicyclo [2.2.1] heptan-2-yl (meth) acrylate, 9-cyanotetracyclo [meth] acrylic acid [6.
2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-yl, (meth)
Acrylic acid 10-cyanotetracyclo [6.2.1.1
^3,6 . 0 ^2,7 ] dodec-4-yl,

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, t-butyl (meth) acrylate, 2-methyl-2-butyl (meth) acrylate, (meth ) 2-Ethyl-2 acrylate
-Butyl, 3-ethyl-3-butyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, adamantane-1-yl (meth) acrylate, bicyclo (meth) acrylate [2. 2.
1] Heptan-2-yl, (meth) acrylic acid 7,7-
Dimethylbicyclo [2.2.1] heptatan-1-yl, tetracyclo (meth) acrylate [6.2.1.1]
^3,6 . 0 ^2,7 ] dodecan-4-yl, trimethy [(meth) acrylate [5.2.1.0 ^2,6 ] decane-8-yl, 1-methylcyclopentyl (meth) acrylate,
1-Ethylcyclopentyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, 2-methyladamantan-2-yl (meth) acrylate, (meth) acrylic acid 2 -Methyl-3-hydroxyadamantan-2-yl, (meth) acrylic acid 2-ethyladamantan-2-
2-methylbicyclo [meth.acrylic acid [2.
2.1] Heptan-2-yl, (meth) acrylic acid 2-
Ethylbicyclo [2.2.1] heptan-2-yl,
(Meth) acrylic acid 4-methyltetracyclo [6.2.
1.1 ^3,6 . 0 ^2,7 ] Dodecan-4-yl, 4-ethyltetracyclo [meth] acrylate [6.2.1.1]
^3,6 . 0 ^2,7 ] dodecan-4-yl, (meth) acrylic acid 8-methyltricyclo [5.2.1.0 ^2,6 ] decan-8-yl, (meth) acrylic acid 8-ethyltricyclo
[5.2.1.0 ^2,6 ] decane-8-yl,

1-Methyl-1-cyclopentylethyl (meth) acrylate, 1-methyl-1 (meth) acrylate
-Cyclohexylethyl, 1-methyl- (1-adamantan-1-yl) ethyl (meth) acrylate, (meth)
1-Methyl-1- (acrylic acid 1-bicyclo [2.2.1]
Heptan-2-yl) ethyl, (meth) acrylic acid 1-
Methyl-1- (tetracyclo [6.2.1.1 ^{3, 6} .0
^2,7 ] Dodecan-4-yl) ethyl, 1-methyl-1- (tricyclo [5.2.1.0] (meth) acrylate
^2,6 ] decane-2-yl) ethyl, 1-methyl-1- (2-hydroxycyclopentyl) ethyl (meth) acrylate, 1-methyl-1- (3-hydroxycyclopentyl) ethyl (meth) acrylate, (Meth) acrylic acid 1
-Methyl-1- (3-hydroxycyclohexyl) ethyl, (meth) acrylic acid 1-methyl-1- (4-hydroxycyclohexyl) ethyl, (meth) acrylic acid 1-
Methyl-1- (3-hydroxycycloheptyl) ethyl, 1-methyl-1- (4-hydroxycycloheptyl) ethyl (meth) acrylate, 1- (meth) acrylate
Methyl-1- (3-hydroxyadamantan-1-yl) ethyl, 1,1-dicyclopentylethyl (meth) acrylate, 1,1-dicyclohexylethyl (meth) acrylate, 1,1- (meth) acrylate Di (adamantan-1-yl) ethyl, (meth) acrylic acid 1,1-
Di (bicyclo [2.2.1] heptan-2-yl) ethyl, 1,1-di (tetracyclo [meth] acrylate
6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) ethyl, 1,1-di (tricyclo [meth] acrylic acid
5.2.1.0 ^2,6 ] Decan-8-yl) ethyl, (tetrahydrofuran-2-yl) methyl (meth) acrylate, 1,1-dimethyl-2-oxopropyl (meth) acrylate,

5-Methoxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl (meth) acrylate, 9-methoxycarbonyl-5- (meth) acrylate
Oxo-4-oxatricyclo [4.2.1.0 ^3,7 ]
Nonan-2-yl, 7-oxo-6 (meth) acrylic acid
-Oxabicyclo [3.2.1] octan-4-yl,
(Meth) acrylic acid-2-methoxycarbonyl-7-oxo-6-oxabicyclo [3.2.1] octane-4
-Yl, (meth) acrylic acid 2-oxotetrahydropyran-4-yl, (meth) acrylic acid 4-methyl-2-
Oxotetrahydropyran-4-yl, 4-ethyl-2-oxotetrahydropyran-4- (meth) acrylate
-Yl, (meth) acrylic acid 4-n-propyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid 5-oxotetrahydrofuran-3-yl, (meth) acrylic acid 2,2-dimethyl-5- Oxotetrahydrofuran-3-yl, (meth) acrylic acid 4,4-dimethyl-5-oxotetrahydrofuran-3-yl, (meth)
2-oxotetrahydrofuran-3-yl acrylate,
(Meth) acrylic acid 4,4-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid 5,5
-Dimethyl-2-oxotetrahydrofuran-3-yl, 2-oxotetrahydrofuran-3-yl (meth) acrylate, (5-oxotetrahydrofuran-2-yl) methyl (meth) acrylate, (meth) acrylic acid (3 , 3-dimethyl-5-oxotetrahydrofuran-
2-yl) methyl, (meth) acrylic acid (4,4-dimethyl-5-oxotetrahydrofuran-2-yl) methyl and the like can be mentioned.

Examples of the repeating units other than the repeating unit (III) and the repeating unit (IV) include bicyclo [2.2.1] hept-2-ene and bicyclo [2.2.1] hept. 2-en-5-acetic acid, bicyclo [2.2.1] hept-2-ene-5-propionic acid, 5-cyanobicyclo [2.2.1] hept-2-ene, 5-cyanomethylbicyclo [ 2.2.1] Hept-2-ene, 5- (2-cyanoethyl) bicyclo [2.
2.1] hept-2-ene, 5- (3-cyanopropyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5
-Hydroxymethylbicyclo [2.2.1] hept-2
-Ene, 5- (2-hydroxyethyl) bicyclo [2.
2.1] hept-2-ene, 5- (3-hydroxypropyl) bicyclo [2.2.1] hept-2-ene, 5-
[(Fluoro) (hydroxy) methyl] bicyclo [2.
2.1] hept-2-ene, 5-[(difluoro) (hydroxy) methyl] bicyclo [2.2.1] hept-2
-Ene, 5- (1,2-difluoro-2-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-
(1,1,2,2-Tetrafluoro-2-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-
(2-Trifluoromethyl-2-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5- [2,2
-Di (trifluoromethyl) -2-hydroxyethyl]
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- n-Propylbicyclo [2.2.1] hept-2-ene, 5-
n-butylbicyclo [2.2.1] hept-2-ene,
5-n-hexylbicyclo [2.2.1] hept-2-
Bicyclo [2.2.1] hept such as ene, 5-n-octylbicyclo [2.2.1] hept-2-ene and 5-n-decylbicyclo [2.2.1] hept-2-ene. -2
-Ene or its derivatives;

Tetracyclo [6.2.1.1^3,6 ． 0
^2,7 ] Dodeca-4-ene, tetracyclo [6.2.1.
1^3,6 ． 0^2,7 ] Dodeca-4-ene-9-acetic acid, tetra
Cyclo [6.2.1.1^3,6 ． 0^2,7 ] Dodeca-4-d
-9-propionic acid, 9-cyanotetracyclo [6.
2.1.1^3,6 ． 0^2,7 ] Dodeca-4-ene, 9-sia
Nomethyltetracyclo [6.2.1.1^3,6 ． 0^2,7 ]
Dodeca-4-ene, 9- (2-cyanoethyl) tetracy
Black [6.2.1.1^3,6 ． 0^2,7 ] Dodeca-4-d
And 9- (3-cyanopropyl) tetracyclo [6.
2.1.1^3,6． 0^2,7 ] Dodeca-4-ene, 9-hid
Roxytetracyclo [6.2.1.1^3,6 ． 0^2,7 ] Do
Deca-4-ene, 9-hydroxymethyl tetracyclodo
Deca [6.2.1.1^3,6 ． 0^2,7 ] Dodeca-4-d
9- (2-hydroxyethyl) tetracyclo [6.
2.1.1 ^3,6 ． 0^2,7 ] Dodeca-4-ene, 9- (3
-Hydroxypropyl) tetracyclo [6.2.1.1
^3,6 ． 0^2,7 ] Dodeca-4-ene, 9-[(fluoro)
(Hydroxy) methyl] tetracyclo [6.2.1.1]
^3,6 ． 0^2,7 ] Dodeca-4-ene, 9-[(difluo
(B) (Hydroxy) methyl] tetracyclo [6.2.
1.1^3,6 ． 0^2,7 ] Dodeca-4-ene, 9- (1,2
-Difluoro-2-hydroxyethyl) tetracyclo [
6.2.1.1^3,6 ． 0^2,7 ] Dodeca-4-ene, 9-
(1,1,2,2-tetrafluoro-2-hydroxye
Cyl) tetracyclo [6.2.1.1^3,6 ． 0^2,7 ] Do
Deca-4-ene, 9- (2-trifluoromethyl-2-
Hydroxyethyl) tetracyclo [6.2.1.1
^3,6 ． 0^2,7 ] Dodeca-4-ene, 9- [2,2-di]
(Trifluoromethyl) -2-hydroxyethyl) teto
Lacyclo [6.2.1.1^3,6 ． 0^2,7 ] Dodeca-4-
Ene, 9-methyltetracyclo [6.2.1.1^3,6 ．
0^2,7 ] Dodeca-4-ene, 9-ethyltetracyclo [
6.2.1.1^3,6 ． 0^2,7 ] Dodeca-4-ene, 9-
n-Propyltetracyclo [6.2.1.1^3,6 ． 0
^2,7 ] Dodeca-4-ene, 9-n-butyltetracyclo
[6.2.1.1^3,6 ． 0^2,7 ] Dodeca-4-en, 9
-N-hexyltetracyclo [6.2.1.1]^3,6 ． 0
^2,7 ] Dodeca-4-ene, 9-n-octyltetrasic
B [6.2.1.1^3,6 ． 0^2,7 ] Dodeca-4-en,
9-n-decyltetracyclo [6.2.1.1^3,6 ． 0
^2,7 ] Dodeca-4-ene and other tetracyclo [6.2.
1.1^3,6 ． 0^2,7 ] Dodeca-4-ene or its induction
Body type;

Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate; (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile,
Unsaturated nitrile compounds such as malein nitrile, fumaronitrile, mesacone nitrile, citracon nitrile and itacone nitrile; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleinamide, maleimide, N-phenylmaleimide, N
-Unsaturated amide compounds or unsaturated imide compounds such as cyclohexylmaleimide, fumaramide, mesacone amide, citracone amide, itacone amide; N-vinyl-
Other nitrogen-containing vinyl compounds such as ε-caprolactam, N-vinylpyrrolidone, vinylpyridine, vinylimidazole; crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, Other unsaturated carboxylic acids (anhydrides) such as mesaconic acid; monofunctional monomers such as

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

Among these monomers, especially bicyclo [2.2.1] hept-2-ene, 5-cyanobicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2]. 1.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5-
[2,2-di (trifluoromethyl) -2-hydroxyethyl] bicyclo [2.2.1] hept-2-ene, 5
-Ethylbicyclo [2.2.1] hept-2-ene, 5
-N-butylbicyclo [2.2.1] hept-2-ene, 5-n-hexylbicyclo [2.2.1] hept-
2-ene, tetracyclo [6.2.1.1 ^3,6 . 0
^2,7 ] dodec-4-ene, 9-cyanotetracyclo [
6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-ene, 9-
Hydroxytetracyclo [6.2.1.1 ^3,6 . 0
^2,7 ] Dodeca-4-ene, 9-hydroxymethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9- [2,2-di (trifluoromethyl) -2-hydroxyethyl] tetracyclo [6.2.1.1 ^3,6 .
0 ^2,7 ] dodec-4-ene, 9-ethyltetracyclo [
6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-ene, 9-
n-Butyltetracyclo [6.2.1.1 ^3,6 . 0
^2,7 ] Dodeca-4-ene, 9-n-hexyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-ene,
(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonic acid, maleic anhydride and the like are preferable.

Preferable combinations of repeating units in the resin (A) include, for example, the following formulas (A1) to (A
6) (In each formula, R represents a hydrogen atom or a methyl group.)
Can be mentioned.

[0079]

[Chemical 10]

[0080]

[Chemical 11]

[0081]

[Chemical 12]

[0082]

[Chemical 13]

[0083]

[Chemical 14]

[0084]

[Chemical 15]

In the resin (A), the repeating unit (I)
The total content of the repeating units (II) is usually 10 to 100 mol%, preferably 10 to 60 mol%, more preferably 10 to 50 mol%, particularly preferably 20 to 50%, based on all repeating units. Mol%. In this case, if the total content is less than 10 mol%, the resolution as a resist tends to decrease. The total content of repeating units (III) and repeating units (IV) is usually 90 mol% or less, preferably 10 to 80 mol%, more preferably 10 to 60 mol%, based on all repeating units. It is particularly preferably 20 to 60 mol%. In this case, if the total content exceeds 90 mol%, the resolution as a resist and the solubility of the composition in a solvent tend to be lowered. Further, the content of the repeating unit other than the repeating unit (III) and the repeating unit (IV) is usually 20 mol% or less, preferably 10 mol% or less, based on all repeating units.

The resin (A) contains, for example, a monomer corresponding to each repeating unit and a radical polymerization initiator such as hydroperoxides, dialkylperoxides, diacylperoxides, and azo compounds, and is required. It can be produced by polymerizing in a suitable solvent in the presence of a chain transfer agent. Examples of the solvent used for the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; cyclohexane, cycloheptane, cyclooctane, decalin, Cycloalkanes such as norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, fluorochloroethanes, hexamethylene dibromide and chlorobenzene Kinds; ethyl acetate, n-butyl acetate, i-acetic acid
Esters such as butyl, methyl propionate and propylene glycol monomethyl ether acetate; lactones such as γ-butyrolactone; ethers such as tetrahydrofuran, dimethoxyethanes and diethoxyethanes;
Examples thereof include ketones such as 2-butanone, 2-heptanone, methyl isobutyl ketone and cyclohexanone; alcohols such as isopropanol and propylene glycol monomethyl ether. These solvents may be used alone or in admixture of two or more.
Moreover, the reaction temperature in the said superposition | polymerization is 40-12 normally.
0 ° C, preferably 50 to 100 ° C, and the reaction time is
Usually, it is 1 to 48 hours, preferably 1 to 24 hours.

The resin (A) in the present invention is a halogen,
Of course, the less impurities such as metals, the better, but
The residual monomer and oligomer components are also below the specified value,
For example, the value measured by high performance liquid chromatography (HPLC) is preferably 0.1% by weight or less, whereby the sensitivity as a resist, resolution, process stability, pattern shape, etc. can be further improved. In addition, it is possible to provide a radiation-sensitive resin composition exhibiting stable resist performance with less variation in the amount of foreign matter in a composition solution used for forming a resist pattern and changes with time in sensitivity and the like. Examples of the purification method of the resin (A) include the following methods. First, as a method of removing impurities such as metal, a method of adsorbing a metal in a resin solution using a zeta potential filter, or a method of washing the resin solution with an acidic aqueous solution of oxalic acid, sulfonic acid, or the like to chelate the metal A method of removing it can be mentioned. Further, as a method for reducing the residual monomer or oligomer component to below the specified value, washing with water; liquid extraction for removing the residual monomer or oligomer component by selecting or combining an appropriate solvent, and identifying by selecting or combining an appropriate solvent Liquid phase purification method such as ultrafiltration to extract and remove only low molecular weight components below the molecular weight; A solid phase purification method such as a method of washing with a poor solvent can be mentioned, and these methods can be combined. The solvent used in the liquid phase purification method and the poor solvent used in the solid phase purification method are appropriately selected according to the resin to be purified.

The polystyrene equivalent weight average molecular weight (hereinafter referred to as "Mw") of the resin (A) by gel permeation chromatography (GPC) is usually 1,0.
00-300,000, preferably 2,000-20
10,000, more preferably 3,000 to 100,0
00. In this case, the Mw of the resin (A) is 1,000.
If it is less than 100%, the heat resistance as a resist tends to decrease, while if it exceeds 300,000, the developability as a resist tends to decrease. Also, the Mw of the resin (A)
And gel permeation chromatography (GPC)
Polystyrene-reduced number average molecular weight (hereinafter "Mn")
Say. The ratio (Mw / Mn) is usually 1 to 5, preferably 1 to 3. In the present invention, the resin (A)
Can be used alone or in admixture of two or more.

Component (B) The component (B) in the present invention is a radiation-sensitive acid generator (hereinafter referred to as “acid”) that generates an acid upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. Generator (B) "
Say. ) Consists of. The acid generator (B) dissociates the acid dissociable groups present in the resin (A) by the action of the acid generated by exposure, and as a result, the exposed portion of the resist film becomes readily soluble in an alkali developing solution, and It has a function of forming a resist pattern of the mold. Acid generator (B)
As the acid generated from, those represented by the following formulas (BA-1) to (BA-5) are preferable.

[0090]

[Chemical 16]

[In the formula (BA-1), each Rf independently represents a fluorine atom or a trifluoromethyl group, and Rf
a is a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms A monovalent hydrocarbon group or is a cyclic monovalent fluorinated hydrocarbon group having 3 to 20 carbon atoms, and the cyclic monovalent hydrocarbon group and the cyclic monovalent fluorinated hydrocarbon group are substituted. It may have been done.

In the formula (BA-2), Rf represents a fluorine atom or a trifluoromethyl group, Rf 'represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and Rb represents a hydrogen atom or a carbon number of 1 To a linear or branched alkyl group having 20 to 20 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic monovalent fluorinated hydrocarbon group having 3 to 20 carbon atoms. The monovalent hydrocarbon group and the cyclic monovalent fluorinated hydrocarbon group may be substituted.

In the formula (BA-3), Rs has 1 to 2 carbon atoms.
0 straight-chain or branched alkyl group or 3 carbon atoms
To 20 cyclic monovalent hydrocarbon groups, and the cyclic monovalent hydrocarbon groups may be substituted.

In the formula (BA-4), Rc has 1 to 2 carbon atoms.
0 straight-chain or branched alkyl group having 1 to 2 carbon atoms
0 straight-chain or branched fluorinated alkyl group, C 3-20 cyclic monovalent hydrocarbon group or C 3-
20 cyclic monovalent fluorinated hydrocarbon groups are shown, and the cyclic monovalent hydrocarbon group and the cyclic monovalent fluorinated hydrocarbon group may be substituted.

In the formula (BA-5), Re is Ra --SO ₂
Represents a group or Ra-CO- group, and Ra has the same meaning as Ra in formula (B-1). However, when the acid generated from the acid generator (B) contains a mixture of the acid represented by the formula (BA-1) and the acid represented by the formula (BA-5), it is represented by the formula (BA-1). Ra of the acid represented and Ra of the acid represented by the formula (BA-5) may be the same or different. ]

In the formulas (BA-1) to (BA-5), Ra and R
Examples of the linear or branched alkyl group having 1 to 20 carbon atoms of b, Rs, Rc and Re include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-
Butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, n-hexyl group,
Examples thereof include n-heptyl group and n-octyl group. Examples of the linear or branched fluorinated alkyl group having 1 to 20 carbon atoms for Ra, Rc and Re include, for example, trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group and heptafluoro-i. -Propyl group, nonafluoro-n-butyl group, nonafluoro-2-methylpropyl group, nonafluoro-1-
Methylpropyl group, nonafluoro-t-butyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, perfluoro-n-heptyl group, perfluoro-
An n-octyl group etc. can be mentioned.

Further, Ra, Rb, Rs, Rc and Re
As the cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms,
For example, phenyl group, 2-naphthyl group, 2-naphthyl group, cycloalkyl group, adamantane-1-yl group, bicyclo [2.2.1] heptan-2-yl group, tetracyclo [6.2.1.1]. ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 10-campanyl group and the like can be mentioned.

The cyclic monovalent fluorinated hydrocarbon group having 3 to 20 carbon atoms for Ra, Rb, Rc and Re is, for example, a phenyl group, a 2-naphthyl group, a 2-naphthyl group or a cycloalkyl group. An adamantane-1-yl group,
Bicyclo [2.2.1] heptan-2-yl group, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecane-4-
Examples thereof include groups in which an yl group or a 10-campanyl group is substituted with one or more fluorine atoms.

Examples of the acid represented by the above formula (BA-1) include trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, 1,1,2,2-tetrafluoro-
n-propanesulfonic acid, heptafluoro-n-propanesulfonic acid, 1,1,2,2-tetrafluoro-n-
Linear or branched fluorinated alkyl sulfonic acids such as butane sulfonic acid, nonafluoro-n-butane sulfonic acid, 1,1,2,2-tetrafluoro-n-octane sulfonic acid, perfluoro-n-octane sulfonic acid ;

1,1,2,2-Tetrafluoroethanesulfonic acid, 1-trifluoromethyl-1,2,2-trifluoroethanesulfonic acid, 2-trifluoromethyl-
1,1,2-trifluoroethanesulfonic acid, 1,2-
Di (trifluoromethyl) -1,2-difluoroethanesulfonic acid, 1,1-di (trifluoromethyl) -2,
The hydrogen atom located at each 2-position of 2-difluoroethanesulfonic acid or 2,2-di (trifluoromethyl) -1,1-difluoroethanesulfonic acid is replaced with a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, 4- Trifluoromethylphenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group,
2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 3,6-difluorophenyl group,
2,3,4,5,6-pentafluorophenyl group, naphthalen-1-yl group, naphthalen-2-yl group, adamantane-1-yl group, adamantane-2-yl group, 3-
Hydroxyadamantan-1-yl group, 3-hydroxyadamantan-2-yl group, bicyclo [2.2.1] heptan-2-yl group, 5-hydroxybicyclo [2.
2.1] heptan-2-yl group, 6-hydroxybicyclo [2.2.1] heptan-2-yl group, 7,7-dimethylbicyclo [2.2.1] heptan-2-yl group, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecane-
4-yl group, 9-hydroxytetracyclo [6.2.
1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group or 10
-Hydroxytetracyclo [6.2.1.1 ^3,6 . 0
^Examples include acids substituted with a ^2,7 ] dodecane-4-yl group.

Further, as the acid represented by the formula (BA-2),
For example, 1-fluoroethanesulfonic acid, 1-fluoro-n-propanesulfonic acid, 1-fluoro-n-butanesulfonic acid, 1-fluoro-n-octanesulfonic acid,
1,1-difluoroethanesulfonic acid, 1,1-difluoro-n-propanesulfonic acid, 1,1-difluoro-
n-butanesulfonic acid, 1,1-difluoro-n-octanesulfonic acid, 1-trifluoromethyl-n-propanesulfonic acid, 1-trifluoromethyl-n-butanesulfonic acid, 1-trifluoromethyl-n- Octanesulfonic acid, 1,1-di (trifluoromethyl) ethanesulfonic acid, 1,1-di (trifluoromethyl) -n-propanesulfonic acid, 1,1-bis (trifluoromethyl)
Linear or branched fluorinated alkyl sulfonic acids such as -n-butane sulfonic acid and 1,1-di (trifluoromethyl) -n-octane sulfonic acid;

Monofluoromethanesulfonic acid, difluoromethanesulfonic acid, 1-fluoroethanesulfonic acid,
1,1-difluoroethanesulfonic acid, (trifluoromethyl) methanesulfonic acid, 1- (trifluoromethyl) ethanesulfonic acid, di (trifluoromethyl) methanesulfonic acid or 1,1-di (trifluoromethyl)
A hydrogen atom located at each 1-position or a hydrogen atom located at each 2-position of ethanesulfonic acid is represented by a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a 4-trifluoromethylphenyl group, and a 2,3-difluoro group. Phenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group,
3,4-difluorophenyl group, 3,5-difluorophenyl group, 3,6-difluorophenyl group, 2,3
4,5,6-Pentafluorophenyl group, naphthalene-
1-yl group, naphthalen-2-yl group, adamantane-
1-yl group, adamantane-2-yl group, 3-hydroxyadamantan-1-yl group, 3-hydroxyadamantan-2-yl group, bicyclo [2.2.1] heptane-
2-yl group, 5-hydroxybicyclo [2.2.1] heptan-2-yl group, 6-hydroxybicyclo [2.
2.1] heptan-2-yl group, 7,7-dimethylbicyclo [2.2.1] heptan-2-yl group, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 9-hydroxytetracyclo [6.2.1.1]
^3,6 . 0 ^2,7 ] dodecan-4-yl group or 10-hydroxytetracyclo [6.2.1.1 ^3,6 . ^Examples thereof include acids substituted with a 0 ^2,7 ] dodecan-4-yl group.

Further, as the acid represented by the formula (BA-3),
For example, methanesulfonic acid, ethanesulfonic acid, n-propanesulfonic acid, n-butanesulfonic acid, 2-methylpropanesulfonic acid, 1-methylpropanesulfonic acid,
t-butane sulfonic acid, n-pentane sulfonic acid, n-
Linear, branched or cyclic alkyl sulfonic acids such as hexane sulfonic acid, n-octane sulfonic acid, cyclopentane sulfonic acid, cyclohexane sulfonic acid; benzene sulfonic acid, p-toluene sulfonic acid, benzyl sulfonic acid, α-naphthalene Aromatic sulfonic acids such as sulfonic acid and β-naphthalene sulfonic acid; 10-camphor sulfonic acid and the like.

Further, as the acid represented by the formula (BA-4),
For example, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, benzoic acid, salicylic acid,
Phthalic acid, terephthalic acid, α-naphthalenecarboxylic acid,
β-naphthalenecarboxylic acid, cyclobutanecarboxylic acid,
Cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, adamantane-1-carboxylic acid, bicyclo [2.
2.1] Heptane-2-carboxylic acid, adamantane-1
-Acetic acid, bicyclo [2.2.1] heptane-2-acetic acid,
Monocarboxylic acids such as lithocholic acid, deoxycholic acid, chenodeoxycholic acid and cholic acid; cyclobutane-
1,1-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid, cyclopentane-1,1-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, cyclopentane-
1,3-dicarboxylic acid, cyclohexane-1,1-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, adamantane-1,3-dicarboxylic acid Acid, bicyclo [2.2.1] heptane-2,3-
Examples thereof include dicarboxylic acids, adamantane-1,3-diacetic acid, and dicarboxylic acids such as bicyclo [2.2.1] heptane-2,3-diacetic acid.

Further, as the acid represented by the formula (BA-5), for example, N, N-bis (trifluoromethanesulfonyl) imidic acid, N, N-bis (pentafluoroethanesulfonyl) imidic acid, N, N-bis (1, 1, 2, 2
-Tetrafluoro-n-propanesulfonyl) imidic acid, N, N-bis (heptafluoro-n-propanesulfonyl) imidic acid, N, N-bis (1,1,2,2-tetrafluoro-n-butanesulfonyl) ) Imidic acid, N,
N-bis (nonafluoro-n-butanesulfonyl) imidic acid, N, N-bis (1,1,2,2-tetrafluoro-n-octanesulfonyl) imidic acid, N, N-bis (perfluoro-n-) Octanesulfonyl) imidic acid,
N-trifluoromethanesulfonyl / N-pentafluoroethanesulfonylimidic acid, N-trifluoromethanesulfonyl / N-heptafluoro-n-propanesulfonylimidic acid, N-trifluoromethanesulfonyl / N
-Nonafluoro-n-butanesulfonylimidic acid, N-
Pentafluoroethanesulfonyl / N-heptafluoro-n-propanesulfonylimidic acid, N-pentafluoroethanesulfonyl / N-nonafluoro-n-butanesulfonylimidic acid, N-heptafluoro-n-propanesulfonyl / N-nonafluoro-n -Butane sulfonylimidic acid etc. can be mentioned.

Examples of the compounds which generate the acids represented by the above formulas (BA-1) to (BA-5) include onium salt compounds,
Sulfonimide compounds, sulfone compounds, sulfonate compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds,
A hydrazine sulfonate compound etc. can be mentioned.

Examples of the onium salt compounds include iodonium salts, sulfonium salts (including tetrahydrothiophenium salts), phosphonium salts, diazonium salts, pyridinium salts and the like. Preferred onium salt compounds include, for example, diphenyliodonium salt, di (4-t-butylphenyl) iodonium salt, di (p-toluyl) iodonium salt, di (3,4-dimethylphenyl) iodonium salt, 4-nitrophenyl. -Phenyliodonium salt, di (3-nitrophenyl) iodonium salt, 4-methoxyphenyl-phenyliodonium salt, di (4-chlorophenyl) iodonium salt, di (4-trifluoromethylphenyl) iodonium salt,
Iodonium salts such as biphenylene iodonium salts, di (naphthalen-2-yl) iodonium salts, 2-chlorobiphenylene iodonium salts; triphenylsulfonium salts, 4-t-butylphenyl diphenylsulfonium salts, 4-t-butoxyphenyl diphenyl Sulfonium salt, 4-hydroxyphenyl / diphenylsulfonium salt, tri (4-methoxyphenyl) sulfonium salt,
Di (4-methoxyphenyl) -p-toluylsulfonium salt, phenyl-biphenylenesulfonium salt, 4-phenylthiophenyl-diphenylsulfonium salt, 4,
An arylsulfonium salt such as a 4'-bis (diphenylsulfoniophenyl) sulfide salt;

Tri (cyclo) alkylsulfonium salts such as dicyclohexyl.methylsulfonium salt, dimethyl.cyclohexylsulfonium salt, tricyclohexylsulfonium salt; cyclohexyl.2-oxocyclohexyl.methylsulfonium salt, dicyclohexyl.
2-oxocyclohexylsulfonium salt, 2-oxocyclohexyldimethylsulfonium salt, bicyclo [2.2.1] heptan-2-ylmethyl-2-oxocyclohexylsulfonium salt, bicyclo [2.2.
1] Heptan-2-ylcyclohexyl-2-oxocyclohexylsulfonium salt, 1- [2- (naphthalen-1-yl) -2-oxoethyl] tetrahydrothiophenium salt, 1- [2- (naphthalene-2- Ill)-
2-oxoethyl] tetrahydrothiophenium salt, 1
2- (2-oxo-n-butyl) tetrahydrothiophenium salt and other 2-oxosulfonium salts; naphthalene-1
-Yl dimethyl sulfonium salt, naphthalen-1-yl diethyl sulfonium salt, 4-cyanonaphthalene-
1-yl dimethylsulfonium salt, 4-cyanonaphthalen-1-yl diethylsulfonium salt, 4-nitronaphthalen-1-yl dimethylsulfonium salt, 4-
Nitronaphthalen-1-yl-diethylsulfonium salt, 4-methylnaphthalen-1-yl-dimethylsulfonium salt, 4-methylnaphthalen-1-yl-diethylsulfonium salt, 4-hydroxynonaphthalen-1-yl-dimethylsulfonium salt A naphthalen-1-yl dialkylsulfonium salt such as 4-hydroxynaphthalen-1-yl diethylsulfonium salt;

1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium salt, 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium salt, 1- (4-ethoxynaphthalen-1-yl) ) Tetrahydrothiophenium salt, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium salt, 1
-(4-Methoxymethoxynaphthalen-1-yl) tetrahydrothiophenium salt, 1- (4-ethoxymethoxynaphthalen-1-yl) tetrahydrothiophenium salt, 1- [4- (1-methoxyethoxy) naphthalene-
1-yl] tetrahydrothiophenium salt, 1- [4-
(2-Methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium salt, 1- (4-methoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium salt, 1- (4-ethoxycarbonyloxynaphthalene-1-) 1) tetrahydrothiophenium salt, 1
-(4-n-propoxycarbonyloxynaphthalene-
1-yl) tetrahydrothiophenium salt, 1- (4-
i-Propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium salt, 1- (4-n-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium salt, 1- (4-t-butoxycarbonyloxynaphthalene -1-yl) tetrahydrothiophenium salt, 1- [4- (2-tetrahydrofuranyloxy) naphthalen-1-yl] tetrahydrothiophenium salt, 1- [4- (2-tetrahydropyranyloxy) naphthalene- 1-yl] tetrahydrothiophenium salt, 1- (4-benzyloxynaphthalen-1-yl) tetrahydrothiophenium salt, 4- (4-n-butoxynaphthalen-1-yl) -4-thioniatricyclo [5.2.1.0 ^2,6 ] decane salt, (4-ethoxynaphthalen-1-yl)- 4-thioniatricyclo [5.
2.1.0 ^2,6 ] decane salt, 1- [4- (bicyclo [2.2.1] heptan-2-yl) oxynaphthalen-1-yl] tetrahydrothiophenium salt, 1-
(3,5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium salt, 1- (3,5-dimethyl-4)
-Ethoxyphenyl) tetrahydrothiophenium salt,
1- (3,5-dimethyl-4-n-butoxyphenyl)
An arylthiophenium salt such as a tetrahydrothiophenium salt can be used.

Examples of the sulfonimide compound include compounds represented by the following general formula (B1).

[0111]

[Chemical 17] [In the general formula (B1), [RA] is the above formula (BA-1)
~ (BA-4) represents a residue of any acid represented by the formula (BA-4), and is a group which, when dissociated, produces an acid represented by the formulas (BA-1) to (BA-4); ¹ represents a divalent organic group. ]

The compound represented by the general formula (B1) is a compound obtained by substituting a hydrogen atom for the [RA] group in the general formula (B1) (hereinafter referred to as "mother nucleus compound (B1)") and the above formula. A compound having a structure in which the acid residues represented by (BA-1) to (BA-4) are bonded via a sulfonyl bond or a carbonyl bond. Examples of the mother nucleus compound (B1) include N-hydroxysuccinimide, N-hydroxydiphenylmaleimide, N-hydroxybicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N-hydroxy-7-oxabicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N-hydroxybicyclo [2.2.1] heptane-5,
Examples thereof include 6-oxy-2,3-dicarboximide, N-hydroxynaphthylimide and N-hydroxyphthalimide.

Examples of the sulfone compound include β
Examples thereof include keto sulfone, β-sulfonyl sulfone, and these α-diazo compounds. Examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, imino sulfonate and the like. Examples of the disulfonyldiazomethane compound include compounds represented by the following general formula (B2).

[0114]

[Chemical 18] [In the general formula (B2), each [RA] independently has the same meaning as [RA] in the general formula (B1). ]

Examples of the disulfonylmethane compound include
For example, a compound represented by the following general formula (B3) can be given.

[0116]

[Chemical 19] [In the general formula (B3), each [RA] independently has the same meaning as [RA] in the general formula (B1), and
And at least one of W is an aryl group, or V and W are connected to each other to form a monocyclic or polycyclic structure having at least one unsaturated bond,
Or V and W are connected to each other

[0117]

[Chemical 20] (However, V ′ and W ′ may be the same or different from each other, and a plurality of V ′ and W ′ may be the same or different from each other, and a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, V ′ and W ′, which represent an aryl group or an aralkyl group, or are bonded to the same or different carbon atoms are linked to each other to form a carbon monocyclic structure, and k is an integer of 2 to 10. ) Form a group represented by. ]

Examples of the oxime sulfonate compound include the following general formula (B4-1) or general formula (B4)
The compound represented by -2) can be mentioned.

[0119]

[Chemical 21] [In the general formula (B4-1) and the general formula (B4-2),
Each [RA] independently of each other in the general formula (B1)
It has the same meaning as [RA] and each R ¹² independently represents a monovalent organic group. ]

General formula (B4-1) and general formula (B4-2)
In the above, specific examples of R ¹² include a methyl group, an ethyl group, an n-propyl group, a phenyl group and a tosyl group.

Examples of the hydrazine sulfonate compound include bis (benzene) sulfonyl hydrazine,
Bis (p-toluene) sulfonylhydrazine, bis (trifluoromethane) sulfonylhydrazine, bis (nonafluoro-n-butane) sulfonylhydrazine, bis (n-propane) sulfonylhydrazine, benzenesulfonylhydrazine, p-toluenesulfonylhydrazine, trifluoromethanesulfonyl Examples thereof include hydrazine, nonafluoro-n-butanesulfonylhydrazine, n-propanesulfonylhydrazine, trifluoromethanesulfonyl.p-toluenesulfonylhydrazine and the like.

Specific examples of the preferred acid generator (B) include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2- (bicyclo [2 1.2.1] heptan-2-yl)
-1,1,2,2-Tetrafluoroethanesulfonate, diphenyliodonium 2- (5-hydroxybicyclo [2.2.1] heptan-2-yl) -1,1,
2,2-tetrafluoroethanesulfonate, diphenyliodonium 2- (6-hydroxybicyclo [2.
2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, diphenyliodonium 2- (tetracyclo [6.2.1.1 ^3,6 0.0 ^2,7 ]]
Dodecane-4-yl) -1,1,2,2-tetrafluoroethanesulfonate, diphenyliodonium 2-
(9-Hydroxytetracyclo [6.2.1.1 ^3,6 .
0 ^2,7 ] dodecan-4-yl) -1,1,2,2-tetrafluoroethanesulfonate, diphenyliodonium 2- (10-hydroxytetracyclo [6.2.1.
1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) -1,1,2,
2-tetrafluoroethane sulfonate,

Diphenyliodonium N, N-bis (trifluoromethanesulfonyl) imidate, diphenyliodonium N, N-bis (pentafluoroethanesulfonyl) imidate, diphenyliodonium N, N-
Bis (heptafluoro-n-propanesulfonyl) imidate, diphenyliodonium N, N-bis (nonafluoro-n-butanesulfonyl) imidate, diphenyliodonium benzenesulfonate, diphenyliodonium 4-trifluoromethylbenzenesulfonate, diphenyliodonium 2,4- Difluorobenzene sulfonate, diphenyliodonium 2,3,4
5,6-pentafluorobenzene sulfonate, diphenyliodonium 10-camphor sulfonate,

Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-)
(Butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2- (bicyclo [2.2.1] ] Heptan-2-yl) -1,1,
2,2-tetrafluoroethane sulfonate, bis (4
-T-Butylphenyl) iodonium 2- (5-hydroxybicyclo [2.2.1] heptan-2-yl)-
1,1,2,2-tetrafluoroethane sulfonate,
Bis (4-t-butylphenyl) iodonium 2- (6
-Hydroxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium 2
-(Tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecane-4-yl) -1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium 2- (9-hydroxytetracyclo [6.
2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) -1,
1,2,2-Tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium 2- (10-
Hydroxytetracyclo [6.2.1.1 ^3,6 . 0
^2,7 ] dodecan-4-yl) -1,1,2,2-tetrafluoroethanesulfonate,

Bis (4-t-butylphenyl) iodonium N, N-bis (trifluoromethanesulfonyl) imidate, bis (4-t-butylphenyl) iodonium N, N-bis (pentafluoroethanesulfonyl) imidate, bis ( 4-t-butylphenyl) iodonium N, N-bis (heptafluoro-n-propanesulfonyl) imidate, bis (4-t-butylphenyl) iodonium N, N-bis (nonafluoro-n-butanesulfonyl) imidate, bis (4-t-butylphenyl) iodonium benzene sulfonate, bis (4-t
-Butylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium 2,4-difluorobenzenesulfonate, bis (4-t-butylphenyl) iodonium 2,3,4,5,6 -Pentafluorobenzenesulfonate, bis (4-t-butylphenyl) iodonium 1
0-camphor sulfonate,

Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2- (bicyclo [2.2.1] heptane-2- Yl) -1,1,2,2-tetrafluoroethane sulfonate, triphenylsulfonium 2- (5
-Hydroxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (6-hydroxybicyclo [2.2.1] heptane-2 -Il) -1,
1,2,2-Tetrafluoroethanesulfonate, triphenylsulfonium 2- (tetracyclo [6.2.
1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) -1,1,
2,2-Tetrafluoroethanesulfonate, triphenylsulfonium 2- (9-hydroxytetracyclo [
6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl)-
1,1,2,2-tetrafluoroethane sulfonate,
Triphenylsulfonium 2- (10-hydroxy-tetracyclo [6.2.1.1 ^3,6 .0 ^2,7] dodecane -4
-Yl) -1,1,2,2-tetrafluoroethane sulfonate,

Triphenylsulfonium N, N-bis (trifluoromethanesulfonyl) imidate, triphenylsulfonium N, N-bis (pentafluoroethanesulfonyl) imidate, triphenylsulfonium N, N-bis (heptafluoro-n-propanesulfonyl) ) Imidate, triphenylsulfonium N, N-bis (nonafluoro-n-butanesulfonyl) imidate, triphenylsulfonium benzene sulfonate,
Triphenylsulfonium 4-trifluoromethylbenzene sulfonate, triphenylsulfonium 2,4-
Difluorobenzene sulfonate, triphenyl sulfonium 2,3,4,5,6-pentafluorobenzene sulfonate, triphenyl sulfonium 10-camphor sulfonate,

Bicyclo [2.2.1] heptan-2-ylcyclohexyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate, bicyclo [2.2.1] heptan-2-ylcyclohexyl.
2-oxocyclohexylsulfonium nonafluoro-
n-butane sulfonate, bicyclo [2.2.1] heptan-2-yl cyclohexyl 2-oxocyclohexyl sulfonium perfluoro-n-octane sulfonate, bicyclo [2.2.1] heptan-2-yl
Cyclohexyl-2-oxocyclohexylsulfonium 2- (bicyclo [2.2.1] heptan-2-yl)
-1,1,2,2-Tetrafluoroethanesulfonate, Bicyclo [2.2.1] heptan-2-ylcyclohexyl-2-oxocyclohexylsulfonium 2
-(5-Hydroxybicyclo [2.2.1] hept-2
-Yl) -1,1,2,2-tetrafluoroethanesulfonate, bicyclo [2.2.1] heptan-2-ylcyclohexyl-2-oxocyclohexylsulfonium 2- (6-hydroxybicyclo [2.2. 1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, bicyclo [2.2.1] heptane-2
-Yl cyclohexyl-2-oxocyclohexylsulfonium 2- (tetracyclo [6.2.1.1 ^3,6 .
0 ^2,7 ] dodecan-4-yl) -1,1,2,2-tetrafluoroethanesulfonate, bicyclo [2.2.
1] heptan-2-ylcyclohexyl-2-oxocyclohexylsulfonium 2- (9-hydroxytetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecane-4
-Yl) -1,1,2,2-tetrafluoroethanesulfonate, bicyclo [2.2.1] heptan-2-ylcyclohexyl-2-oxocyclohexylsulfonium 2- (10-hydroxytetracyclo [6.2] ．
1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) -1,1,
2,2-tetrafluoroethane sulfonate,

Bicyclo [2.2.1] heptane-2-ylcyclohexyl-2-oxocyclohexylsulfonium N, N-bis (trifluoromethanesulfonyl)
Imidate, bicyclo [2.2.1] heptane-2-ylcyclohexyl.2-oxocyclohexylsulfonium N, N-bis (pentafluoroethanesulfonyl) imidate, bicyclo [2.2.1] heptane-2
-Ylcyclohexyl-2-oxocyclohexylsulfonium N, N-bis (heptafluoro-n-propanesulfonyl) imidate, bicyclo [2.2.1] heptan-2-ylcyclohexyl-2-oxocyclohexylsulfonium N, N -Bis (nonafluoro-n
-Butanesulfonyl) imidate, bicyclo [2.2.
1] heptan-2-yl cyclohexyl 2-oxocyclohexylsulfonium benzene sulfonate, bicyclo [2.2.1] heptan-2-yl cyclohexyl 2-oxocyclohexyl sulfonium 4-trifluoromethylbenzene sulfonate, bicyclo [2] ．
2.1] heptan-2-ylcyclohexyl-2-oxocyclohexylsulfonium 2,4-difluorobenzenesulfonate, bicyclo [2.2.1] heptan-2-ylcyclohexyl-2-oxocyclohexylsulfonium 2,3 4,5,6-pentafluorobenzenesulfonate, bicyclo [2.2.1] heptan-2-ylcyclohexyl-2-oxocyclohexylsulfonium 10-camphorsulfonate,

1- [2- (naphthalen-1-yl) -2
-Oxoethyl] tetrahydrothiophenium trifluoromethanesulfonate, 1- [2- (naphthalene-1
-Yl) -2-oxoethyl] tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- [2
-(Naphthalen-1-yl) -2-oxoethyl] tetrahydrothiophenium perfluoro-n-octane sulfonate, 1- [2- (naphthalen-1-yl) -2
-Oxoethyl] tetrahydrothiophenium 2- (bicyclo [2.2.1] heptan-2-yl) -1,1,
2,2-tetrafluoroethane sulfonate, 1- [2
-(Naphthalen-1-yl) -2-oxoethyl] tetrahydrothiophenium 2- (5-hydroxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2
-Tetrafluoroethanesulfonate, 1- [2- (naphthalen-1-yl) -2-oxoethyl] tetrahydrothiophenium 2- (6-hydroxybicyclo [2.
2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- [2- (naphthalen-1-yl) -2-oxoethyl] tetrahydrothiophenium 2- (tetracyclo [ 6.2.1.1 ^3,6 .
0 ^2,7 ] dodecan-4-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- [2- (naphthalen-1-yl) -2-oxoethyl] tetrahydrothiophenium 2- (9 -Hydroxytetracyclo [6.
2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) -1,
1,2,2-tetrafluoroethane sulfonate, 1-
[2- (naphthalen-1-yl) -2-oxoethyl]
Tetrahydrothiophenium 2- (10-hydroxytetracyclo [6.2.1.1 ^3,6, 0 ^2,7 ] dodecane-
4-yl) -1,1,2,2-tetrafluoroethane sulfonate,

1- [2- (naphthalen-1-yl) -2
-Oxoethyl] tetrahydrothiophenium N, N-
Bis (trifluoromethanesulfonyl) imidate, 1
-[2- (naphthalen-1-yl) -2-oxoethyl] tetrahydrothiophenium N, N-bis (pentafluoroethanesulfonyl) imidate, 1- [2-
(Naphthalen-1-yl) -2-oxoethyl] tetrahydrothiophenium N, N-bis (heptafluoro-
n-propanesulfonyl) imidate, 1- [2- (naphthalen-1-yl) -2-oxoethyl] tetrahydrothiophenium N, N-bis (nonafluoro-n-butanesulfonyl) imidate, 1- [2- (naphthalene -1-yl) -2-oxoethyl] tetrahydrothiophenium benzene sulfonate, 1- [2- (naphthalen-1-yl) -2-oxoethyl] tetrahydrothiophenium 4-trifluoromethylbenzene sulfonate, 1- [2 -(Naphthalen-1-yl) -2-oxoethyl] tetrahydrothiophenium 2,4-difluorobenzenesulfonate, 1- [2- (naphthalene-1)
-Yl) -2-oxoethyl] tetrahydrothiophenium 2,3,4,5,6-pentafluorobenzenesulfonate, 1- [2- (naphthalen-1-yl) -2-
Oxoethyl] tetrahydrothiophenium 10-camphorsulfonate,

1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- ( 4-hydroxynaphthalen-1-yl) tetrahydrothiophenium 2- (bicyclo [2.2.1] heptan-2-yl) -1,1,2,
2-tetrafluoroethanesulfonate, 1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium 2- (5-hydroxybicyclo [2.2.1] heptan-2-yl) -1,1,2, 2-Tetrafluoroethanesulfonate, 1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium 2- (6-hydroxybicyclo [2.2.1] heptan-2-yl)
-1,1,2,2-Tetrafluoro-ethanesulfonate, 1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium 2- (tetracyclo [6.2.
1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) -1,1,
2,2-tetrafluoroethane sulfonate, 1- (4
-Hydroxynaphthalen-1-yl) tetrahydrothiophenium 2- (9-hydroxytetracyclo [6.
2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) -1,
1,2,2-tetrafluoroethane sulfonate, 1-
(4-Hydroxynaphthalen-1-yl) tetrahydrothiophenium 2- (10-hydroxytetracyclo [
6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl)-
1,1,2,2-tetrafluoroethane sulfonate,

1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium N, N-bis (trifluoromethanesulfonyl) imidate, 1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium N, N -Bis (pentafluoroethanesulfonyl)
Imidate, 1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium N, N-bis (heptafluoro-n-propanesulfonyl) imidate, 1-
(4-Hydroxynaphthalen-1-yl) tetrahydrothiophenium N, N-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium benzenesulfonate, diphenyliodonium 4-trifluoromethylbenzenesulfonate, 1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium 2,4-difluorobenzenesulfonate, 1- (4-
(Hydroxynaphthalen-1-yl) tetrahydrothiophenium 2,3,4,5,6-pentafluorobenzenesulfonate, 1- (4-hydroxynaphthalen-1-
Yl) tetrahydrothiophenium 10-camphor sulfonate,

1- (4-n-butoxynaphthalene-1-
Yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalene-1)
-Yl) tetrahydrothiophenium nonafluoro-n
-Butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (Bicyclo [2.2.1] heptan-2-yl)
-1,1,1,2,2-Tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (5-hydroxybicyclo [2.2.1] heptane-2- Ill) -1, 1, 2,
2-tetrafluoroethane sulfonate, 1- (4-n
-Butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (6-hydroxybicyclo [2.2.1]
Heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (tetracyclo [6.2.1.1] ^3,6 .0 ^2,7] dodecane -
4-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalene-1-
Yl) Tetrahydrothiophenium 2- (9-hydroxytetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecane-4-yl) -1,1,2,2-tetrafluoroethane sulfonate , 1- (4-n-Butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (10-hydroxytetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ].
Dodecane-4-yl) -1,1,2,2-tetrafluoroethanesulfonate,

1- (4-n-butoxynaphthalene 11-
1) tetrahydrothiophenium N, N-bis (trifluoromethanesulfonyl) imidate, 1- (4-n
-Butoxynaphthalene 11-yl) tetrahydrothiophenium N, N-bis (pentafluoroethanesulfonyl) imidate, 1- (4-n-butoxynaphthalene-
1-yl) tetrahydrothiophenium N, N-bis (heptafluoro-n-propanesulfonyl) imidate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium N, N-bis (nonafluoro- n-butanesulfonyl) imidate, 1- (4-n-
Butoxynaphthalen-1-yl) tetrahydrothiophenium benzene sulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 4
-Trifluoromethylbenzene sulfonate, 1- (4
-N-butoxynaphthalen-1-yl) tetrahydrothiophenium 2,4-difluorobenzenesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2,3,4,5,6- Pentafluorobenzene sulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 10-camphor sulfonate,

(4-n-Butoxynaphthalen-1-yl) -4-thioniatricyclo [5.2.1.0 ^2,6 ].
Decane trifluoromethanesulfonate, (4-n-butoxynaphthalen-1-yl) -4-thioniatricyclo [5.2.1.0 ^2,6 ] decane nonafluoro-n-butanesulfonate, (4-n- Butoxynaphthalene-1
-Yl) -4-thioniatricyclo [5.2.1.0
^2,6 ] Decane perfluoro-n-octane sulfonate, (4-n-butoxynaphthalen-1-yl) -4-
Thioniatricyclo [5.2.1.0 ^2,6 ] decane 2-
(Bicyclo [2.2.1] heptan-2-yl) -1,
1,2,2-tetrafluoroethane sulfonate, (4
-N-Butoxynaphthalen-1-yl) -4-thioniatricyclo [5.2.1.0 ^2,6 ] decane 2- (5-hydroxybicyclo [2.2.1] hept-2-yl) −
1,1,2,2-tetrafluoroethane sulfonate,
(4-n-Butoxynaphthalen-1-yl) -4-thioniatricyclo [5.2.1.0 ^2,6 ] decane 2- (6
-Hydroxybicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, (4-n-butoxynaphthalen-1-yl) -4
-Thioniatricyclo [5.2.1.0 ^2,6 ] decane 2
-2- (tetracyclo [6.2.1.1 ^3,6 0.0 ^2,7 ]]
Dodecan-4-yl) -1,1,2,2-tetrafluoroethanesulfonate, (4-n-butoxynaphthalen-1-yl) -4-thioniatricyclo [5.2.1.
0 ^2,6 ] decane 2- (9-hydroxytetracyclo [
6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl)-
1,1,2,2-tetrafluoroethane sulfonate,
(4-n-Butoxynaphthalen-1-yl) -4-thioniatricyclo [5.2.1.0 ^2,6 ] decane 2- (1
0-Hydroxytetracyclo [6.2.1.1 ^3,6 . 0
^2,7 ] dodecan-4-yl) -1,1,2,2-tetrafluoroethanesulfonate,

(4-n-Butoxynaphthalen-1-yl) -4-thioniatricyclo [5.2.1.0 ^2,6 ].
Decane N, N-bis (trifluoromethanesulfonyl)
Imidate, (4-n-butoxynaphthalen-1-yl) -4-thioniatricyclo [5.2.1.0 ^2,6 ].
Decane N, N-bis (pentafluoroethanesulfonyl) imidate, (4-n-butoxynaphthalene-1-
Yl) -4-thioniatricyclo [5.2.1.0
^2,6 ] decane N, N-bis (heptafluoro-n-propanesulfonyl) imidate, (4-n-butoxynaphthalen-1-yl) -4-thioniatricyclo [5.
2.1.0 ^2,6 ] decane N, N-bis (nonafluoro-
n-butanesulfonyl) imidate, (4-n-butoxynaphthalen-1-yl) -4-thioniatricyclo [
5.2.1.0 ^2,6 ] decanebenzene sulfonate,
(4-n-Butoxynaphthalen-1-yl) -4-thioniatricyclo [5.2.1.0 ^2,6 ] decane 4-trifluoromethylbenzenesulfonate, (4-n-butoxynaphthalene-1-) Ill) -4-thioniatricyclo
[5.2.1.0 ^2,6 ] decane 2,4-difluorobenzenesulfonate, (4-n-butoxynaphthalene-1
-Yl) -4-thioniatricyclo [5.2.1.0
^2,6 ] decane 2,3,4,5,6-pentafluorobenzene sulfonate, (4-n-butoxynaphthalene-1
-Yl) -4-thioniatricyclo [5.2.1.0
^2,6 ] decane 10-camphor sulfonate,

1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate , 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octane sulfonate, 1-
(3,5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2- (bicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- ( 3,5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2-
(5-hydroxybicyclo [2.2.1] hept-2-
Yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2- (6-hydroxybicyclo [2.2.1] hept- 2-yl) -1,
1,2,2-tetrafluoroethane sulfonate, 1-
(3,5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2- (tetracyclo [6.2.
1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) -1,1,
2,2-tetrafluoroethane sulfonate, 1-
(3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2- (9-hydroxy tetracyclo [6.2.1.1 ^3,6 .0 ^2,7] dodecane-4-yl) -1, 1,2,2-tetrafluoroethane sulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2- (10-hydroxy-tetracyclo [6.2.1.1 ^{3, 6} .0 ^2,7 ] dodecan-4-yl) -1,1,2,2-tetrafluoroethanesulfonate,

1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium N, N-bis (trifluoromethanesulfonyl) imidate, 1-
(3,5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium N, N-bis (pentafluoroethanesulfonyl) imidate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium N, N -Bis (heptafluoro-n-propanesulfonyl) imidate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium N, N-
Bis (nonafluoro-n-butanesulfonyl) imidate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium benzene sulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 4-trifluoromethylbenzene sulfonate, 1- (3,5-dimethyl-4
-Hydroxyphenyl) tetrahydrothiophenium 2,4-difluorobenzenesulfonate, 1- (3,
5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2,3,4,5,6-pentafluorobenzene sulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 10-
Camphor sulfonate,

1- (3,5-Dimethyl-4-butoxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-butoxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate , 1- (3,5-dimethyl-
4-butoxyphenyl) tetrahydrothiophenium perfluoro-n-octane sulfonate, 1- (3,5
-Dimethyl-4-butoxyphenyl) tetrahydrothiophenium 2- (bicyclo [2.2.1] heptane-2
-Yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4-butoxyphenyl) tetrahydrothiophenium 2- (5-hydroxybicyclo [2.2.1] heptane -2-yl) -1,
1,2,2-tetrafluoroethane sulfonate, 1-
(3,5-Dimethyl-4-butoxyphenyl) tetrahydrothiophenium 2- (6-hydroxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2
-Tetrafluoroethane sulfonate, 1- (3,5-
Dimethyl-4-butoxyphenyl) tetrahydrothiophenium 2- (tetracyclo [6.2.1.1 ^{3, 6} .0
^2,7 ] Dodecan-4-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4-butoxyphenyl) tetrahydrothiophenium 2- (9-hydroxytetracyclo [6.2.1.1
^3,6 . 0 ^2,7 ] dodecan-4-yl) -1,1,2,2
-Tetrafluoroethane sulfonate, 1- (3,5-
Dimethyl-4-butoxyphenyl) tetrahydrothiophenium 2- (10-hydroxytetracyclo [6.
2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) -1,
1,2,2-tetrafluoroethane sulfonate,

1- (3,5-dimethyl-4-butoxyphenyl) tetrahydrothiophenium N, N-bis (trifluoromethanesulfonyl) imidate, 1- (3
5-Dimethyl-4-butoxyphenyl) tetrahydrothiophenium N, N-bis (pentafluoroethanesulfonyl) imidate, 1- (3,5-dimethyl-4-butoxyphenyl) tetrahydrothiophenium N, N-
Bis (heptafluoro-n-propanesulfonyl) imidate, 1- (3,5-dimethyl-4-butoxyphenyl) tetrahydrothiophenium N, N-bis (nonafluoro-n-butanesulfonyl) imidate, 1-
(3,5-dimethyl-4-butoxyphenyl) tetrahydrothiophenium benzene sulfonate, 1- (3,
5-dimethyl-4-butoxyphenyl) tetrahydrothiophenium 4-trifluoromethylbenzenesulfonate, 1- (3,5-dimethyl-4-butoxyphenyl) tetrahydrothiophenium 2,4-difluorobenzenesulfonate, 1- ( 3,5-dimethyl-4-butoxyphenyl) tetrahydrothiophenium 2,3,3
4,5,6-pentafluorobenzene sulfonate, 1
-(3,5-dimethyl-4-butoxyphenyl) tetrahydrothiophenium 10-camphorsulfonate,

N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (perfluoro-n-octanesulfonyloxy) succinimide,
N- [2- (bicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonyloxy] succinimide, N- [2- (5-hydroxybicyclo [2. 2.1] heptan-2-yl) -1,
1,2,2-Tetrafluoroethanesulfonyloxy]
Succinimide, N- [2- (6-hydroxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2
-Tetrafluoroethanesulfonyloxy] succinimide, N- [2- (tetracyclo [6.2.1.1]
^3,6 . 0 ^2,7 ] dodecan-4-yl) -1,1,2,2
-Tetrafluoroethanesulfonyloxy] succinimide, N- [2- (9-hydroxytetracyclo [6.
2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) -1,
1,2,2-Tetrafluoroethanesulfonyloxy]
Succinimide, N- [2- (10-hydroxy-tetracyclo [6.2.1.1 ^3,6 .0 ^2,7] dodecane-4
Il) -1,1,2,2-tetrafluoroethanesulfonyloxy] succinimide, N- (benzenesulfonyloxy) succinimide, N- (4-trifluoromethylbenzenesulfonyloxy) succinimide, N-
(2,4-Difluorobenzenesulfonyloxy) succinimide, N- (2,3,4,5,6-pentafluorobenzenesulfonyloxy) succinimide, N-
(10-camphorsulfonyloxy) succinimide,

N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- [2 -(Bicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonyloxy] bicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, N- [2-
(5-hydroxybicyclo [2.2.1] heptane-2
-Yl) -1,1,2,2-tetrafluoroethanesulfonyloxy] bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- [2- (6-hydroxybicyclo] [2.2.1] heptan-2-yl)
-1,1,2,2-Tetrafluoroethanesulfonyloxy] bicyclo [2.2.1] hept-5-ene-2,
3-dicarboximide, N- [2- (tetracyclo [
6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl)-
1,1,2,2-Tetrafluoroethanesulfonyloxy] bicyclo [2.2.1] hept-5-ene-2,3
- dicarboximide, N- [2- (9-hydroxy tetracyclo [6.2.1.1 ^3,6 .0 ^2,7] dodecane -
4-yl) -1,1,2,2-tetrafluoroethanesulfonyloxy] bicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide, N- (benzenesulfonyloxy) bicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2,4 -Difluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (2,3,4,5,5
6-Pentafluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5 -En-2,3
-Dicarboximide,

N- (trifluoromethanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( Perfluoro-n-octanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- [2
-(Bicyclo [2.2.1] heptan-2-yl)-
1,1,2,2-Tetrafluoroethanesulfonyloxy] -7-oxabicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide, N- [2- (5-
Hydroxybicyclo [2.2.1] hept-2-yl)
-1,1,2,2-Tetrafluoroethanesulfonyloxy] -7-oxabicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide, N- [2- (6
-Hydroxybicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonyloxy] -7-oxabicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N- [2-
(Tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecan-4-yl) -1,1,2,2-tetrafluoroethanesulfonyloxy] -7-oxabicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N- [2- (9-hydroxytetracyclo [6.2.
1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl) -1,1,
2,2-Tetrafluoroethanesulfonyloxy] -7
-Oxabicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- [2- (10-hydroxytetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecan-4-yl) -1,1,2,2 -Tetrafluoroethanesulfonyloxy] -7-oxabicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N- (benzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide , N- (4-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N- (2,4-difluorobenzenesulfonyloxy)
-7-Oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2,3,4,
5,6-Pentafluorobenzenesulfonyloxy)-
7-oxabicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.
1] Hept-5-ene-2,3-dicarboximide and the like.

Of these acid generators (B), more preferred are diphenyliodonium trifluoromethanesulfonate and diphenyliodonium nonafluoro-.
n-butane sulfonate, diphenyl iodonium perfluoro-n-octane sulfonate, diphenyl iodonium 2- (bicyclo [2.2.1] heptane-2-
Yl) -1,1,2,2-tetrafluoroethanesulfonate, diphenyliodonium 2- (tetracyclo [
6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl)-
1,1,2,2-tetrafluoroethane sulfonate,
Diphenyliodonium N, N-bis (nonafluoro-
n-butanesulfonyl) imidate, diphenyliodonium 10-camphorsulfonate, bis (4-t-
Butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-
t-butylphenyl) iodonium perfluoro-n-
Octane sulfonate, bis (4-t-butylphenyl) iodonium 2- (bicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethane sulfonate, bis (4-t- butylphenyl) iodonium 2- (tetracyclo [6.2.1.1 ^{3, 6} .0
^2,7 ] Dodecan-4-yl) -1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium N, N-bis (nonafluoro-n
-Butanesulfonyl) imidate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate,

Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2- (bicyclo [2.2.1] heptane-2- yl) 1,1,2,2-tetrafluoroethane sulfonate, triphenylsulfonium 2- (tetracyclo [6.2.1.1 ^3,6 .0 ^2,7] dodecane -
4-yl) -1,1,2,2-tetraluroethanesulfonate, triphenylsulfonium N, N-bis (nonafluoro-n-butanesulfonyl) imidate, triphenylsulfonium 10-camphorsulfonate,
1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalene-1-
Il) tetrahydrothiophenium perfluoro-n-
Octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (bicyclo [2.2.1] heptan-2-yl) -1,1,
2,2-tetrafluoroethane sulfonate, 1- (4
-N-Butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (tetracyclo [6.2.1.1]
^3,6 . 0 ^2,7 ] dodecan-4-yl) -1,1,2,2
-Tetrafluoroethane sulfonate, 1- (4-n-
Butoxynaphthalen-1-yl) tetrahydrothiophenium N, N-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 10-camphorsulfonate,

1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate , 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octane sulfonate, 1-
(3,5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2- (bicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- ( 3,5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2-
(Tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecane-4-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4-) Hydroxyphenyl) tetrahydrothiophenium N, N-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 10-camphorsulfonate, N- (trifluoromethane Sulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (perfluoro-n-octanesulfonyloxy) succinimide,
N- [2- (bicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonyloxy] succinimide, N- [2- (tetracyclo
[6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl)
-1,1,2,2-tetrafluoroethanesulfonyloxy] succinimide, N- (10-camphorsulfonyloxy) succinimide,

N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- [2 -(Bicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonyloxy] bicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, N- [2-
(Tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecan-4-yl) -1,1,2,2-tetrafluoroethanesulfonyloxy] bicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, N- (10-
Camphorsulfonyloxy) bicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide and the like.

In the present invention, the acid generator (B) may be used alone or in combination of two or more kinds. The amount of the acid generator (B) used is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the resin (A) from the viewpoint of ensuring sensitivity and developability as a resist. 1 to 7 parts by weight. In this case, if the amount of the acid generator (B) used is less than 0.1 parts by weight, the sensitivity and developability as a resist tend to be decreased, while the value of 10
If it exceeds the amount by weight, the transparency to radiation decreases,
It tends to be difficult to obtain a rectangular resist pattern.

Various Additives In the radiation-sensitive resin composition of the present invention, the diffusion phenomenon of the acid generated from the acid generator (B) upon exposure in the resist film is controlled to suppress an undesired chemical reaction in the unexposed area. It is preferable to add an acid diffusion control agent having the action of By compounding such an acid diffusion controller, the storage stability of the resulting radiation-sensitive resin composition is further improved, and the resolution as a resist is further improved, and the storage time from exposure to development processing is also increased. (P
A change in the line width of the resist pattern due to a change in ED) can be suppressed, and a composition having extremely excellent process stability can be obtained. The acid diffusion controller is preferably a nitrogen-containing organic compound whose basicity does not change due to exposure or heat treatment during the resist pattern forming step. Examples of such nitrogen-containing organic compounds include compounds represented by the following general formula (C) (hereinafter referred to as "acid diffusion control agent (C)").

[0151]

[Chemical formula 22] [In the general formula (C), each R ¹³ independently represents a hydrogen atom, a linear, branched, or cyclic alkyl group, an aryl group, or an aralkyl group.
The aryl group and aralkyl group may be substituted with a functional group such as a hydroxyl group, U ² represents a divalent organic group, and b is an integer of 0-2. ]

In the acid diffusion controller (C), the compound with b = 0 is referred to as “nitrogen-containing compound (α)”, and the compound with b = 1 to 2 is referred to as “nitrogen-containing compound (β)”. Further, the polyamino compound and the polymer having three or more nitrogen atoms are collectively referred to as "nitrogen-containing compound (γ)". Furthermore, as the nitrogen-containing organic compound other than the acid diffusion controller (C), for example, 4
Examples thereof include secondary ammonium hydroxide compounds, amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds.

As the nitrogen-containing compound (α), for example, n
-Hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine and other mono (cyclo) alkylamines;
Di-n-butylamine, di-n-pentylamine, di-
n-hexylamine, di-n-heptylamine, di-n
-Di (cyclo) alkylamines such as octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine; triethylamine, tri-n-propylamine, tri-n-
Butylamine, tri-n-pentylamine, tri-n-
Hexylamine, tri-n-heptylamine, tri-n
-Octylamine, tri-n-nonylamine, tri-n
-Tri (cyclo) alkylamines such as decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, tricyclohexylamine; aniline, N-
Methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, 2,6-dimethylaniline,
2,6-diisopropylaniline, diphenylamine,
Aromatic amines such as triphenylamine and naphthylamine can be mentioned.

Examples of the nitrogen-containing compound (β) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, tetra Methylenediamine, 1,3-bis [1- (4-aminophenyl)
-1-Methylethyl] benzenetetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2 -Bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2-
(4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane,
2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- ( 4-aminophenyl) -1-methylethyl] benzene, bis (2-dimethylaminoethyl) ether,
Examples thereof include bis (2-diethylaminoethyl) ether. As the nitrogen-containing compound (γ), for example,
Examples thereof include polymers of polyethyleneimine, polyallylamine, and 2-dimethylaminoethylacrylamide. Examples of the quaternary ammonium hydroxide compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-
n-Propyl ammonium hydroxide, tetra-n-
Butyl ammonium hydroxide etc. can be mentioned.

Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-
Adamantylamine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4 ′. -Diaminodiphenylmethane, N, N'-di-t-butoxycarbonylhexamethylenediamine, N, N, N ', N'-tetra-t-butoxycarbonylhexamethylenediamine,
N, N'-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N'-di-t-butoxycarbonyl-1,8-diaminooctane, N, N'-di-t-butoxycarbonyl- 1,9-diaminononane, N, N'-
Di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12
-Diaminododecane, N, N'-di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt
-Butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, N
In addition to Nt-butoxycarbonyl group-containing amino compounds such as -t-butoxycarbonyl-2-phenylbenzimidazole, formamide, N-methylformamide,
Examples thereof include N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone and N-methylpyrrolidone.

Examples of the urea compound include urea, methylurea, 1,1-dimethylurea and 1,3-
Examples thereof include dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea and tri-n-butylthiourea. Examples of the nitrogen-containing heterocyclic compound include imidazole, 4-methylimidazole, 1-benzyl-2-methylimidazole, 4-
Imidazoles such as methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenyl Pyridine, 2-methyl-
4-phenylpyridine, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 4-hydroxyquinoline, 8-
Pyridines such as oxyquinoline and acridine; piperazines such as piperazine and 1- (2-hydroxyethyl) piperazine, as well as pyrazine, pyrazole, pyridazine,
Quinozaline, purine, pyrrolidine, piperidine, 3-piperidino-1,2-propanediol, morpholine, 4
-Methylmorpholine, 1,4-dimethylpiperazine,
1,4-diazabicyclo [2.2.2] octane and the like can be mentioned.

These acid diffusion control agents may be used alone or in combination with 2
A mixture of two or more species can be used. The compounding amount of the acid diffusion controller is usually 100 parts by weight of the resin (A),
It is 15 parts by weight or less, preferably 10 parts by weight or less, more preferably 5 parts by weight or less. In this case, if the amount of the acid diffusion controller is more than 15 parts by weight, the sensitivity of the resist and the developability of the exposed area tend to be lowered. If the amount of the acid diffusion controller is less than 0.001 part by weight, the pattern shape and dimensional fidelity of the resist may be reduced depending on the process conditions.

Further, the radiation-sensitive resin composition of the present invention can be blended with an additive exhibiting an action of further improving dry etching resistance, pattern shape, adhesion to a substrate, etc. It can have an acid dissociable group. Examples of such additives include t-butyl adamantane-1-carboxylate, t-butoxycarbonylmethyl adamantane-1-carboxylate, adamantane-
1-carboxylic acid α-butyrolactone ester, adamantane-1,3-dicarboxylic acid di-t-butyl, adamantane-1-t-butyl acetate, adamantane-1-acetic acid t
-Butoxycarbonylmethyl, adamantane-1,3-
Adamantane derivatives such as di-t-butyl diacetate and 2,5-dimethyl-2,5-di (adamantan-1-ylcarbonyloxy) hexane; t-butyl deoxycholate, t-butoxycarbonylmethyl deoxycholate ,
Deoxycholic acid esters such as 2-ethoxyethyl deoxycholic acid, 2-cyclohexyloxyethyl deoxycholic acid, 3-oxocyclohexyl deoxycholic acid, tetrahydropyranyl deoxycholic acid and mevalonolactone deoxycholic acid; lithocholic acid t
-Butyl, t-butoxycarbonylmethyl lithocholic acid, 2-ethoxyethyl lithocholic acid, lithocholic acid 2
-Lithocholic acid esters such as cyclohexyloxyethyl, 3-oxocyclohexyl lithocholic acid, tetrahydropyranyl lithocholic acid, mevalonolactone lithocholic acid: dimethyl adipate, diethyl adipate, propyl adipate, di-n-butyl adipate. , Alkyl carboxylic acid esters such as di-t-butyl adipate; and the like.

These additives may be used alone or in admixture of two or more. The amount of the additive compounded is usually 50 parts by weight or less, preferably 30 parts by weight or less, based on 100 parts by weight of the resin (A). in this case,
When the amount of the additive compounded exceeds 50 parts by weight, the heat resistance of the resist tends to be lowered.

Further, the radiation-sensitive resin composition of the present invention may contain a surfactant having an effect of improving coating property, developability and the like. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene. In addition to nonionic surfactants such as glycol distearate, KP341 (produced by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, the same No. 95
(Manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF301, E
F303, EF352 (Tochem Products Co., Ltd.)
Made), Megafax F171, same F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC430, same F
C431 (Sumitomo 3M Limited), Asahi Guard A
G710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, S
Examples thereof include C-105 and SC-106 (manufactured by Asahi Glass Co., Ltd.).

These surfactants can be used alone or in admixture of two or more. The compounding amount of the surfactant is 10 in total of the resin (A) and the acid generator (B).
It is usually 2 parts by weight or less with respect to 0 parts by weight.

Further, the radiation-sensitive resin composition of the present invention may contain a sensitizer having an effect of improving sensitivity and the like. Examples of preferable sensitizers include carbazoles, benzophenones, rose bengals, anthracenes, and phenols. These sensitizers can be used alone or in admixture of two or more. The compounding amount of the sensitizer is 100% of resin (A).
It is preferably 50 parts by weight or less per part by weight. Further, as additives other than the above, an antihalation agent,
Adhesion aids, storage stabilizers, defoamers and the like can be mentioned.

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

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

These solvents may be used alone or in admixture of two or more, and among them, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, Preferred are 2-hydroxypropionate alkyls, 3-alkoxypropionate alkyls, γ-butyrolactone and the like.

Method of Forming Resist Pattern The radiation-sensitive resin composition of the present invention is particularly useful as a chemically amplified resist. In the chemically amplified resist, the acid dissociable group in the resin (A) is dissociated by the action of the acid generated from the acid generator (B) upon exposure to generate a carboxyl group, and as a result, the resist is exposed to light. Part has a higher solubility in an alkaline developer, and the exposed part is dissolved and removed by the alkaline developer to obtain a positive resist pattern. When forming a resist pattern from the radiation-sensitive resin composition of the present invention, the composition solution is applied by a suitable coating means such as spin coating, cast coating, roll coating, and spray coating, for example, a silicon wafer or aluminum. A resist film is formed by applying it on a substrate such as a wafer covered with, and in some cases, a heat treatment (hereinafter referred to as “PB”) is performed in advance, and then a predetermined resist pattern is formed. Expose the resist coating. The radiation used at that time is, for example, ultraviolet rays, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193n).
m), F ₂ excimer laser (wavelength 157 nm), EUV
Far ultraviolet rays (extreme ultraviolet rays, wavelength 13 nm, etc.), charged particle beams such as electron beams, X-rays such as synchrotron radiation, etc. can be appropriately selected and used. Of these, far ultraviolet rays and electron beams are used. preferable. Also, the exposure conditions such as the exposure amount are
It is appropriately selected according to the composition of the radiation-sensitive resin composition, the type of each additive, and the like. In the present invention, in order to stably form a highly precise fine pattern, it is preferable to perform a heat treatment (hereinafter referred to as “PEB”) after the exposure. Due to this PEB, the dissociation reaction of the acid dissociable group in the resin (A) proceeds smoothly. The heating condition of PEB varies depending on the composition of the radiation-sensitive resin composition, but is usually 3
The temperature is 0 to 200 ° C, preferably 50 to 170 ° C.

In the present invention, in order to maximize the potential of the radiation-sensitive resin composition, for example, Japanese Patent Publication No. 6-
As disclosed in Japanese Unexamined Patent Publication No. 12452, an organic or inorganic antireflection film can be formed on a substrate to be used, and the influence of basic impurities contained in an environmental atmosphere can be prevented. To prevent this, for example, JP-A-5-18
As disclosed in Japanese Patent No. 8598, a protective film may be provided on the resist film, or these techniques may be used in combination. Then, the exposed resist film is developed to form a predetermined resist pattern. Examples of the developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine. , Triethylamine,
Methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4. 3.0] -5-Nonene is preferably an alkaline aqueous solution in which at least one alkaline compound is dissolved. The concentration of the alkaline aqueous solution is usually
It is 10% by weight or less. In this case, if the concentration of the alkaline aqueous solution exceeds 10% by weight, the unexposed area may be dissolved in the developing solution, which is not preferable.

An organic solvent may be added to the developing solution containing the alkaline aqueous solution. Examples of the organic solvent include acetone, methyl ethyl ketone,
Linear, branched or cyclic ketones such as methyl i-butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone and 2,6-dimethylcyclohexanone; methyl alcohol, ethyl alcohol, n
-Propyl alcohol, i-propyl alcohol, n-
Alcohols such as butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane;
Esters such as ethyl acetate, n-butyl acetate, i-amyl acetate; aromatic hydrocarbons such as toluene and xylene;
Phenol, acetonylacetone, dimethylformamide, etc. can be mentioned. These organic solvents may be used alone or in admixture of two or more. The amount of the organic solvent used is 100 with respect to the alkaline aqueous solution.
Volume% or less is preferable. In this case, if the amount of the organic solvent used exceeds 100% by volume, the developability may be deteriorated and the undeveloped portion in the exposed area may increase. Further, an appropriate amount of a surfactant or the like can be added to the developer containing an alkaline aqueous solution. After developing with a developing solution composed of an alkaline aqueous solution, it is generally washed with water and dried.

[0169]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described more specifically below with reference to examples. However, the present invention is not limited to these examples. All parts are by weight unless otherwise specified. Each measurement / evaluation in Examples and Comparative Examples was carried out in the following manner. Mw: Tosoh Corp. GPC column (G2000HXL 2
, G3000HXL (1), G4000HXL (1), using a flow rate of 1.0 ml / min, an elution solvent of tetrahydrofuran, and a column temperature of 40 ° C. under the analysis conditions of gel permeation chromatography (GPC) using monodisperse polystyrene as a standard. It was measured. Radiation transmittance: The composition solution was applied onto quartz glass by spin coating and subjected to PB on a hot plate kept at 130 ° C. for 60 seconds to obtain a resist film having a film thickness of 0.34 μm from the absorbance at a wavelength of 193 nm. The radiation transmittance was calculated and used as a measure of transparency in the deep ultraviolet region.

Sensitivity: AR with a film thickness of 820Å on the wafer surface
Using C25 (manufactured by Brewer Science) film-formed silicon wafer (ARC25), each composition solution was applied onto a substrate by spin coating, and the conditions shown in Table 2 were applied on a hot plate. NiB ArF excimer laser exposure equipment (numerical aperture 0.5
5) was used to expose an ArF excimer laser through a mask pattern. Then, PEB was performed under the conditions shown in Table 2, followed by development with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 60 seconds, washing with water, and drying to form a positive resist pattern. did. At this time, the exposure amount for forming a line-and-space pattern (1L1S) having a line width of 0.16 μm with a line width of 1: 1 was set as the optimum exposure amount, and this optimum exposure amount was set as the sensitivity. Resolution: The dimension of the smallest resist pattern that can be resolved with the optimum exposure amount was defined as the resolution.

Dry etching resistance: PM was applied to a resist film having a film thickness of 0.5 μm formed by applying the composition solution onto a silicon wafer by spin coating and drying.
Using a dry etching system (Pinnacle8000) manufactured by T
The etching gas is CF ₄ , the gas flow rate is 75 sccm,
Dry etching was performed under the conditions of a pressure of 2.5 mTorr and an output of 2,500 W, the etching rate was measured, and the relative etching rate was evaluated by the relative value to the etching rate of the film formed from the resin used in Comparative Example 1. The smaller the etching rate, the better the dry etching resistance. Pattern shape: Bottom dimension L of a rectangular cross section of a line and space pattern (1L1S) with a line width of 0.16 μm
b and the upper side dimension La are measured with a scanning electron microscope,
When 0.85 ≦ La / Lb ≦ 1 is satisfied and the pattern shape is not tailed, the condition is “good”, and 0.85> L
When it was a / Lb or the pattern shape had a hem, it was defined as “poor”.

Mask pattern dependency: line width 0.16 μm
When the line and space pattern (1L1S) of No. 1 is exposed at the optimum exposure amount, the line width of the formed resist pattern is 1L / 10S pattern (0.16um line / 1. When the mask design dimension (0.16 μm) of 70 μm exceeds 70%, the condition is “good”, and when it is 70% or less, the condition is “defective”. If the exposure amount is intentionally increased / decreased by 1% with respect to the optimum exposure amount for resolving a line-and-space pattern (1L1S) with an exposure margin line width of 0.16 μm, the line width changes and the resolution also deteriorates. To do. When the line width obtained at that time is within ± 10% of the design line width of 0.16 μm, the range of the exposure amount is ± 10% or more of the optimum exposure amount, it is regarded as “good”, and the optimum The case of less than ± 10% with respect to the exposure amount was defined as “defective”.

Synthesis Example 1 The above formula (i-
59.65 g (30 mol%) of a compound represented by 1) (hereinafter referred to as “compound (i-1)”), a compound represented by the following formula (iii-1) (hereinafter referred to as “compound (iii- 1) ”.)
40.35 g (40 mol%) was dissolved in 150 ml of chlorobenzene to prepare a monomer solution. Apart from
Silver hexafluoroantimonate 3.62 g (10.5
(1 mmol) was dissolved in 150 ml of chlorobenzene, 1.39 g (3.76 mmol) of η3-allylpalladium chloride dimer was added over 30 minutes, and the precipitated silver chloride was filtered by a micropore filter medium. After removal, a catalyst solution was prepared. Then, the catalyst solution was added to the monomer solution and reacted for 36 hours. At this time, ¹ H-NMR analysis confirmed that there was no unreacted monomer. After that, the reaction solution was put into 2,000 g of methanol, the precipitated white powder was separated by filtration, and the washing operation of mixing with 400 g of methanol was performed twice, followed by filtration and drying at 50 ° C. for 17 hours, 68 g (yield 68% by weight) of a white powder resin was obtained. This resin has an Mw of 26,900, and the compound (i
-1) and the content of each repeating unit derived from the compound (iii-1) was 49.5 / 50.5 (mol%), which was a copolymer. This resin is referred to as resin (A-1).

[0174]

[Chemical formula 23]

Synthesis Example 2 A 1,000 ml three-necked flask was charged with the compound (i
-1) 51.32 g (30 mol%), compound (iii-1) 2
3.15 g (20 mol%), maleic anhydride 25.53
g (50 mol%) and 2-butanone (200 g) were added, and methyl azobisisovalerate (4.79 g) was added, followed by nitrogen purge for 30 minutes. Then, it was polymerized at 80 ° C. for 5 hours. After the completion of the polymerization, the reaction solution was cooled with water to 30 ° C. or lower, and then poured into 2,000 g of n-heptane, and the precipitated white powder was separated by filtration. After that, a washing operation of mixing the filtered white powder with 400 g of isopropanol was performed twice, and then filtered and dried at 50 ° C. for 17 hours to obtain 72 g (yield 72% by weight) of a white powder resin. It was
This resin has an Mw of 6,800 and has a compound (i-1)
The copolymer had a content of each repeating unit derived from the compound (iii-1) and maleic anhydride of 29.5 / 19.6 / 50.9 (mol%). This resin is referred to as resin (A-2).

Synthesis Example 3 50.44 g of a compound represented by the above formula (ii-1) in which R is a methyl group (hereinafter referred to as "compound (ii-1-1)")
(45 mol%), a compound represented by the following formula (iv-1) (hereinafter referred to as "compound (iv-1)") 49.56 g (55
(Mol%) was dissolved in 200 g of 2-butanone, and 3.73 g of methyl azobisisovalerate was further added to prepare a monomer solution. Separately, 1 containing 100 g of 2-butanone
A 3,000 ml three-necked flask was purged with nitrogen for 30 minutes, then heated to 80 ° C. with stirring, and the monomer solution was added dropwise using a dropping funnel at a rate of 10 ml / 5 minutes. Polymerization was carried out for 5 hours, with the start of dropping being the start of polymerization. After the polymerization is completed, the reaction solution is cooled with water to 30
After cooling to below ℃, it was put into 2,000 g of methanol, and the precipitated white powder was filtered off. After that, the washing operation of mixing the filtered white powder with 400 g of methanol is carried out in 2
After repeating, it is filtered and dried at 50 ° C for 17 hours.
71 g (yield 71% by weight) of a white powder resin was obtained. This resin had an Mw of 10,600 and a content of each repeating unit derived from the compound (ii-1-1) and the compound (iv-1) was 41.2 / 58.8 (mol%). It was a coalescence.
This resin is referred to as resin (A-3).

[0177]

[Chemical formula 24]

Synthesis Example 4 54.66 g (50 mol%) of compound (ii-1-1), 21.97 g (25 mol%) of compound (iv-1), the following formula (iv-2)
23.37 g (25 mol%) of the compound represented by the formula (hereinafter, referred to as “compound (iv-2)”) was added to 2-butanone 20.
It is dissolved in 0 g and further methyl azobisisovalerate 3.6
A monomer solution containing 4 g was prepared. Separately, a 1,000 ml three-necked flask containing 100 g of 2-butanone was purged with nitrogen for 30 minutes, and then stirred for 8 hours.
Heat to 0 ° C. and add the monomer solution using a dropping funnel, 1
It was added dropwise at a rate of 0 ml / 5 minutes. Polymerization was carried out for 5 hours, with the start of dropping being the start of polymerization. After the polymerization was completed, the reaction solution was water-cooled and cooled to 30 ° C. or lower, then, poured into 2,000 g of methanol, and the precipitated white powder was filtered off. Then, the filtered white powder was mixed with methanol 40
After performing a washing operation for mixing with 0 g twice, filtering and
After drying at 0 ° C. for 17 hours, 73 g of a white powder resin (yield 73% by weight) was obtained. This resin has Mw of 10,400
And the content of each repeating unit derived from compound (ii-1-1), compound (iv-1) and compound (iv-2) is 45.
It was a copolymer of 2 / 29.6 / 25.2 (mol%). This resin is designated as resin (A-4).

[0179]

[Chemical 25]

Synthesis Example 5 A 1,000 ml three-necked flask was charged with bicyclo.
[2.2.1] Hept-2-ene 7.04 g (15 mol%), maleic anhydride 7.33 g (15 mol%), compound (ii-1-1) 41.33 g (30 mol%), Compound (iv
-1) 44.30 g (40 mol%), 2-butanone 200
g, and then methyl azobisisovalerate 4.59 g
Was added and then purged with nitrogen for 30 minutes. Then 8
Polymerization was carried out at 0 ° C. for 5 hours. After completion of the polymerization, the reaction solution was cooled with water to 30 ° C. or lower, and then n-heptane 2,000 was used.
Then, the white powder deposited was filtered off. afterwards,
The washing operation of mixing the filtered white powder with 400 g of isopropanol was performed twice, and then filtered and filtered at 50 ° C. for 17 hours.
After drying for 67 hours, 67 g of a white powder resin (yield 67% by weight) was obtained. This resin has Mw of 7,200, and each repeating unit derived from bicyclo [2.2.1] hept-2-ene, maleic anhydride, compound (ii-1-1) and compound (iv-1). Content of 15.2 / 15.4 / 29.
It was a copolymer of 6 / 39.8 (mol%). This resin is referred to as resin (A-5).

Synthesis Example 6 In a 1,000 ml three-necked flask, the compound (i
-1) 61.90 g (40 mol%), maleic anhydride 1
8.48 g (40 mol%), a compound represented by the following formula (iv-3) (hereinafter referred to as "compound (iv-3)") 19.6
2 g (20 mol%) and 200 g of 2-butanone were added, and further 4.34 g of methyl azobisisovalerate was added, followed by nitrogen purge for 30 minutes. Then, it was polymerized at 80 ° C. for 5 hours. After the completion of the polymerization, the reaction solution was cooled with water to 30 ° C. or lower, and then poured into 2,000 g of n-heptane, and the precipitated white powder was separated by filtration. After that, a washing operation of mixing the filtered white powder with 400 g of isopropanol was carried out twice, followed by filtering and drying at 50 ° C. for 17 hours to obtain 78 g (yield 78% by weight) of a white powder resin. It was
This resin has an Mw of 5,200 and has a compound (i-1)
The content of each repeating unit derived from maleic anhydride and the compound (iv-3) was 39.6 / 40.2 / 20.2 (mol%), which was a copolymer. This resin is referred to as resin (A-6).

[0182]

[Chemical formula 26]

Examples 1 to 6 Various evaluations were performed on each composition solution containing the components shown in Table 1. The evaluation results are shown in Table 3. In Table 1, the components other than the resins (A-1) to (A-6) are as follows. Acid generator (B) B-1: 1- (4-n-butoxynaphthalen-1-yl)
Tetrahydrothiophenium nonafluoro-n-butane sulfonate acid diffusion control agent (C) C-1: 2-phenylbenzimidazole solvent (E) E-1: propylene glycol monomethyl ether acetate

[0184]

[Table 1]

[0185]

[Table 2]

[0186]

[Table 3]

[0187]

Industrial Applicability The radiation-sensitive resin composition of the present invention contains actinic radiation, particularly ArF excimer laser (wavelength: 193n).
As a chemically amplified resist sensitive to deep ultraviolet rays represented by m), it is highly transparent to radiation and has excellent basic physical properties as a resist such as sensitivity, resolution, dry etching resistance, and pattern shape, and the mask pattern can be changed. And the fluctuation value of the line width with respect to the increase or decrease of the exposure amount is small,
Further, the developability and the adhesiveness to the substrate are also good, and it can be used very suitably for the production of semiconductor devices which are expected to be further miniaturized in the future.

Continued front page    (72) Inventor Isao Nishimura             2-11-21 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. (72) Inventor Eiichi Kobayashi             2-11-21 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. F-term (reference) 2H025 AA01 AA02 AA03 AA09 AB16                       AC04 AC08 AD03 BE00 BE10                       BG00 CB08 CB10 CB13 CB14                       CB41 CB43 CB45                 4J100 AK32T AL08Q AL08S AR09P                       AR11P AR11R BA03R BA03S                       BA15P BC09P BC09Q BC09R                       BC09S BC53R BC53S CA03                       CA04 CA05 CA06 FA03 JA38

Claims (3)

[Claims] 1. An (A) alkali-insoluble or sparingly alkali-soluble having at least one selected from the group of repeating units represented by the following general formula (I) and repeating units represented by the following general formula (II). A radiation-sensitive resin composition comprising a resin, which becomes alkali-soluble by the action of an acid, and (B) a radiation-sensitive acid generator. [Chemical 1] [In the general formula (I), each R ¹ is independently a linear or branched alkyl group having 1 to 6 carbon atoms, or 1 carbon atom.
To a linear or branched alkoxyl group having 6 to 6 carbon atoms, a linear or branched alkoxycarbonyl group having 2 to 6 carbon atoms, or a monovalent hydrocarbon group having 4 to 20 carbon atoms having an alicyclic structure, or The derivative is shown and R ² has 1 carbon atom.
To a linear or branched alkyl group having 20 to 20 carbon atoms, or a monovalent hydrocarbon group having 4 to 20 carbon atoms having an alicyclic structure or a derivative thereof, X ¹ is a methylene group, and 2 carbon atoms.
To a linear or branched alkylene group having from 9 to 9 or a divalent hydrocarbon group having 4 to 20 carbon atoms and having an alicyclic structure or a derivative thereof, and n is an integer from 0 to 2. In the general formula (II), each R ³ independently has 1 to 1 carbon atoms.
6 straight-chain or branched alkyl group, having 1 to 6 carbon atoms
A linear or branched alkoxyl group having 2 to 2 carbon atoms
A linear or branched alkoxycarbonyl group of 6,
Or a monovalent hydrocarbon group having 4 to 20 carbon atoms having an alicyclic structure or a derivative thereof, wherein R ⁴ is 1 to 2 carbon atoms
0 represents a straight-chain or branched alkyl group having 0 to 4 carbon atoms, or a monovalent hydrocarbon group having 4 to 20 carbon atoms having an alicyclic structure or a derivative thereof, and X ² represents a methylene group or 2 to 9 carbon atoms.
Represents a linear or branched alkylene group, or a divalent hydrocarbon group having 4 to 20 carbon atoms having an alicyclic structure or a derivative thereof, and R ⁵ represents a hydrogen atom, a methyl group, or 1 to 4 carbon atoms. Is a linear or branched hydroxyalkyl group or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms. ] 2. The resin as the component (A) further comprises a repeating unit represented by the following general formula (III) and a general formula (I
The radiation-sensitive resin composition according to claim 1, which has at least one selected from the group of repeating units represented by V). [Chemical 2] [In the general formula (III), Z ¹ represents a hydrogen atom or a monovalent organic group, and m is an integer of 0 to 2. General formula (IV)
In, Z ² represents a hydrogen atom or a monovalent organic group,
R ⁶ is a hydrogen atom, a methyl group, a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms
4 represents a linear or branched fluorinated alkyl group. ] 3. The radiation-sensitive resin composition according to claim 1, wherein the resin as the component (A) further has a repeating unit derived from maleic anhydride.