JP6271650B2 - Polymer compounds, compounds - Google Patents

Description

  The present invention relates to a polymer compound useful as a resist composition and a compound useful as a raw material for the polymer compound.

In lithography technology, for example, a resist film made of a resist material is formed on a substrate, and the resist film is selectively exposed and developed to form a resist pattern having a predetermined shape on the resist film. The process to perform is performed. A resist material in which the exposed portion of the resist film changes to a property that dissolves in the developer is referred to as a positive type, and a resist material that changes to a property in which the exposed portion does not dissolve in the developer is referred to as a negative type.
In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, pattern miniaturization has been rapidly progressing due to advances in lithography technology. As a technique for miniaturization, the exposure light source is generally shortened in wavelength (increased energy). Specifically, conventionally, ultraviolet rays typified by g-line and i-line have been used, but at present, mass production of semiconductor elements using a KrF excimer laser or an ArF excimer laser has started. Further, studies have been made on EUV (extreme ultraviolet), EB (electron beam), X-rays and the like having shorter wavelengths (higher energy) than these excimer lasers.

Resist materials are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing a pattern with fine dimensions.
Conventionally, as a resist material satisfying such requirements, there is a chemically amplified resist composition containing a base material component whose solubility in a developing solution is changed by the action of an acid and an acid generator component that generates an acid upon exposure. It is used. For example, when the developer is an alkali developer (alkaline development process), the positive chemically amplified resist composition includes a resin component (base resin) whose solubility in an alkali developer is increased by the action of an acid, an acid Those containing a generator component are generally used. When a resist film formed using such a resist composition is selectively exposed at the time of resist pattern formation, an acid is generated from the acid generator component in the exposed portion, and the polarity of the base resin increases due to the action of the acid. Thus, the exposed portion becomes soluble in the alkaline developer. Therefore, by performing alkali development, a positive pattern in which an unexposed portion remains as a pattern is formed. On the other hand, when such a chemically amplified resist composition is applied to a solvent development process using a developer containing an organic solvent (organic developer), the organic development is relatively increased when the polarity of the base resin increases. Since the solubility in the solution is lowered, the unexposed portion of the resist film is dissolved and removed by the organic developer, and a negative resist pattern in which the exposed portion remains as a pattern is formed. Such a solvent development process for forming a negative resist pattern is sometimes referred to as a negative development process (for example, Patent Document 1).

The base resin of the chemically amplified resist composition generally contains a plurality of structural units in order to improve lithography characteristics and the like. For example, in the case of a resin component whose solubility in an alkaline developer is increased by the action of an acid, a structural unit having an acid-decomposable group that is decomposed by the action of an acid generated from an acid generator and increases in polarity is used. However, a structural unit having a lactone-containing cyclic group, a structural unit having a polar group such as a hydroxyl group, and the like are used (see, for example, Patent Document 2).
In recent years, with the development and practical application of new lithography techniques such as immersion exposure, various studies have been conducted on base resins. For example, in Patent Documents 3 to 4, a polymer containing a monomer unit containing a lactone skeleton, which is represented by a specific general formula, is used as a polymer compound for a chemically amplified resist, particularly as a polymer compound used in immersion exposure. Compounds are disclosed.

JP 2009-025723 A JP 2003-241385 A JP 2010-150447 A JP 2010-150448 A

In the future, with further advancement of lithography technology and further miniaturization of resist patterns, further improvements in various lithography characteristics are desired for resist materials.
For example, not only sensitivity and resolution, but also exposure margin (EL), line width roughness (LWR), mask reproducibility, and the like are required.
Further, when a resist pattern is formed using a chemically amplified resist composition containing a polymer compound having a structural unit having a lactone-containing cyclic group as a base resin, the resist film is subjected to post-exposure baking. The film thickness may decrease. This decrease in film thickness is particularly likely to occur in the exposed area. Further, the above-described negative development process has a problem that the film thickness of the exposed portion remaining as a resist pattern is reduced during development with an organic developer. Reduction in film thickness (film shrinkage) due to post-exposure baking or development causes etching failure when the substrate is etched using the formed resist pattern as a mask, and thus improvement is required.

  The present invention has been made in view of the above circumstances, and is a resist composition excellent in lithography characteristics, a resist pattern forming method using the resist composition, a polymer compound useful for the resist composition, It aims at providing a compound useful as a raw material of a high molecular compound.

  The first aspect of the present invention is a polymer compound having a structural unit (a0) represented by the following general formula (a0).

［式中、Ａ”は、酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、Ｒ^１は、下記一般式（ａ２−ｒ−４）、（ａ２−ｒ−５）もしくは（ａ２−ｒ−７）のいずれかで表されるラクトン含有環式基、−ＳＯ_２−含有環式基またはカーボネート含有環式基であり、Ｗ^２は、Ｒ ^２ ’−Ｌ ^１ −で表される基から重合反応により形成される基である。前記Ｒ ^２ ’は、エチレン性二重結合を含み、置換基を有していてもよい炭化水素基であり、前記Ｌ ^１ は、ヘテロ原子を含む２価の連結基または単結合である。］

[Wherein, A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and R ¹ represents the following general formula (a2-r-4) , (A2-r-5) or (a2-r-7), a lactone-containing cyclic group, an —SO ₂ -containing cyclic group, or a carbonate-containing cyclic group, and W ² is A group formed by a polymerization reaction from a group represented by R ² ′ -L ¹ —, wherein R ² ′ is an optionally substituted hydrocarbon group containing an ethylenic double bond; And L ¹ is a divalent linking group containing a hetero atom or a single bond. ]

［式中、Ｒａ’^２１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり；Ｒ”は水素原子またはアルキル基であり；Ａ”は酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、ｍ’は０または１である。］

[Wherein, Ra ′ ²¹ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR ″, —OC (═O) R ″, a hydroxyalkyl group or a cyano group. Yes; R ″ is a hydrogen atom or an alkyl group; A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and m ′ is 0 or 1 It is. ]

  The second aspect of the present invention is a compound represented by the following general formula (I).

［式中、Ａ”は、酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、Ｒ^１は、下記一般式（ａ２−ｒ−４）、（ａ２−ｒ−５）もしくは（ａ２−ｒ−７）のいずれかで表されるラクトン含有環式基、−ＳＯ_２−含有環式基またはカーボネート含有環式基であり、Ｒ^２は、Ｒ ^２ ’−Ｌ ^１ −で表される基である。前記Ｒ ^２ ’は、エチレン性二重結合を含み、置換基を有していてもよい炭化水素基であり、前記Ｌ ^１ は、ヘテロ原子を含む２価の連結基または単結合である。］

[Wherein, A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and R ¹ represents the following general formula (a2-r-4) A lactone-containing cyclic group represented by any one of (a2-r-5) and (a2-r-7), an —SO ₂ -containing cyclic group, or a carbonate-containing cyclic group, and R ² is R ² '-L 1 ^-. a group represented by the R ^2' contains an ethylenic double bond, a hydrocarbon group which may have a substituent group, wherein L ¹ is heteroaryl A divalent linking group containing atoms or a single bond. ]

［式中、Ｒａ’^２１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり；Ｒ”は水素原子またはアルキル基であり；Ａ”は酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、ｍ’は０または１である。］

[Wherein, Ra ′ ²¹ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR ″, —OC (═O) R ″, a hydroxyalkyl group or a cyano group. Yes; R ″ is a hydrogen atom or an alkyl group; A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and m ′ is 0 or 1 It is. ]

  A third aspect of the present invention is a compound represented by the following general formula (II).

［式中、Ａ”は、酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、Ｒ^１は、下記一般式（ａ２−ｒ−２）〜（ａ２−ｒ−７）のいずれかで表されるラクトン含有環式基、−ＳＯ_２−含有環式基またはカーボネート含有環式基である。］

[Wherein, A ″ represents an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and R ¹ represents the following general formula (a2-r-2) A lactone-containing cyclic group, an —SO ₂ -containing cyclic group, or a carbonate-containing cyclic group represented by any one of (a2-r-7)]

［式中、Ｒａ’^２１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり；Ｒ”は水素原子またはアルキル基であり；Ａ”は酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、ｍ’は０または１である。］

[Wherein, Ra ′ ²¹ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR ″, —OC (═O) R ″, a hydroxyalkyl group or a cyano group. Yes; R ″ is a hydrogen atom or an alkyl group; A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and m ′ is 0 or 1 It is. ]

  According to the present invention, a resist composition having excellent lithography properties, a resist pattern forming method using the resist composition, a polymer compound useful for the resist composition, a compound useful as a raw material for the polymer compound, Can be provided.

In the present specification and claims, “aliphatic” is a relative concept with respect to aromatics, and is defined to mean groups, compounds, etc. that do not have aromaticity.
Unless otherwise specified, the “alkyl group” includes linear, branched and cyclic monovalent saturated hydrocarbon groups.
The “alkylene group” includes linear, branched, and cyclic divalent saturated hydrocarbon groups unless otherwise specified. The same applies to the alkyl group in the alkoxy group.
The “halogenated alkyl group” is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
“Fluorinated alkyl group” or “fluorinated alkylene group” refers to a group in which part or all of the hydrogen atoms of an alkyl group or alkylene group are substituted with fluorine atoms.
“Structural unit” means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
“A structural unit derived from an acrylate ester” means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.
“Acrylic acid ester” is a compound in which the hydrogen atom at the carboxy group terminal of acrylic acid (CH ₂ ═CH—COOH) is substituted with an organic group.
In the acrylate ester, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The substituent (R ^α ) for substituting the hydrogen atom bonded to the α-position carbon atom is an atom or group other than a hydrogen atom, such as an alkyl group having 1 to 5 carbon atoms or a halogenated group having 1 to 5 carbon atoms. An alkyl group etc. are mentioned. In addition, itaconic acid diesters in which the substituent (R ^α ) is substituted with a substituent containing an ester bond, and α-hydroxyacrylic esters in which the substituent (R ^α ) is substituted with a hydroxyalkyl group or a group with a modified hydroxyl group thereof Shall be included. The α-position carbon atom of the acrylate ester is a carbon atom to which a carbonyl group of acrylic acid is bonded unless otherwise specified.
Hereinafter, an acrylate ester in which a hydrogen atom bonded to the α-position carbon atom is substituted with a substituent may be referred to as an α-substituted acrylate ester. Further, the acrylate ester and the α-substituted acrylate ester may be collectively referred to as “(α-substituted) acrylate ester”.
“Structural unit derived from acrylamide” means a structural unit formed by cleavage of the ethylenic double bond of acrylamide.
In acrylamide, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, and one or both of the hydrogen atoms of the amino group of acrylamide may be substituted with a substituent. The α-position carbon atom of acrylamide is a carbon atom to which the carbonyl group of acrylamide is bonded unless otherwise specified.
As the substituent for substituting the hydrogen atom bonded to the α-position carbon atom of acrylamide, the same as the substituent (substituent (R ^A )) given as the α-position substituent in the α-substituted acrylate ester may be used. Can be mentioned.
“A structural unit derived from hydroxystyrene or a hydroxystyrene derivative” means a structural unit formed by cleavage of an ethylenic double bond of hydroxystyrene or a hydroxystyrene derivative.
“Hydroxystyrene derivative” is a concept including those in which the hydrogen atom at the α-position of hydroxystyrene is substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. The derivatives include those in which the hydrogen atom at the α-position may be substituted with a substituent, the hydrogen atom of the hydroxyl group of hydroxystyrene substituted with an organic group, and the hydrogen atom at the α-position substituted with a substituent. Examples include those in which a substituent other than a hydroxyl group is bonded to a good benzene ring of hydroxystyrene. The α-position (α-position carbon atom) means a carbon atom to which a benzene ring is bonded unless otherwise specified.
Examples of the substituent for substituting the hydrogen atom at the α-position of hydroxystyrene include the same substituents as those mentioned as the substituent at the α-position in the α-substituted acrylic ester.
The “structural unit derived from vinyl benzoic acid or a vinyl benzoic acid derivative” means a structural unit configured by cleavage of an ethylenic double bond of vinyl benzoic acid or a vinyl benzoic acid derivative.
The “vinyl benzoic acid derivative” is a concept including a compound in which the hydrogen atom at the α-position of vinyl benzoic acid is substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. These derivatives include those obtained by substituting the hydrogen atom of the carboxy group of vinyl benzoic acid with an organic group, which may be substituted with a hydrogen atom at the α-position, and the hydrogen atom at the α-position with a substituent. Examples thereof include those in which a substituent other than a hydroxyl group and a carboxy group is bonded to the benzene ring of vinyl benzoic acid. The α-position (α-position carbon atom) means a carbon atom to which a benzene ring is bonded unless otherwise specified.
“Styrene” is a concept that includes styrene and those in which the α-position hydrogen atom of styrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group.
“Structural unit derived from styrene” and “structural unit derived from styrene derivative” mean a structural unit formed by cleavage of an ethylenic double bond of styrene or a styrene derivative.
The alkyl group as a substituent at the α-position is preferably a linear or branched alkyl group, specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group). , N-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.
Specific examples of the halogenated alkyl group as the substituent at the α-position include groups in which part or all of the hydrogen atoms of the above-mentioned “alkyl group as the substituent at the α-position” are substituted with a halogen atom. It is done. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
Specific examples of the hydroxyalkyl group as a substituent at the α-position include a group in which part or all of the hydrogen atoms of the “alkyl group as the substituent at the α-position” are substituted with a hydroxyl group. 1-5 are preferable and, as for the number of the hydroxyl groups in this hydroxyalkyl group, 1 is the most preferable.
When it is described as “may have a substituent”, when a hydrogen atom (—H) is substituted with a monovalent group, and when a methylene group (—CH ₂ —) is substituted with a divalent group And both.
“Exposure” is a concept including general irradiation of radiation.

≪Resist composition≫
The resist composition of the present invention is a resist composition that generates an acid upon exposure and changes its solubility in a developer by the action of an acid, and is a base material component that changes its solubility in a developer by the action of an acid ( A) (hereinafter referred to as “component (A)”).
When a resist film is formed using such a resist composition and the resist film is selectively exposed, an acid is generated in the exposed portion, and the action of the acid causes the solubility of the component (A) in the developer. On the other hand, since the solubility of the component (A) in the developer does not change in the unexposed area, a difference in solubility in the developer occurs between the exposed area and the unexposed area. Therefore, when the resist film is developed, when the resist composition is positive, the exposed portion is dissolved and removed to form a positive resist pattern. When the resist composition is negative, the unexposed portion is dissolved and removed. As a result, a negative resist pattern is formed.
In this specification, a resist composition in which an exposed portion is dissolved and removed to form a positive resist pattern is referred to as a positive resist composition, and a resist composition that forms a negative resist pattern in which an unexposed portion is dissolved and removed. Is referred to as a negative resist composition.
The resist composition of the present invention may be a positive resist composition or a negative resist composition.
In addition, the resist composition of the present invention may be used for an alkali development process using an alkali developer for development processing at the time of forming a resist pattern, and a developer (organic developer) containing an organic solvent is used for the development processing. It may be for the solvent development process used.

The resist composition of the present invention has an acid generating ability to generate an acid upon exposure, and the (A) component may generate an acid upon exposure, and the additive component blended separately from the (A) component May generate an acid upon exposure.
Specifically, the resist composition of the present invention comprises:
(1) It may contain an acid generator component (B) (hereinafter referred to as “component (B)”) that generates an acid upon exposure;
(2) The component (A) may be a component that generates an acid upon exposure;
(3) The component (A) is a component that generates an acid upon exposure, and may further contain a component (B).
That is, in the case of the above (2) and (3), the component (A) is a “base material component that generates an acid upon exposure and changes its solubility in a developer due to the action of the acid”. When the component (A) is a base material component that generates an acid upon exposure and the solubility in the developer changes due to the action of the acid, the later-described component (A1) generates an acid upon exposure, and the acid A polymer compound whose solubility in a developing solution is changed by the action is preferable. As such a polymer compound, a resin having a structural unit that generates an acid upon exposure can be used. A well-known thing can be used as a structural unit which generate | occur | produces an acid by exposure.
In the resist composition of the present invention, the case (1) above is particularly preferable.

<(A) component>
In the present invention, the “base component” is an organic compound having a film forming ability, and preferably an organic compound having a molecular weight of 500 or more is used. When the molecular weight of the organic compound is 500 or more, the film-forming ability is improved and a nano-level resist pattern is easily formed.
Organic compounds used as the base material component are roughly classified into non-polymers and polymers.
As the non-polymer, those having a molecular weight of 500 or more and less than 4000 are usually used. Hereinafter, the “low molecular compound” refers to a non-polymer having a molecular weight of 500 or more and less than 4000.
As the polymer, those having a molecular weight of 1000 or more are usually used. Hereinafter, the term “resin” refers to a polymer having a molecular weight of 1000 or more.
As the molecular weight of the polymer, a polystyrene-reduced mass average molecular weight by GPC (gel permeation chromatography) is used.
As the component (A), a resin may be used, a low molecular compound may be used, or these may be used in combination.
Component (A) may have increased solubility in a developer due to the action of an acid, or may decrease solubility in a developer due to the action of an acid.
In the present invention, the component (A) may generate an acid upon exposure.

When the resist composition of the present invention is a “negative resist composition for an alkali development process” that forms a negative resist pattern in an alkali development process, or a “solvent development process that forms a positive resist pattern in a solvent development process” In the case of the “positive resist composition for use”, the component (A) is preferably a substrate component (A-2) (hereinafter referred to as “component (A-2)”) that is soluble in an alkaline developer. Furthermore, a crosslinking agent component is blended. In such a resist composition, when an acid is generated by exposure, the acid acts to cause crosslinking between the component (A-2) and the crosslinking agent component, resulting in a decrease in solubility in an alkaline developer (organic). The solubility in the system developer increases). Therefore, in the formation of a resist pattern, when a resist film obtained by coating the resist composition on a support is selectively exposed, the exposed portion is hardly soluble in an alkali developer (to an organic developer). On the other hand, the unexposed area remains soluble (almost insoluble in the organic developer) while remaining undissolved in the alkali developer, so that a negative resist pattern can be formed by developing with an alkali developer. . At this time, if an organic developer is used as the developer, a positive resist pattern can be formed.
As the component (A-2), a resin that is soluble in an alkali developer (hereinafter referred to as “alkali-soluble resin”) is used.
Examples of the alkali-soluble resin include α- (hydroxyalkyl) acrylic acid or α- (hydroxyalkyl) acrylic acid alkyl ester (preferably having 1 to 5 carbon atoms) disclosed in, for example, JP-A-2000-206694. A resin having a unit derived from at least one selected from alkyl ester); a hydrogen atom bonded to a carbon atom at the α-position having a sulfonamide group, which is disclosed in US Pat. No. 6,949,325, is substituted with a substituent. Acrylic resin or polycycloolefin resin which may be contained; disclosed in US Pat. No. 6,949,325, Japanese Patent Application Laid-Open No. 2005-336252, Japanese Patent Application Laid-Open No. 2006-317803, containing fluorinated alcohol, and α-position carbon The hydrogen atom bonded to the atom may be substituted with a substituent. Le resin; Japanese Patent disclosed in 2006-259582, JP-polycycloolefin resins having fluorinated alcohol, with minimal swelling can formation of a satisfactory resist pattern.
The α- (hydroxyalkyl) acrylic acid is a hydrogen atom bonded to the α-position carbon atom to which the carboxy group is bonded, among the acrylic acid in which the hydrogen atom bonded to the α-position carbon atom may be substituted with a substituent. One or both of acrylic acid having an atom bonded thereto and α-hydroxyalkylacrylic acid having a hydroxyalkyl group (preferably a hydroxyalkyl group having 1 to 5 carbon atoms) bonded to the α-position carbon atom are shown. .
As the crosslinking agent component, for example, it is usually preferable to use an amino crosslinking agent such as glycoluril having a methylol group or an alkoxymethyl group, a melamine crosslinking agent, or the like because a good resist pattern with less swelling can be formed. It is preferable that the compounding quantity of a crosslinking agent component is 1-50 mass parts with respect to 100 mass parts of alkali-soluble resin.

When the resist composition of the present invention is a “positive resist composition for an alkali development process” in which a positive pattern is formed in an alkali development process and a negative pattern is formed in a solvent development process, or a negative in a solvent development process. In the case of a “negative resist composition for solvent development process” that forms a mold resist pattern, as the component (A), the base component (A-1) (hereinafter referred to as “(A− 1) Component ")) is used. By using the component (A-1), since the polarity of the base material component changes before and after exposure, a good development contrast can be obtained not only in the alkali development process but also in the solvent development process.
When an alkali development process is applied, the component (A-1) is hardly soluble in an alkali developer before exposure. When an acid is generated by exposure, the polarity is increased by the action of the acid, and the alkali development is performed. The solubility in the liquid is increased. Therefore, in the formation of a resist pattern, when a resist film obtained by applying the resist composition on a support is selectively exposed, the exposed portion changes from slightly soluble to soluble in an alkaline developer. Since the unexposed portion remains hardly soluble in alkali and does not change, a positive pattern can be formed by alkali development.
On the other hand, when a solvent development process is applied, the component (A-1) is highly soluble in an organic developer before exposure, and when an acid is generated by exposure, the component is highly polar due to the action of the acid. The solubility in an organic developer is reduced. Therefore, in the formation of the resist pattern, when the resist film obtained by applying the resist composition on the support is selectively exposed, the exposed portion changes from soluble to poorly soluble in an organic developer. On the other hand, since the unexposed portion remains soluble and does not change, by developing with an organic developer, a contrast can be provided between the exposed portion and the unexposed portion, and a negative pattern can be formed.
In the present invention, the component (A) is preferably the component (A-1).

[Polymer Compound (A1)]
(A) component contains the high molecular compound (A1) (henceforth (A1) component) which has the following structural unit (a0).
The component (A1) is preferably the component (A-1).

(Structural unit (a0))
The structural unit (a0) is a structural unit represented by the following general formula (a0).
The structural unit (a0) has R ¹ (lactone-containing cyclic group, —SO ₂ — containing cyclic group or carbonate-containing cyclic group) at the terminal, and between W ² and R ¹ , “— By having the structure of “O-specific lactone-containing cyclic group —C (═O) —O—”, it has three-dimensional bulkiness and high polarity. Thereby, the adhesiveness of the resist film to the substrate, the affinity with a developer containing water such as an alkaline developer, and the like are improved, and the lithography properties are improved. In addition, the problem of film thickness reduction (film shrinkage) after post-exposure baking (PEB) or after development is improved, and a negative pattern can be formed with a high residual film rate even in a solvent development process, for example.

［式中、Ａ”は、酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、Ｒ^１は、ラクトン含有環式基、−ＳＯ_２−含有環式基またはカーボネート含有環式基であり、Ｗ^２は、重合性基を含む基から重合反応により形成される基である。］

[Wherein, A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and R ¹ represents a lactone-containing cyclic group, —SO ₂ — Containing cyclic group or carbonate-containing cyclic group, and W ² is a group formed by a polymerization reaction from a group containing a polymerizable group.]

In formula (a0), A ″ represents an alkylene group having 1 to 5 carbon atoms, oxygen atom or sulfur atom which may contain an oxygen atom (—O—) or a sulfur atom (—S—). The alkylene group having 1 to 5 carbon atoms is preferably a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include a group in which —O— or —S— is interposed between the terminal or carbon atoms of the alkylene group, such as —O—CH _{2. -, - CH 2 -O-CH} 2 -, - S-CH 2 -, - CH 2 -S-CH 2 - , and the like. A ″ is preferably an alkylene group having 1 to 5 carbon atoms or —O—, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.

In formula (a0), R ¹ is a lactone-containing cyclic group, an —SO ₂ — containing cyclic group, or a carbonate-containing cyclic group.
The “lactone-containing cyclic group” refers to a cyclic group containing a ring (lactone ring) containing —O—C (═O) — in the ring skeleton. The lactone ring is counted as the first ring. When only the lactone ring is present, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of the structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.
The lactone-containing cyclic group for R ¹ is not particularly limited, and any lactone-containing cyclic group can be used. Specific examples include groups represented by the following general formulas (a2-r-1) to (a2-r-7). In addition, in this specification, * mark in a formula shows a bond.

［式中、Ｒａ’^２１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり；Ｒ”は水素原子またはアルキル基であり；Ａ”は酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、ｎ’は０〜２の整数であり、ｍ’は０または１である。］

[Wherein, Ra ′ ²¹ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR ″, —OC (═O) R ″, a hydroxyalkyl group or a cyano group. Yes; R ″ is a hydrogen atom or an alkyl group; A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and n ′ is 0 to 2 And m ′ is 0 or 1. ]

In the general formulas (a2-r-1) to (a2-r-7), A ″ is the same as A ″ in the general formula (a0).
The alkyl group in ra ^'21, preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a hexyl group. Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.
The alkoxy group in the ra ^'21, preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, the group couple | bonded with the oxygen atom (-O-) to the alkyl group quoted as the alkyl group as the said substituent is mentioned.
Examples of the halogen atom in Ra ′ ²¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
Examples of the halogenated alkyl group for Ra ′ ²¹ include groups in which part or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.
In —COOR ″ and —OC (═O) R ″ in Ra ′ ²¹ , R ″ is a hydrogen atom or an alkyl group.
The alkyl group for R ″ may be linear, branched or cyclic, and preferably has 1 to 15 carbon atoms.
When R ″ is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably a methyl group or an ethyl group. preferable.
When R ″ is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, a fluorine atom Alternatively, one or more hydrogen atoms are removed from a polycycloalkane such as a monocycloalkane, bicycloalkane, tricycloalkane, or tetracycloalkane, which may or may not be substituted with a fluorinated alkyl group. More specifically, one or more hydrogen atoms are removed from a monocycloalkane such as cyclopentane or cyclohexane, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane. Group.
The hydroxyalkyl group in Ra ′ ²¹ is preferably one having 1 to 6 carbon atoms. Specifically, at least one hydrogen atom of the alkyl group mentioned as the alkyl group as the substituent is substituted with a hydroxyl group. Groups.

  Specific examples of groups represented by general formulas (a2-r-1) to (a2-r-7) are given below.

The “—SO ₂ -containing cyclic group” refers to a cyclic group containing a ring containing —SO ₂ — in the ring skeleton, specifically, the sulfur atom (S) in —SO ₂ — is It is a cyclic group that forms part of the ring skeleton of the cyclic group. The ring containing —SO ₂ — in the ring skeleton is counted as the first ring, and when it is only the ring, it is a monocyclic group, and when it has another ring structure, it is a polycyclic group regardless of the structure. Called. The —SO ₂ — containing cyclic group may be monocyclic or polycyclic.
-SO ₂ - containing cyclic group, in particular, -O-SO ₂ - within the ring skeleton cyclic group containing, i.e. -O-SO ₂ - -O-S- medium is a part of the ring skeleton A cyclic group containing a sultone ring to be formed is preferable.
More specifically, examples of the —SO ₂ -containing cyclic group include groups represented by the following general formulas (a5-r-1) to (a5-r-4).

［式中、Ｒａ’^５１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり；Ｒ”は水素原子またはアルキル基であり；Ａ”は酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、ｎ’は０〜２の整数である。］

[Wherein, Ra ′ ⁵¹ independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR ″, —OC (═O) R ″, a hydroxyalkyl group or a cyano group. Yes; R ″ is a hydrogen atom or an alkyl group; A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and n ′ is 0 to 2 Is an integer. ]

In the general formulas (a5-r-1) to (a5-r-4), A ″ is the same as A ″ in the general formula (a0).
As the alkyl group, alkoxy group, halogen atom, halogenated alkyl group, —COOR ″, —OC (═O) R ″, and hydroxyalkyl group in Ra ′ ⁵¹ , the above general formulas (a2-r-1) to ( a2-r-7) as in the same as those exemplified in the description of the Ra ^'21 of the like.

  Specific examples of groups represented by general formulas (a5-r-1) to (a5-r-4) are given below. “Ac” in the formula represents an acetyl group.

The “carbonate-containing cyclic group” refers to a cyclic group containing a ring (carbonate ring) containing —O—C (═O) —O— in the ring skeleton. When the carbonate ring is counted as the first ring, the carbonate ring alone is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of the structure. The carbonate-containing cyclic group may be a monocyclic group or a polycyclic group.
The carbonate ring-containing cyclic group for R ¹ is not particularly limited, and any one can be used. Specific examples include groups represented by the following general formulas (ax3-r-1) to (ax3-r-3).

［式中、Ｒａ’^ｘ３１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり；Ｒ”は水素原子またはアルキル基であり；Ａ”は酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子でありｑ’は０または１である。］

[ ^Wherein , Ra ′ ^x31 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR ″, —OC (═O) R ″, a hydroxyalkyl group or a cyano group. Yes; R ″ is a hydrogen atom or an alkyl group; A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and q ′ is 0 or 1. is there. ]

In the general formulas (ax3-r-1) to (ax3-r-3), A ″ is the same as A ″ in the general formula (a0).
As the alkyl group, alkoxy group, halogen atom, halogenated alkyl group, —COOR ″, —OC (═O) R ″, and hydroxyalkyl group in Ra ′ ³¹ , the above general formulas (a2-r-1) to ( a2-r-7) as in the same as those exemplified in the description of the Ra ^'21 of the like.

  Specific examples of groups represented by general formulas (ax3-r-1) to (ax3-r-3) are given below.

Among them, R ¹ is preferably a lactone-containing cyclic group or an —SO ₂ — containing cyclic group, and the general formula (a2-r-1), (a2-r-2) or (a5-r— 1) is preferable, and the chemical formulas (r-lc-1-1) to (r-lc-1-7), (r-lc-2-1) to (r-lc-2-13) are preferable. ), (R-sl-1-1), or (r-sl-1-18) is more preferred.

In formula (a0), W ² is a group formed by a polymerization reaction from a group containing a polymerizable group.
The “polymerizable group” is a group that allows the compound having the polymerizable group to be polymerized by radical polymerization or the like, and refers to a group including a multiple bond between carbon atoms such as an ethylenic double bond. .
As the polymerizable group, for example, vinyl group, allyl group, acryloyl group, methacryloyl group, fluorovinyl group, difluorovinyl group, trifluorovinyl group, difluorotrifluoromethylvinyl group, trifluoroallyl group, perfluoroallyl group, Trifluoromethylacryloyl group, nonylfluorobutylacryloyl group, vinyl ether group, fluorine-containing vinyl ether group, allyl ether group, fluorine-containing allyl ether group, styryl group, vinyl naphthyl group, fluorine-containing styryl group, fluorine-containing vinyl naphthyl group, norbornyl group , Fluorine-containing norbornyl group, silyl group and the like.

The group containing a polymerizable group in W ² may be a group composed only of a polymerizable group, or may be a group composed of a polymerizable group and another group other than the polymerizable group. .
Examples of the group containing a polymerizable group, R 2 ^-L 1 - in ^the Formula, R ² comprises an ethylenic double bond, a hydrocarbon group which may have a substituent, L ¹ is, A divalent linking group containing a hetero atom or a single bond. ] Is preferable.
The hydrocarbon group in R ² is not particularly limited as long as it contains an ethylenic double bond, and may be a chain hydrocarbon group or a hydrocarbon group containing a ring in the structure.

The chain hydrocarbon group for R ² is preferably a chain alkenyl group. The chain alkenyl group may be either linear or branched, preferably has 2 to 10 carbon atoms, more preferably 2 to 5, more preferably 2 to 4, more preferably 2 or 3 Particularly preferred.
Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butynyl group. Examples of the branched alkenyl group include a 1-methylpropenyl group and a 2-methylpropenyl group. Among these, a vinyl group or a propenyl group is preferable.

Examples of the hydrocarbon group containing a ring in the structure of R ² include an unsaturated aliphatic hydrocarbon cyclic group containing an ethylenic double bond in the ring skeleton, and the unsaturated aliphatic hydrocarbon cyclic group is a straight chain. And a group in which a chain-like alkenyl group is bonded to the terminal of a cyclic hydrocarbon group, and the like.

  Examples of the unsaturated aliphatic hydrocarbon cyclic group having an ethylenic double bond in the ring skeleton include a group obtained by removing one hydrogen atom from a monocyclic or polycyclic cycloolefin. The cycloolefin preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. Examples of the cycloolefin include cyclopropene, cyclobutene, cyclopropene, cyclohexene, cycloheptene, cyclooctene, norbornene, 7-oxanorbornene, and tetracyclododecene. Among these, norbornene is preferable.

In the group in which the unsaturated aliphatic hydrocarbon cyclic group is bonded to the end of the linear or branched aliphatic hydrocarbon group, the linear or branched chain to which the unsaturated aliphatic hydrocarbon cyclic group is bonded The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, and most preferably 1 to 3.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group [—CH ₂ —], an ethylene group [— (CH ₂ ) ₂ —], a trimethylene group [ — (CH ₂ ) ₃ —], tetramethylene group [— (CH ₂ ) ₄ —], pentamethylene group [— (CH ₂ ) ₅ —] and the like can be mentioned.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH _{3) 2} -CH ₂ - alkyl groups such _{as; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such as; -CH _(CH 3) _{CH 2 CH 2 CH 2 -,} - CH 2 CH (CH 3) CH 2 CH 2 - And the like alkyl alkylene group such as an alkyl tetramethylene group of. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

In the group in which the chain alkenyl group is bonded to the end of the cyclic hydrocarbon group, examples of the chain alkenyl group include the same groups as described above.
The cyclic hydrocarbon group to which the chain alkenyl group is bonded may be a cyclic aliphatic hydrocarbon group (aliphatic cyclic group) or a cyclic aromatic hydrocarbon group (aromatic cyclic group).
The cyclic aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
The aliphatic cyclic group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The aliphatic cyclic group may be polycyclic or monocyclic. As the monocyclic aliphatic cyclic group, a group in which one hydrogen atom has been removed from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. As the polycyclic aliphatic cyclic group, a group in which two hydrogen atoms are removed from a polycycloalkane is preferable, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically, adamantane, Examples include norbornane, isobornane, tricyclodecane, and tetracyclododecane.
An aromatic cyclic group is a group obtained by removing one hydrogen atom from an aromatic ring.
The aromatic cyclic group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, further preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; A heterocyclic ring; and the like. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom.

The hydrocarbon group for R ² may have a substituent for substituting a hydrogen atom. Examples of the substituent include a halogen atom, a hydroxyl group, a hydroxyalkyl group, an alkoxy ^group, -V ²¹ -COOR ⁰ include ", -V 21 -OC (= O ) R 0". V ²¹ is a single bond or an alkylene group, and R ⁰ ″ is a hydrogen atom, an optionally substituted hydrocarbon group or an anion group.
Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
The hydroxyalkyl group and alkoxy group as the substituent are the same as those described for Ra ′ ²¹ above.

^-V 21 -COOR ⁰ as a substituent Examples of the alkylene group for ^{V 21} in ^{", -V 21 -OC (= O} ) R 0", straight chain or branched alkylene group is preferable. Examples of the linear alkylene group and the branched alkylene group are the same as those described in the description of the linear or branched aliphatic hydrocarbon group. 1-5 are preferable, as for carbon number of this alkylene group, 1-3 are more preferable, and 1 is the most preferable.

Examples of the hydrocarbon group which may have a substituent in R ⁰ ″ include, for example, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, and a substituent. Examples thereof include a chain alkenyl group which may have a group, and these are the same as those described for R ¹⁰¹ in the general formula (b-1) described in the description of the component (B) described later.
As the hydrocarbon group optionally having substituent (s) for R ⁰ ″,
Acid dissociable groups represented by the following general formulas (a1-r-1) and (a1-r-2);
The same alkyl group as R ″ mentioned for Ra ′ ²¹ ;
(A2-r-1) to (a2-r-7), (a5-r-1) to (a5-r-4), (ax3-r-1) to (ax3-r-3) Group which is made;

Examples of the anionic group for R ⁰ ″ include those represented by general formulas (r-an-1) to (r-an-4) shown below.

［式中、Ｖａ’^６１〜Ｖａ’^６４は単結合または置換基を有していてもよい２価の炭化水素基であり；Ｌａ’^６１〜Ｌａ’^６２はそれぞれ独立に−ＳＯ_２−、−ＣＯ−、または単結合であり；Ｌａ’^６３〜Ｌａ’^６５はそれぞれ独立に−ＳＯ_２−、−ＣＯ−、または単結合であり；Ｒａ’^６１〜Ｒａ’^６３はそれぞれ独立に置換基を有していてもよい炭化水素基である。Ｍ^ｍ＋はそれぞれ独立にｍ価の有機カチオンである。］

[In the formula, Va ′ ^{61 to} Va ′ ⁶⁴ are a single bond or a divalent hydrocarbon group which may have a substituent; La ′ ^{61 to} La ′ ⁶² are each independently —SO ₂ —, — CO— or a single bond; La ′ ^{63 to} La ′ ⁶⁵ are each independently —SO ₂ —, —CO— or a single bond; Ra ′ ^{61 to} Ra ′ ⁶³ each independently have a substituent. It may be a hydrocarbon group. M ^{m +} is each independently an m-valent organic cation. ]

Examples of the divalent hydrocarbon group which may have a substituent of Va ′ ^{61 to} Va ′ ⁶⁴ include the same divalent hydrocarbon groups as described in the later-described formula (a2-1). It is done. Among these, an alkylene group having 1 to 15 carbon atoms, an arylene group, a fluorinated alkylene group, or a fluorinated arylene group is preferable.
The hydrocarbon group which may have a substituent of Ra ′ ^{61 to} Ra ′ ⁶³ is the same as the hydrocarbon group which may have a substituent in R ⁰ ″.

Specific examples of R ² include, for example, vinyl group, allyl group, fluorovinyl group, difluorovinyl group, trifluorovinyl group, difluorotrifluoromethylvinyl group, trifluoroallyl group, perfluoroallyl group, styryl group, vinyl. naphthyl group, a fluorine-containing styryl group, a fluorine-containing vinylnaphthyl group, a norbornyl group, a fluorine-containing norbornyl group or a hydroxyl group, a hydroxyalkyl group, an alkoxy ^group, -V 21 -COOR ⁰ "or ^{-V 21 -OC (= O) R} , Examples thereof include a vinyl group and an allyl group substituted with ⁰ ″.

In the “divalent linking group containing a hetero atom” of L ¹ , the hetero atom is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.
When L ¹ is a divalent linking group containing a hetero atom, the linking group preferably contains at least one of an oxygen atom, a sulfur atom, and a nitrogen atom. For example, —C (═O ^{) -O-V 1 -C (=} O) -, - C (= O) -O-V 2 -O-V 1 -C (= O) -, - C (= O) -O-V 3 - C (═O) —O—V ¹ —C (═O) —, —C (═O) —O—Ar—O—R ¹¹ —C (═O) —, —C (═O) —NH— V ¹ —C (═O) —, —C (═O) —NH—Ar—C (═O) —, —C (═O) —O—V ⁴ —NH—C (═O) —, — _{C (= O) -, -} S (= O) 2 -, - C (= O) -O-V 5 -, - O-V 5 -, - O-V 1 -C (= O) -, etc. Is mentioned.
In the formula, V ^{1 to} V ⁵ are each independently an alkylene group, and Ar is an arylene group.
The alkylene group for V ^{1 to} V ⁵ may be linear or cyclic. The chain alkylene group may be linear or branched, and the linear alkylene group and the branched alkylene group mentioned as the linear or branched aliphatic hydrocarbon group, respectively, The same thing is mentioned. Examples of the cyclic alkylene group include groups obtained by further removing one hydrogen atom from the aliphatic cyclic group.
The alkylene group for V ¹ , V ³ , and V ⁵ is preferably a linear or branched alkylene group, and more preferably a methylene group, an ethylene group, or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
As the alkylene group for V ² and V ⁴ , a linear or branched alkylene group is preferable, a linear alkylene group is more preferable, and a linear alkylene group having 1 to 5 carbon atoms is more preferable. An ethylene group is particularly preferred.
Examples of the arylene group for Ar include a group obtained by further removing one hydrogen atom from the aromatic cyclic group. As the arylene group, a phenylene group or a naphthylene group is particularly preferable.
As the divalent linking group containing a hetero atom in L ¹ , among the above, the end on the oxygen atom (—O— bonded to R ¹ ) side adjacent to W ² is − Those which are C (═O) — or an alkylene group (for example, V ⁵ ) are preferred, and those where the terminal on the oxygen atom side adjacent to W ² is —C (═O) — are more preferred.

As a group containing a polymerizable group in W ² , in particular, CH ₂ ═C (R) —V ¹⁰ -L ¹ — [wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, 1 to 1 carbon atoms. 5 halogenated alkyl group, hydroxyalkyl group, alkoxy group, —V ²¹ —COOR ⁰ ″, or —V ²¹ —OC (═O) R ⁰ ″, and V ¹⁰ represents an arylene group, an alkylene group, or a single bond And L ¹ is a divalent linking group containing a hetero atom or a single bond. ] Is preferable.
In the formula, A ″, R ¹ and L ¹ are the same as defined above.
R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a halogenated alkyl group of 1 to 5 carbon atoms, a hydroxyalkyl group, an alkoxy ^group, -V 21 -COOR ⁰ ", or ^-V 21 -OC (= O ) R ⁰ ″.
The alkyl group having 1 to 5 carbon atoms in R is preferably linear or branched, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl. Group, pentyl group, isopentyl group, neopentyl group and the like.
Examples of the halogenated alkyl group having 1 to 5 carbon atoms include groups in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
Hydroxyalkyl group in R, alkoxy ^{group, -V 21 -COOR 0 ", -V} 21 -OC (= O) R 0" is the same as those described for the ^{R 2.}
R is most preferably a hydrogen atom or a methyl group from the viewpoint of industrial availability.

Examples of the arylene group for V ¹⁰ include a group obtained by further removing one hydrogen atom from the aromatic cyclic group. As the arylene group, a phenylene group or a naphthylene group is particularly preferable.
The alkylene group for V ¹⁰ may be linear or cyclic. The chain alkylene group may be linear or branched, and the linear alkylene group and the branched alkylene group mentioned as the linear or branched aliphatic hydrocarbon group, respectively, The same thing is mentioned. Examples of the cyclic alkylene group include groups obtained by further removing one hydrogen atom from the aliphatic cyclic group.
Y ¹⁰ is preferably an arylene group or a single bond, particularly preferably a phenylene group, a naphthylene group or a single bond.

Group containing a polymerizable group in W ² is ^{_{CH 2 = C (R) -V}} 10 -L 1 - when it is, ^{W 2} is a structure in which the ethylenic double bond in the formula is cleaved.
That is, when the group containing a polymerizable group is CH ₂ ═C (R) —V ¹⁰ -L ¹ —, the structural unit (a0) is a structural unit represented by the following general formula (a0-1). .
R, V ¹⁰ , L ¹ , A ″, and R ¹ in formula (a0-1) are the same as described above.

［式中、Ｒは水素原子、炭素数１〜５のアルキル基、炭素数１〜５のハロゲン化アルキル基、ヒドロキシアルキル基、アルコキシ基、−Ｖ^２１−ＣＯＯＲ^０”、又は−Ｖ^２１−ＯＣ（＝Ｏ）Ｒ^０”であり、Ａ”は、酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、Ｒ^１はラクトン含有環式基、−ＳＯ_２−含有環式基またはカーボネート含有環式基であり、Ｖ^１０は、アリーレン基、アルキレン基または単結合であり、Ｌ^１はヘテロ原子を含む２価の連結基または単結合である。Ｖ^２１は単結合またはアルキレン基であり、Ｒ^０”は水素原子、置換基を有していてもよい炭化水素基またはアニオン基である。］

In the formula, R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a halogenated alkyl group of 1 to 5 carbon atoms, a hydroxyalkyl group, an alkoxy ^group, -V 21 -COOR ⁰ ", or ^-V 21 -OC (= O) R ⁰ ″, A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and R ¹ is a lactone-containing cyclic group. , -SO ₂ -containing cyclic group or carbonate-containing cyclic group, V ¹⁰ is an arylene group, an alkylene group or a single bond, and L ¹ is a divalent linking group or a single bond containing a hetero atom. V ²¹ represents a single bond or an alkylene group, and R ⁰ ″ represents a hydrogen atom, an optionally substituted hydrocarbon group or an anion group. ]

  As the structural unit (a0), a structural unit represented by general formula (a0-11) or (a0-12) shown below is particularly desirable.

［式中、Ｒは水素原子、炭素数１〜５のアルキル基、炭素数１〜５のハロゲン化アルキル基、ヒドロキシアルキル基、アルコキシ基、−Ｖ^２１−ＣＯＯＲ^０”、又は−Ｖ^２１−ＯＣ（＝Ｏ）Ｒ^０”であり、Ａ”は、酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、Ｒ^１はラクトン含有環式基、−ＳＯ_２−含有環式基またはカーボネート含有環式基であり、Ｌ^１１は、−Ｃ（＝Ｏ）−Ｏ−Ｖ^１−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−Ｖ^２−Ｏ−Ｖ^１−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−Ｖ^３−Ｃ（＝Ｏ）−Ｏ−Ｖ^１−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−Ａｒ−Ｏ−Ｒ^１１−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＮＨ−Ｖ^１−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＮＨ−Ａｒ−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−Ｖ^４−ＮＨ−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−、−Ｓ（＝Ｏ）_２−、または−Ｃ（＝Ｏ）−Ｏ−Ｖ^５−であり、Ｖ^１２は、アリーレン基であり、Ｌ^１２は、−Ｃ（＝Ｏ）−ＮＨ−Ｖ^１−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−、−Ｏ−Ｖ^１−Ｃ（＝Ｏ）−、または−Ｏ−Ｖ^５−である。Ｖ^２１は単結合またはアルキレン基であり、Ｒ^０”は水素原子、置換基を有していてもよい炭化水素基またはアニオン基である。Ｖ^１〜Ｖ^５はそれぞれ独立してアルキレン基であり、Ａｒはアリーレン基である。］

In the formula, R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a halogenated alkyl group of 1 to 5 carbon atoms, a hydroxyalkyl group, an alkoxy ^group, -V 21 -COOR ⁰ ", or ^-V 21 -OC (= O) R ⁰ ″, A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and R ¹ is a lactone-containing cyclic group. , —SO ₂ — containing cyclic group or carbonate-containing cyclic group, and L ¹¹ is —C (═O) —O—V ¹ —C (═O) —, —C (═O) —O—. V ² —O—V ¹ —C (═O) —, —C (═O) —O—V ³ —C (═O) —O—V ¹ —C (═O) —, —C (═O ^{) -O-Ar-O-R} 11 -C (= O) -, - C (= O) -NH-V 1 -C (= O) -, - C (= O) -NH-Ar-C ^{= O) -, - C (} = O) -O-V 4 -NH-C (= O) -, - C (= O) -, - S (= O) 2 -, or -C (= O) —O—V ⁵ —, V ¹² is an arylene group, and L ¹² is —C (═O) —NH—V ¹ —C (═O) —, —C (═O) —, — O—V ¹ —C (═O) —, or —O—V ⁵ —, V ²¹ represents a single bond or an alkylene group, and R ⁰ ″ represents a hydrogen atom or a carbon atom which may have a substituent. A hydrogen group or an anion group. V ^{1 to} V ⁵ are each independently an alkylene group, and Ar is an arylene group. ]

Wherein (a0-11) or (a0-12), R, A " , R 1 is ^V 1 ~V ⁵ in which. ^{L 11, L 12} the same as defined above are the same as defined above.
Examples of the arylene group for V ¹² include the same as the arylene group for V ¹⁰ .

The structural unit (a0) may have an acid-decomposable site in the structure.
An “acid-decomposable site” is a site containing a bond that can be cleaved by the action of an acid.
Examples of the acid decomposable site include a tertiary alkyl ester structure and an acetal structure.
For example, when W ² has a tertiary carbon atom bonded to the oxy group (—O—) of the carbonyloxy group, a tertiary alkyl ester structure is formed, and by the action of an acid, an oxygen atom of the carbonyloxy group and , The bond with the tertiary carbon atom bonded thereto is cleaved.
When W ² has an (alkyl) methylene group interposed between an oxy group (—O—) or an etheric oxygen atom (—O—) of the carbonyloxy group and another etheric oxygen atom, An acetal structure is formed, and the bond between the oxy group or etheric oxygen atom of the carbonyloxy group and the carbon atom of the (alkyl) methylene group bonded thereto is cleaved by the action of an acid.
Further, among the carbon atoms constituting the ring skeleton of R ¹ , when an alkyl group as a substituent is bonded to a carbon atom bonded to an adjacent oxygen atom to form a tertiary carbon atom, a tertiary alkyl ester A structure is formed, and the action of the acid cleaves the bond between the oxygen atom and the tertiary carbon atom bonded thereto.
When it has such an acid-decomposable site, it can function as the component (A-1) even when the component (A1) is composed only of the structural unit (a0).

Specific examples of the monomer that derives the structural unit (a0), that is, the compound in which W ² in the formula (a0) is a “group containing a polymerizable group” are shown below. In each formula, R is the same as described above.
These compounds correspond to the compounds of the fourth aspect of the present invention. The structural unit derived from these compounds has a structure in which the ethylenic double bond moiety (CH ₂ ═C (R)) in the formula is — (CH ₂ —C (R)) —.

As the structural unit (a0) contained in the component (A1), 1 type of structural unit may be used, or 2 or more types may be used.
In the component (A1), the proportion of the structural unit (a0) is preferably 2 to 80 mol%, more preferably 5 to 70 mol%, and more preferably 7 to 60 mol based on all structural units constituting the component (A1). % Is more preferable. When the ratio of the structural unit (a0) is equal to or higher than the lower limit, the effects of having the structural unit (a0), for example, improvement of lithography properties such as EL, LWR, mask reproducibility, and the remaining film of the exposed portion of the resist film Effects such as an improvement in rate can be sufficiently obtained. On the other hand, by being below the upper limit value, it becomes easy to balance with other structural units.

  When the component (A) contains two or more polymer compounds (resin components), the proportion of the structural unit (a0) in the component (A) is 2 with respect to all structural units constituting the component (A) -80 mol% is preferable, 5-70 mol% is more preferable, and 7-60 mol% is further more preferable. The effects of having the structural unit (a0), such as the improvement of lithography properties such as EL, LWR, and mask reproducibility, and the improvement of the remaining film ratio of the exposed portion of the resist film, can be sufficiently obtained. On the other hand, by being below the upper limit value, it becomes easy to balance with other structural units.

(Structural unit (a1))
When the component (A1) is the component (A-1), in addition to the structural unit (a0), the component (A1) includes a structural unit (a1) containing an acid-decomposable group that increases in polarity by the action of an acid. It is preferable to have.
In addition, when the structural unit (a0) includes an acid-decomposable group in the structure, the structural unit also corresponds to the structural unit (a1). However, such a structural unit is included in the structural unit (a0). Applicable and not applicable to the structural unit (a1).

The “acid-decomposable group” is an acid-decomposable group that can cleave at least part of bonds in the structure of the acid-decomposable group by the action of an acid.
Examples of the acid-decomposable group whose polarity increases by the action of an acid include a group that decomposes by the action of an acid to generate a polar group.
Examples of the polar group include a carboxy group, a hydroxyl group, an amino group, a sulfo group (—SO ₃ H), and the like. Among these, a polar group containing —OH in the structure (hereinafter sometimes referred to as “OH-containing polar group”) is preferable, a carboxy group or a hydroxyl group is preferable, and a carboxy group is particularly preferable.
More specifically, examples of the acid-decomposable group include groups in which the polar group is protected with an acid-dissociable group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected with an acid-dissociable group).
Here, “acid-dissociable group” means
(I) an acid-dissociable group capable of cleaving a bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group by the action of an acid, or
(Ii) a group capable of cleaving a bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group by further decarboxylation after partial bond cleavage by the action of an acid ,
Both.
The acid-dissociable group constituting the acid-decomposable group must be a group having a lower polarity than the polar group generated by dissociation of the acid-dissociable group. Is dissociated, a polar group having a polarity higher than that of the acid dissociable group is generated to increase the polarity. As a result, the polarity of the entire component (A1) increases. As the polarity increases, the solubility in the developer changes relatively. When the developer is an alkaline developer, the solubility increases. When the developer is an organic developer, the solubility increases. Decrease.

The acid-dissociable group is not particularly limited, and those that have been proposed as acid-dissociable groups for base resins for chemically amplified resists can be used.
Examples of the acid dissociable group that protects a carboxy group or a hydroxyl group among the polar groups include, for example, an acid dissociable group represented by the following general formula (a1-r-1) (hereinafter referred to as “acetal type acid dissociable group”). May be included).

［式中、Ｒａ’^１、Ｒａ’^２は水素原子またはアルキル基であり、Ｒａ’^３は炭化水素基であって、Ｒａ’^３は、Ｒａ’^１、Ｒａ’^２のいずれかと結合して環を形成してもよい。］

[Wherein, Ra ′ ¹ and Ra ′ ² are a hydrogen atom or an alkyl group, Ra ′ ³ is a hydrocarbon group, and Ra ′ ³ is bonded to either Ra ′ ¹ or Ra ′ ² to form a ring. May be formed. ]

In formula (a1-r-1), at least one of Ra ′ ¹ and Ra ′ ² is preferably a hydrogen atom, and more preferably both are hydrogen atoms.
In the case where Ra ′ ¹ or Ra ′ ² is an alkyl group, the alkyl group is the alkyl group mentioned as the substituent that may be bonded to the α-position carbon atom in the description of the α-substituted acrylate ester. The same thing is mentioned, A C1-C5 alkyl group is preferable. Specifically, linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl And a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

In formula (a1-r-1), examples of the hydrocarbon group for Ra ′ ³ include a linear, branched, or cyclic alkyl group. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and still more preferably 1 or 2. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Among these, a methyl group, an ethyl group, or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.
The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group and the like, and isopropyl group is most preferable.
The cyclic alkyl group preferably has 3 to 20 carbon atoms, and more preferably 4 to 12 carbon atoms. Specific examples thereof include monocycloalkanes such as cyclopentane and cyclohexane, and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. A part of carbon atoms constituting the ring of the cyclic alkyl group may be substituted with an etheric oxygen atom (—O—).

When Ra ′ ³ is bonded to either Ra ′ ¹ or Ra ′ ² to form a ring, the cyclic group is preferably a 4- to 7-membered ring, and more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.

  Among the polar groups, examples of the acid dissociable group that protects the carboxy group include an acid dissociable group represented by the following general formula (a1-r-2) (the following formula (a1-r-2) Among the acid dissociable groups represented by), those composed of an alkyl group may hereinafter be referred to as “tertiary alkyl ester type acid dissociable groups” for convenience).

［式中、Ｒａ’^４〜Ｒａ’^６はそれぞれ炭化水素基であって、Ｒａ’^５、Ｒａ’^６は互いに結合して環を形成してもよい。］

[Wherein, Ra ′ ^{4 to} Ra ′ ⁶ are each a hydrocarbon group, and Ra ′ ⁵ and Ra ′ ⁶ may be bonded to each other to form a ring. ]

As the hydrocarbon group for Ra ′ ^{4 to} Ra ′ ^6, the same groups as those described above for Ra ′ ³ can be mentioned.
Ra ^'4 is preferably an alkyl group having 1 to 5 carbon atoms. In the case where Ra ′ ⁵ and Ra ′ ⁶ are bonded to each other to form a ring, a group represented by the following general formula (a1-r2-1) is exemplified. On the other hand, when Ra ′ ^{4 to} Ra ′ ⁶ are not bonded to each other and are independent hydrocarbon groups, groups represented by the following general formula (a1-r2-2) are exemplified.

［式中、Ｒａ’^１０は炭素数１〜１０のアルキル基、Ｒａ’^１１はＲａ’^１０が結合した炭素原子と共に脂肪族環式基を形成する基、Ｒａ’^１２〜Ｒａ’^１４は、それぞれ独立に炭化水素基を示す。］

[Wherein, Ra ′ ¹⁰ is an alkyl group having 1 to ¹⁰ carbon atoms, Ra ′ ¹¹ is a group that forms an aliphatic cyclic group together with a carbon atom to which Ra ′ ¹⁰ is bonded, and Ra ′ ^{12 to} Ra ′ ¹⁴ are Independently represents a hydrocarbon group. ]

In formula (a1-r2-1), the alkyl group of the alkyl group having 1 to ¹⁰ carbon atoms of Ra ′ ¹⁰ is a linear or branched alkyl group of Ra ′ ³ in formula (a1-r-1) The groups mentioned as are preferred. Wherein (a1-r2-1), Ra 'aliphatic cyclic ^{group 11} is configured, Ra in formula (a1-r-1)' group listed as a cyclic alkyl group of ³ is preferred.

In formula (a1-r2-2), Ra ′ ¹² and Ra ′ ¹⁴ are preferably each independently an alkyl group having 1 to 10 carbon atoms, and the alkyl group is represented by Ra in formula (a1-r-1). 'The group mentioned as a linear or branched alkyl group of ³ is more preferable, It is more preferable that it is a C1-C5 linear alkyl group, It is especially preferable that it is a methyl group or an ethyl group .
In formula (a1-r2-2), Ra ′ ¹³ is a linear, branched or cyclic alkyl group exemplified as the hydrocarbon group for Ra ′ ³ in formula (a1-r-1). Is preferred. Among these, a group exemplified as the cyclic alkyl group for Ra ′ ³ is more preferable.

  Specific examples of the formula (a1-r2-1) are given below.

  Specific examples of the formula (a1-r2-2) are given below.

  Examples of the acid dissociable group that protects the hydroxyl group among the polar groups include an acid dissociable group represented by the following general formula (a1-r-3) (hereinafter referred to as “tertiary alkyloxycarbonyl acid dissociable for convenience”). Group ”).

［式中、Ｒａ’^７〜Ｒａ’^９はそれぞれアルキル基である。］

[Wherein, Ra ′ ^{7 to} Ra ′ ⁹ each represents an alkyl group. ]

In the formula (a1-r-3), the Ra ′ ^{7 to} Ra ′ ⁹ groups are preferably alkyl groups having 1 to 5 carbon atoms, and more preferably 1 to 3 groups.
Moreover, it is preferable that the total carbon number of each alkyl group is 3-7, it is more preferable that it is 3-5, and it is most preferable that it is 3-4.

  The structural unit (a1) is a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent, and an acid whose polarity is increased by the action of an acid. Structural unit containing a decomposable group; a structural unit derived from acrylamide and containing an acid-decomposable group whose polarity is increased by the action of an acid; a hydroxyl group of a structural unit derived from hydroxystyrene or a hydroxystyrene derivative A structural unit in which at least a part of the hydrogen atoms in is protected by a substituent containing the acid-decomposable group; a hydrogen atom in —C (═O) —OH of a structural unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative And a structural unit in which at least a part of the group is protected by a substituent containing the acid-decomposable group.

Among the above, the structural unit (a1) is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent.
Preferable specific examples of the structural unit (a1) include the following general formulas (a1-1) and (a1-2).

［式中、Ｒは水素原子、炭素数１〜５のアルキル基、炭素数１〜５のハロゲン化アルキル基、ヒドロキシアルキル基、アルコキシ基、−Ｖ^２１−ＣＯＯＲ^０”、又は−Ｖ^２１−ＯＣ（＝Ｏ）Ｒ^０”である。Ｖａ^１はエーテル結合、ウレタン結合およびアミド結合から選ばれる連結基を有していてもよい２価の炭化水素基であり、ｎ_ａ１はそれぞれ独立に０〜２であり、Ｒａ^１は上記式（ａ１−ｒ−１）〜（ａ１−ｒ−２）で表される酸解離性基である。Ｗａ^１はｎ_ａ２＋１価の炭化水素基であり、ｎ_ａ２は１〜３であり、Ｒａ^２は上記式（ａ１−ｒ−１）または（ａ１−ｒ−３）で表される酸解離性基である。］

In the formula, R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a halogenated alkyl group of 1 to 5 carbon atoms, a hydroxyalkyl group, an alkoxy ^group, -V 21 -COOR ⁰ ", or ^-V 21 -OC (= O) R ⁰ ″. Va ¹ is a divalent hydrocarbon group which may have a linking group selected from an ether bond, a urethane bond and an amide bond, each of n _a1 is independently 0 to 2, and Ra ¹ is a group represented by the above formula ( a1-r-1) to (a1-r-2). Wa ¹ is a n _a2 +1 valent hydrocarbon group, n _a2 is 1 to 3, and Ra ² is an acid dissociation property represented by the above formula (a1-r-1) or (a1-r-3). It is a group. ]

R in the formula (a1-1) is the same as R described in the description of the structural unit (a0).
The divalent hydrocarbon group for Va ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group as a divalent hydrocarbon group in Va ¹ may be saturated or unsaturated, and is usually preferably saturated.
More specifically, examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group or an aliphatic hydrocarbon group containing a ring in the structure.
Examples of Va ¹ include those in which the divalent hydrocarbon group is bonded via a linking group selected from an ether bond, a urethane bond, and an amide bond. One or more linking groups may be present in Va ¹ . When two or more linking groups are present, each linking group may be the same or different.

The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, and most preferably 1 to 3.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group [—CH ₂ —], an ethylene group [— (CH ₂ ) ₂ —], a trimethylene group [ — (CH ₂ ) ₃ —], tetramethylene group [— (CH ₂ ) ₄ —], pentamethylene group [— (CH ₂ ) ₅ —] and the like can be mentioned.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH _{3) 2} -CH ₂ - alkyl groups such _{as; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such as; -CH _(CH 3) _{CH 2 CH 2 CH 2 -,} - CH 2 CH (CH 3) CH 2 CH 2 - And the like alkyl alkylene group such as an alkyl tetramethylene group of. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group that is linear or branched. Examples thereof include a group bonded to the end of a chain aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include those described above.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 8 carbon atoms, and specific examples include cyclopentane, cyclohexane and cyclooctane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically adamantane. , Norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring.
The aromatic hydrocarbon group as the divalent hydrocarbon group in Va ¹ preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, still more preferably 5 to 20 carbon atoms, and 6 to 6 carbon atoms. 15 is particularly preferable, and 6 to 10 is most preferable. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic ring possessed by the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; some of the carbon atoms constituting the aromatic hydrocarbon ring are heterogeneous. Aromatic heterocycles substituted with atoms; and the like. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specifically, the aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene group); a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group) A group in which one of the hydrogen atoms is substituted with an alkylene group (for example, arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.) A group in which one hydrogen atom is further removed from the aryl group in the above); The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

In the formula (a1-2), the n _a2 +1 valent hydrocarbon group in Wa ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity, may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group including a ring in the structure, or a linear or branched aliphatic hydrocarbon group. It includes a group formed by combining an aliphatic hydrocarbon group in the structure containing a ring, and specific examples thereof include the same groups as Va ¹ of the aforementioned formula (a1-1).
The n _a2 +1 valence is preferably 2 to 4, and more preferably 2 or 3.

  As the formula (a1-2), a structural unit represented by general formula (a1-2-01) shown below is particularly desirable.

In formula (a1-2-01), Ra ² is an acid dissociable group represented by the above formula (a1-r-1) or (a1-r-3). n _a2 is an integer of 1 to 3, preferably 1 or 2, and more preferably 1. c is an integer of 0 to 3, preferably 0 or 1, and more preferably 1. R is the same as described above.

  Specific examples of the formula (a1-1) are shown below.

  Specific examples of the formula (a1-2) are shown below.

As the structural unit (a1) contained in the component (A1), 1 type of structural unit may be used, or 2 or more types may be used.
The proportion of the structural unit (a1) in the component (A1) is preferably 20 to 80 mol%, more preferably 20 to 75 mol%, more preferably 25 to 70 mol%, based on all structural units constituting the component (A1). Is more preferable. By setting it to the lower limit value or more, a pattern can be easily obtained, and lithography properties such as sensitivity, resolution, and LWR are also improved. Moreover, the balance with another structural unit can be taken by making it below an upper limit.

(Other structural units)
In addition to the structural unit (a0) and the structural unit (a1), the component (A1) may further have another structural unit that does not correspond to the structural unit (a0) and the structural unit (a1). The other structural unit is not particularly limited as long as it is a structural unit not classified into the structural units described above. Resin resins for ArF excimer laser, KrF excimer laser (preferably for ArF excimer laser), etc. A number of hitherto known compounds can be used, and examples include the structural units (a2) to (a4) shown below.

Structural unit (a2):
The structural unit (a2) is a structural unit containing a lactone-containing cyclic group, an —SO ₂ — containing cyclic group, or a carbonate-containing cyclic group, and does not correspond to the structural unit (a0).
The lactone-containing cyclic group, the carbonate-containing cyclic group, or the —SO ₂ -containing cyclic group of the structural unit (a2) can be obtained by adhering the resist film to the substrate when the component (A1) is used for forming the resist film. It is effective in enhancing the sex.
The lactone-containing cyclic group, —SO ₂ — containing cyclic group, and carbonate-containing cyclic group in the structural unit (a2) are the same as those exemplified in the description of R ^{1 in} the general formula (a0). Is mentioned.
In addition, when the structural unit (a1) includes a lactone-containing cyclic group, an —SO ₂ -containing cyclic group, or a carbonate-containing cyclic group in the structure, the structural unit is also included in the structural unit (a2). Although applicable, such a structural unit corresponds to the structural unit (a1) and does not correspond to the structural unit (a2).

  The structural unit (a2) is preferably a structural unit represented by the following general formula (a2-1).

［式中、Ｒは水素原子、炭素数１〜５のアルキル基、炭素数１〜５のハロゲン化アルキル基、ヒドロキシアルキル基、アルコキシ基、−Ｖ^２１−ＣＯＯＲ^０”、又は−ＯＣ（＝Ｏ）Ｒ^０”であり、Ｙａ^２１は単結合または２価の連結基であり、Ｌａ^２１は−Ｏ−、−ＣＯＯ−、−ＣＯＮ（Ｒ’）−、−ＯＣＯ−、−ＣＯＮＨＣＯ−又は−ＣＯＮＨＣＳ−であり、Ｒ’は水素原子またはメチル基を示す。ただしＬａ^２１が−Ｏ−の場合、Ｙａ^２１は−ＣＯ−にはならない。Ｒａ^２１はラクトン含有環式基、カーボネート含有環式基、又は−ＳＯ_２−含有環式基である。Ｖ^２１は単結合またはアルキレン基であり、Ｒ^０”は水素原子、置換基を有していてもよい炭化水素基またはアニオン基である。］

In the formula, R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a halogenated alkyl group of 1 to 5 carbon atoms, a hydroxyalkyl group, an alkoxy ^group, -V 21 -COOR ⁰ ", or -OC (= O ) R ⁰ ″, Ya ²¹ is a single bond or a divalent linking group, and La ²¹ is —O—, —COO—, —CON (R ′) —, —OCO—, —CONHCO— or —CONHCS. -And R 'represents a hydrogen atom or a methyl group. However, when La ²¹ is —O—, Ya ²¹ is not —CO—. Ra ²¹ is a lactone-containing cyclic group, a carbonate-containing cyclic group, or an —SO ₂ -containing cyclic group. V ²¹ represents a single bond or an alkylene group, and R ⁰ ″ represents a hydrogen atom, an optionally substituted hydrocarbon group or an anion group.]

In formula (a2-1), R is the same as described above.
The divalent linking group of Ya ²¹ is not particularly limited, and preferred examples thereof include a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a hetero atom.

(Divalent hydrocarbon group which may have a substituent)
The hydrocarbon group as the divalent linking group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group or an aliphatic hydrocarbon group having a ring in the structure.

Specific examples of the linear or branched aliphatic hydrocarbon group include the groups exemplified for Va ¹ in the above formula (a1-1).
The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and a carbonyl group.

As the aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group which may contain a substituent containing a hetero atom in the ring structure (excluding two hydrogen atoms from the aliphatic hydrocarbon ring) Group), a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and the cyclic aliphatic hydrocarbon group is a linear or branched chain fatty acid. Group intervening in the middle of the group hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include those described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
Specific examples of the cyclic aliphatic hydrocarbon group include the groups exemplified for Va ¹ in the above formula (a1-1).
The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group or a tert-butoxy group. Most preferred is an ethoxy group.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent include groups in which part or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms.
In the cyclic aliphatic hydrocarbon group, a part of carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. As the substituent containing the hetero atom, —O—, —C (═O) —O—, —S—, —S (═O) ₂ —, and —S (═O) ₂ —O— are preferable.

Specific examples of the aromatic hydrocarbon group as the divalent hydrocarbon group include groups exemplified by Va ¹ in the above formula (a1-1).
In the aromatic hydrocarbon group, a hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
Examples of the alkoxy group, the halogen atom and the halogenated alkyl group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.

(Divalent linking group containing a hetero atom)
The hetero atom in the divalent linking group containing a hetero atom is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.
When Ya ²¹ is a divalent linking group containing a hetero atom, preferred examples of the linking group include —O—, —C (═O) —O—, —C (═O) —, and —O—C. (═O) —O—, —C (═O) —NH—, —NH—, —NH—C (═NH) — (H may be substituted with a substituent such as an alkyl group or an acyl group). _{.), - S -, -} S (= O) 2 -, - S (= O) 2 -O-, the formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 - A group represented by C (═O) —O—, — [Y ²¹ —C (═O) —O] _{m ′} —Y ²² — or —Y ²¹ —O—C (═O) —Y ²² — In the formula, Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m ′ is an integer of 0 to 3. ] Etc. are mentioned.
When the divalent linking group containing a hetero atom is —C (═O) —NH—, —NH—, —NH—C (═NH) —, H is a substituent such as an alkyl group or acyl. May be substituted. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
Formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 -C (= O) -O -, - [Y 21 -C (= O) -O] m '-Y 22 - or ^{-Y 21 -O-C (= O} ) -Y 22 - ^{in, Y 21} and ^{Y 22} are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include those similar to the “divalent hydrocarbon group optionally having substituent (s)” mentioned in the description of the divalent linking group.
Y ²¹ is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group. preferable.
Y ²² is preferably a linear or branched aliphatic hydrocarbon group, and more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
In the group represented by the formula — [Y ²¹ —C (═O) —O] _{m ′} —Y ²² —, m ′ is an integer of 0 to 3, preferably an integer of 0 to 2, Or 1 is more preferable, and 1 is particularly preferable. That is, the group represented by the formula — [Y ²¹ —C (═O) —O] _{m ′} —Y ²² — is represented by the formula —Y ²¹ —C (═O) —O—Y ²² —. The group is particularly preferred. Among these, a group represented by the formula — (CH ₂ ) _{a ′} —C (═O) —O— (CH ₂ ) _{b ′} — is preferable. In the formula, a ′ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further preferably 1 or 2, and most preferably 1. b ′ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, more preferably 1 or 2, and most preferably 1.

Ya ²¹ is preferably a single bond, an ester bond [—C (═O) —O—], an ether bond (—O—), a linear or branched alkylene group, or a combination thereof. .

In the formula (a2-1), Ra ²¹ is a lactone-containing cyclic group, an —SO ₂ -containing cyclic group, or a carbonate-containing cyclic group.
Examples of the lactone-containing cyclic group, -SO ₂ -containing cyclic group, and carbonate-containing cyclic group in Ra ²¹ are the same as those described in the description of R ^{1 in} the general formula (a0). .

The structural unit (a2) contained in the component (A1) may be one type or two or more types.
When the component (A1) has the structural unit (a2), the proportion of the structural unit (a2) is preferably 1 to 80 mol% with respect to the total of all the structural units constituting the component (A1). It is more preferably 10 to 70 mol%, further preferably 10 to 65 mol%, particularly preferably 10 to 60 mol%. By setting it to the lower limit value or more, the effect of containing the structural unit (a2) can be sufficiently obtained, and by setting it to the upper limit value or less, it is possible to balance with other structural units, such as various kinds of DOF, CDU, etc. The lithography characteristics and pattern shape of the film are improved.

Structural unit (a3):
The structural unit (a3) is a structural unit containing a polar group-containing aliphatic hydrocarbon group (excluding those corresponding to the structural units (a0), (a1), and (a2) described above).
It is considered that when the component (A1) has the structural unit (a3), the hydrophilicity of the component (A) is increased and the resolution is improved.
Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, and a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group is substituted with a fluorine atom. A hydroxyl group is particularly preferable.
Examples of the aliphatic hydrocarbon group include a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) and a cyclic aliphatic hydrocarbon group (cyclic group). The cyclic group may be a monocyclic group or a polycyclic group. For example, a resin for a resist composition for an ArF excimer laser can be appropriately selected from those proposed. The cyclic group is preferably a polycyclic group, and more preferably 7 to 30 carbon atoms.
Among them, a structural unit derived from an acrylate ester containing an aliphatic polycyclic group containing a hydroxyalkyl group in which a part of hydrogen atoms of a hydroxyl group, a cyano group, a carboxy group, or an alkyl group is substituted with a fluorine atom Is more preferable. Examples of the polycyclic group include groups in which two or more hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane and the like. Specific examples include groups in which two or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among these polycyclic groups, there are groups in which two or more hydrogen atoms have been removed from adamantane, groups in which two or more hydrogen atoms have been removed from norbornane, and groups in which two or more hydrogen atoms have been removed from tetracyclododecane. Industrially preferable.

The structural unit (a3) is not particularly limited as long as it contains a polar group-containing aliphatic hydrocarbon group, and any structural unit can be used.
The structural unit (a3) is a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, and includes a polar group-containing aliphatic hydrocarbon group A structural unit is preferred.
The structural unit (a3) is derived from a hydroxyethyl ester of acrylic acid when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms. When the hydrocarbon group is a polycyclic group, the structural unit represented by the following formula (a3-1), the structural unit represented by the formula (a3-2), the formula ( The structural unit represented by a3-3) is preferred.

［式中、Ｒは前記と同じであり、ｊは１〜３の整数であり、ｋは１〜３の整数であり、ｔ’は１〜３の整数であり、ｌは１〜５の整数であり、ｓは１〜３の整数である。］

[Wherein, R is the same as above, j is an integer of 1 to 3, k is an integer of 1 to 3, t ′ is an integer of 1 to 3, and l is an integer of 1 to 5] And s is an integer of 1 to 3. ]

In formula (a3-1), j is preferably 1 or 2, and more preferably 1. When j is 2, it is preferable that the hydroxyl group is bonded to the 3rd and 5th positions of the adamantyl group. When j is 1, it is preferable that the hydroxyl group is bonded to the 3-position of the adamantyl group.
j is preferably 1, and it is particularly preferred that the hydroxyl group is bonded to the 3-position of the adamantyl group.

In formula (a3-2), k is preferably 1. The cyano group is preferably bonded to the 5th or 6th position of the norbornyl group.
In formula (a3-3), t ′ is preferably 1. l is preferably 1. s is preferably 1. In these, a 2-norbornyl group or a 3-norbornyl group is preferably bonded to the terminal of the carboxy group of acrylic acid. The fluorinated alkyl alcohol is preferably bonded to the 5th or 6th position of the norbornyl group.

The structural unit (a3) contained in the component (A1) may be one type or two or more types.
When the component (A1) has the structural unit (a3), it is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, based on the total of all structural units constituting the component (A1). 5-25 mol% is more preferable. By setting the proportion of the structural unit (a3) to the lower limit value or more, the effect of including the structural unit (a3) can be sufficiently obtained, and by setting the proportion of the structural unit (a3) to the upper limit value or less, balance with other structural units can be obtained. It becomes easy.

Structural unit (a4):
The structural unit (a4) is a structural unit containing an acid non-dissociable aliphatic cyclic group.
When the component (A1) has the structural unit (a4), the dry etching resistance of the formed resist pattern is improved. Moreover, the hydrophobicity of (A1) component increases. The improvement in hydrophobicity is thought to contribute to the improvement of resolution, resist pattern shape, etc., particularly in the case of organic solvent development.
The “acid non-dissociable cyclic group” in the structural unit (a4) means that when an acid is generated in the resist composition by exposure (for example, when an acid is generated from the component (B) described later), the acid is It is a cyclic group that remains in the structural unit as it is without dissociating even when acting.
As the structural unit (a4), for example, a structural unit derived from an acrylate ester containing a non-acid-dissociable aliphatic cyclic group is preferable. Examples of the cyclic group include those similar to those exemplified for the structural unit (a1), for ArF excimer laser, for KrF excimer laser (preferably for ArF excimer laser), etc. A number of hitherto known materials can be used as the resin component of the resist composition.
In particular, at least one selected from a tricyclodecyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, and a norbornyl group is preferable in terms of industrial availability. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.
Specific examples of the structural unit (a4) include those having the structures of the following general formulas (a4-1) to (a4-6).

［式中、Ｒ^αは前記と同じである。］

[Wherein, R ^α is the same as defined above. ]

The structural unit (a4) contained in the component (A1) may be one type or two or more types.
When the component (A1) has the structural unit (a4), the proportion of the structural unit (a4) is preferably 1 to 30 mol% with respect to the total of all the structural units constituting the component (A1). 3-20 mol% is more preferable.

The component (A1) is a polymer having at least the structural unit (a0).
The component (A1) is preferably a copolymer having the structural units (a0) and (a1). Examples of such a copolymer include a copolymer composed of structural units (a0) and (a1), a copolymer composed of structural units (a0), (a1) and (a2), and structural units (a0) and (a1). And a copolymer comprising (a3), a copolymer comprising the structural units (a0), (a1), (a2) and (a3), and the like.

The mass average molecular weight (Mw) of the component (A1) (polystyrene conversion standard by gel permeation chromatography (GPC)) is not particularly limited, preferably 1000 to 50000, more preferably 1500 to 30000, 2000 to 2000 20000 is most preferred. If it is below the upper limit of this range, it has sufficient solubility in a resist solvent to be used as a resist, and if it is above the lower limit of this range, dry etching resistance and resist pattern cross-sectional shape are good.
The dispersity (Mw / Mn) is not particularly limited, but is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5. In addition, Mn shows a number average molecular weight.

The component (A1) is obtained by polymerizing a monomer for deriving each structural unit by known radical polymerization using a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate. be able to.
Further, for the component (A1), in the polymerization, a chain transfer agent such as HS—CH ₂ —CH ₂ —CH ₂ —C (CF ₃ ) ₂ —OH is used in combination, so that the terminal A —C (CF ₃ ) ₂ —OH group may be introduced into the. As described above, a copolymer introduced with a hydroxyalkyl group in which a part of hydrogen atoms of the alkyl group is substituted with a fluorine atom reduces development defects and LER (line edge roughness: uneven unevenness of line side walls). It is effective in reducing
A method for producing a monomer for deriving the structural unit (a0) will be described later with reference to the compound of the fourth aspect of the present invention. As other monomers for deriving any structural unit, commercially available monomers may be used, or those synthesized using a known method may be used.

As the component (A1), one type may be used alone, or two or more types may be used in combination.
The proportion of the component (A1) in the component (A) is preferably 25% by mass or more, more preferably 50% by mass, further preferably 75% by mass, and 100% by mass with respect to the total mass of the component (A). May be. When the ratio is 25% by mass or more, lithography properties such as MEF, circularity, and roughness reduction are further improved.

The resist composition of the present invention may contain, as the component (A), a base material component (hereinafter referred to as the component (A2)) that does not correspond to the component (A1) and whose polarity is increased by the action of an acid. .
The component (A2) is not particularly limited, and is conventionally known as a substrate component for a chemically amplified resist composition (for example, for ArF excimer laser, for KrF excimer laser (preferably ArF excimer laser). Base resin) and the like may be arbitrarily selected and used. For example, the base resin for ArF excimer laser includes a resin having the structural unit (a1) as an essential structural unit and optionally further including the structural units (a2) to (a4).
(A2) A component may be used individually by 1 type and may be used in combination of 2 or more type.

In the resist composition of the present invention, as the component (A), one type may be used alone, or two or more types may be used in combination.
In the resist composition of the present invention, the content of the component (A) may be adjusted according to the resist film thickness to be formed.

<(B) component>
The resist composition of the present invention preferably further contains a component (B) (an acid generator component that generates an acid upon exposure) in addition to the component (A).
The component (B) is not particularly limited, and those that have been proposed as acid generators for chemically amplified resists can be used. Examples of such acid generators include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyldiazomethanes, and diazomethanes such as poly (bissulfonyl) diazomethanes. There are various known acid generators, nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, disulfone acid generators, and the like.
As the onium salt acid generator, for example, a compound represented by the following general formula (b-1) or (b-2) can be used.

［式中、Ｒ^１０１は置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、または置換基を有していてもよい鎖状のアルケニル基であり、Ｙ^１０１は単結合または酸素原子を含む２価の連結基であり、Ｖ^１０１は単結合、アルキレン基、またはフッ素化アルキレン基であり、Ｒ^１０２はフッ素原子または炭素数１〜５のフッ素化アルキル基であり、Ｒ^１０４、Ｒ^１０５は、それぞれ独立に、炭素数１〜１０のアルキル基または炭素数１〜１０のフッ素化アルキル基であり、互いに結合して環を形成していてもよく、Ｍ^ｍ＋はｍ価の有機カチオンである。］

[Wherein, R ¹⁰¹ represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom, V ¹⁰¹ is a single bond, an alkylene group, or a fluorinated alkylene group, and R ¹⁰² is a fluorine atom or a C 1-5 carbon atom. Each of R ¹⁰⁴ and R ¹⁰⁵ is independently an alkyl group having 1 to 10 carbon atoms or a fluorinated alkyl group having 1 to 10 carbon atoms, which are bonded to each other to form a ring; M ^{m +} is an m-valent organic cation. ]

{Anion part}
In the formula (b-1), R ¹⁰¹ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain which may have a substituent. Alkenyl group.
The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.
The aromatic hydrocarbon group for R ¹⁰¹ is the aromatic hydrocarbon ring mentioned for the divalent aromatic hydrocarbon group for Va ¹ in the formula (a1-1), or an aromatic compound containing two or more aromatic rings. Examples include an aryl group in which one hydrogen atom is removed, and a phenyl group and a naphthyl group are preferable.
The cyclic aliphatic hydrocarbon group for R ¹⁰¹ is a group obtained by removing one hydrogen atom from the monocycloalkane or polycycloalkane mentioned as the divalent aliphatic hydrocarbon group for Va ¹ in the formula (a1-1). And an adamantyl group and a norbornyl group are preferable.
In addition, the cyclic hydrocarbon group in R ¹⁰¹ may contain a hetero atom such as a heterocyclic ring, and is specifically represented by the general formulas (a2-r-1) to (a2-r-7). Lactone-containing cyclic groups, —SO ₂ -containing cyclic groups represented by the above general formulas (a5-r-1) to (a5-r-4), and the following heterocycles.

Examples of the substituent in the cyclic hydrocarbon group of R ¹⁰¹ include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group.
The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and a methoxy group. An ethoxy group is most preferred.
Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
As the halogenated alkyl group as a substituent, a part of hydrogen atoms of an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, or the like A group in which all the halogen atoms are substituted is exemplified.

The linear alkyl group for R ¹⁰¹ may be either linear or branched, and the linear alkyl group preferably has 1 to 20 carbon atoms, and preferably 1 to 15 carbon atoms. Is more preferable, and 1 to 10 is most preferable. Specifically, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group Group, pentadecyl group, hexadecyl group, isohexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group and the like.
The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, for example, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, Examples include 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group and the like.

The chain alkenyl group for R ¹⁰¹ may be either linear or branched, and preferably has 2 to 10 carbon atoms, preferably 2 to 5, preferably 2 to 4, and particularly preferably 3 preferable. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butynyl group. Examples of the branched alkenyl group include a 1-methylpropenyl group and a 2-methylpropenyl group.
Among the above, the chain alkenyl group is particularly preferably a propenyl group.

Examples of the substituent in the chain alkyl group or alkenyl group of R ¹⁰¹ include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the cyclic group in R ¹⁰¹ described above. Can be mentioned.

In the present invention, R ¹⁰¹ is preferably a cyclic hydrocarbon group which may have a substituent, a group obtained by removing one or more hydrogen atoms from a phenyl group, a naphthyl group, or a polycycloalkane, Lactone-containing cyclic groups represented by the formulas (a2-r-1) to (a2-r-7), —SO represented by the general formulas (a5-r-1) to (a5-r-4) ₂ -containing cyclic groups, etc. are preferred.

When Y ¹⁰¹ is a divalent linking group containing an oxygen atom, Y ¹⁰¹ may contain an atom other than an oxygen atom. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms.
Examples of the divalent linking group containing an oxygen atom include an oxygen atom (ether bond: —O—), an ester bond (—C (═O) —O—), and an amide bond (—C (═O) —NH. -), A carbonyl group (-C (= O)-), a non-hydrocarbon oxygen atom-containing linking group such as a carbonate bond (-O-C (= O) -O-); the non-hydrocarbon oxygen atom Examples include a combination of a containing linking group and an alkylene group. A sulfonyl group (—SO ₂ —) may be further linked to the combination. Examples of the combination include linking groups represented by the following formulas (y-al-1) to (y-al-7).

［式中、Ｖ’^１０１は単結合または炭素数１〜５のアルキレン基であり、Ｖ’^１０２は炭素数１〜３０の２価の飽和炭化水素基である。］

[Wherein, V ′ ¹⁰¹ is a single bond or an alkylene group having 1 to 5 carbon atoms, and V ′ ¹⁰² is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms. ]

The divalent saturated hydrocarbon group for V ′ ¹⁰² is preferably an alkylene group having 1 to 30 carbon atoms.

Specific examples of the alkylene group for V ′ ¹⁰¹ and V ′ ¹⁰² include a methylene group [—CH ₂ —]; —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH _{3). ) 2 -, - C (CH} 3) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as Ethylene group [—CH ₂ CH ₂ —]; —CH (CH ₃ ) CH ₂ —, —CH (CH ₃ ) CH (CH ₃ ) —, —C (CH ₃ ) ₂ CH ₂ —, —CH (CH ₂ Alkylethylene groups such as CH ₃ ) CH ₂ —; trimethylene group (n-propylene group) [—CH ₂ CH ₂ CH ₂ —]; —CH (CH ₃ ) CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) CH ₂ -; and alkyltetramethylene groups such as, tetra Styrene group _{[-CH 2 CH 2 CH 2 CH} 2 -]; - CH (CH 3) CH 2 CH 2 CH 2 -, - CH 2 CH (CH 3) CH 2 CH 2 - alkyl tetramethylene group and the like; penta And a methylene group [—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —] and the like, and a linear alkylene group is preferred.
In addition, a part of the methylene groups in the alkylene group in V ′ ¹⁰¹ and V ′ ¹⁰² may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is preferably a divalent group obtained by further removing one hydrogen atom from the cyclic alkyl group of Ra ′ ³ and is a cyclohexylene group, 1,5-adamantylene group or 2,6- An adamantylene group is more preferred.

Y ¹⁰¹ is preferably a divalent linking group containing an ester bond or an ether bond, and those represented by the above formulas (y-al-1) to (y-al-5) are preferable.

In formula (b-1), V ¹⁰¹ is preferably a single bond or a fluorinated alkylene group having 1 to 4 carbon atoms.
In formula (b-1), R ¹⁰² is preferably a fluorine atom or a C 1-5 perfluoroalkyl group, and more preferably a fluorine atom.

As specific examples of the anion moiety of the formula (b-1), for example,
When Y ¹⁰¹ is a single bond, fluorinated alkyl sulfonate anions such as trifluoromethane sulfonate anion and perfluorobutane sulfonate anion can be mentioned;
When Y ¹⁰¹ is a divalent linking group containing an oxygen atom, an anion represented by any of the following formulas (an-1) to (an-3) can be mentioned.

［式中、Ｒ”^１０１は、置換基を有していてもよい脂肪族環式基、前記式（ｒ−ｈｒ−１）〜（ｒ−ｈｒ−６）で表される基、または置換基を有していても良い鎖状のアルキル基であり；Ｒ”^１０２は、置換基を有していてもよい脂肪族環式基、前記式（ａ２−ｒ−１）〜（ａ２−ｒ−７）で表されるラクトン含有環式基、または上記一般式（ａ５−ｒ−１）〜（ａ５−ｒ−４）で表される−ＳＯ_２−含有環式基であり；Ｒ”^１０３は、置換基を有していてもよい芳香族環式基、置換基を有していてもよい脂肪族環式基または置換基を有していてもよい鎖状のアルケニル基であり；ｖ”は、それぞれ独立に０〜３の整数であり；ｑ”はそれぞれ独立に１〜２０の整数であり；ｔ”は１〜３の整数であり；ｎ”は０または１である。］

[Wherein, R ″ ¹⁰¹ represents an aliphatic cyclic group which may have a substituent, groups represented by the above formulas (r-hr-1) to (r-hr-6), or a substituent. R ″ ¹⁰² represents an aliphatic cyclic group that may have a substituent, and the above formulas (a2-r-1) to (a2-r—). 7) represented by a lactone-containing cyclic group or the general formula (a5-r-1) ~ (a5-r-4) represented by -SO _2, - be-containing cyclic ^{group; R "103} is An aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent or a chain alkenyl group which may have a substituent; v ″ Are each independently an integer of 0 to 3; q ″ is independently an integer of 1 to 20; t ″ is an integer of 1 to 3; n ″ is 0 or 1.]

The aliphatic cyclic group which may have a substituent of R ″ ¹⁰¹ , R ″ ¹⁰² and R ″ ¹⁰³ is preferably a group exemplified as the cyclic aliphatic hydrocarbon group in R ¹⁰¹ .
Examples of the substituent, an aliphatic hydrocarbon group substituent which may be substituted cyclic in R ¹⁰¹ can be mentioned as well.

An aromatic cyclic group which may have a substituent in R ^"103, the it is preferred that the R ¹⁰¹ is a group exemplified as the aromatic cyclic hydrocarbon group. Examples of the substituent, in R ¹⁰¹ The substituent which may substitute a cyclic aromatic hydrocarbon group is mentioned similarly.

The chain alkyl group which may have a substituent in R ″ ¹⁰¹ is preferably the group exemplified as the chain alkyl group in R ^101. The chain in R ″ ¹⁰³ has a substituent. The good chain alkenyl group is preferably the group exemplified as the chain alkenyl group in R ¹⁰¹ .

In formula (b-2), R ¹⁰⁴ and R ¹⁰⁵ are each independently an alkyl group having 1 to 10 carbon atoms or a fluorinated alkyl group, and may be bonded to each other to form a ring.
R ¹⁰⁴ and R ¹⁰⁵ are preferably linear or branched (fluorinated) alkyl groups. The (fluorinated) alkyl group has 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, and more preferably 1 to 3 carbon atoms. The number of carbon atoms of the (fluorinated) alkyl group of R ¹⁰⁴ and R ¹⁰⁵ is preferably as small as possible because of good solubility in a resist solvent within the above carbon number range.
Further, in the (fluorinated) alkyl group of R ¹⁰⁴ and R ^105, the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, and the transparency to high energy light and electron beams of 200 nm or less This is preferable because of improved properties.
The proportion of fluorine atoms in the (fluorinated) alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all hydrogen atoms are replaced with fluorine atoms. Perfluoroalkylene group or perfluoroalkyl group.

{Cation part}
In the formulas (b-1) and (b-2), M ^{m +} is an m-valent organic cation. The organic cation is not particularly limited, and an organic cation known as a cation part such as an onium-based acid generator of a conventional resist composition can be used. Among these, a sulfonium cation or an iodonium cation is preferable, and those represented by the following general formulas (ca-1) to (ca-4) are particularly preferable.

［式中、Ｒ^２０１〜Ｒ^２０７およびＲ^２１１〜Ｒ^２１２は、それぞれ独立に置換基を有していてもよいアリール基、アルキル基またはアルケニル基であり、Ｒ^２０１〜Ｒ^２０３、Ｒ^２０６〜Ｒ^２０７、Ｒ^２１１〜Ｒ^２１２は、相互に結合して式中のイオウ原子と共に環を形成してもよく；Ｒ^２０８〜Ｒ^２０９はそれぞれ独立に水素原子または炭素数１〜５のアルキル基であり；Ｒ^２１０は置換基を有していてもよいアリール基、アルキル基、アルケニル基、又は−ＳＯ_２−含有環式基であり；Ｌ^２０１は−Ｃ（＝Ｏ）−または−Ｃ（＝Ｏ）Ｏ−であり；Ｙ^２０１は、それぞれ独立に、アリーレン基、アルキレン基またはアルケニレン基であり；ｘは１または２であり、Ｗ^２０１は（ｘ＋１）価の連結基である。］

[Wherein, R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² are each independently an aryl group, an alkyl group or an alkenyl group which may have a substituent, and R ^{201 to} R ²⁰³ , R ^{206 to} R ²⁰⁷ and R ^{211 to} R ²¹² may be bonded to each other to form a ring together with the sulfur atom in the formula; R ^{208 to} R ²⁰⁹ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ²¹⁰ is an optionally substituted aryl group, alkyl group, alkenyl group, or —SO ₂ — containing cyclic group; L ²⁰¹ is —C (═O) — or —C (═O Y ²⁰¹ is independently an arylene group, an alkylene group or an alkenylene group; x is 1 or 2, and W ²⁰¹ is a (x + 1) -valent linking group. ]

As the aryl group in R ²⁰¹ to R ²⁰⁷ and ^R 210 ^{to R 212,} include unsubstituted aryl group having 6 to 20 carbon atoms, a phenyl group, a naphthyl group.
The alkyl group in R ^{201 to} R ²⁰⁷ and R ^{210 to} R ²¹² is a chain or cyclic alkyl group and preferably has 1 to 30 carbon atoms.
The alkenyl group in R ^{201 to} R ²⁰⁷ and R ^{210 to} R ²¹² preferably has 2 to 10 carbon atoms.
R ^{208 to} R ²⁰⁹ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when they are alkyl groups, they may be bonded to each other to form a ring.
Examples of the —SO ₂ — containing cyclic group which may have a substituent for R ²¹⁰ include the same as the “—SO ₂ — containing cyclic group” of Ra ²¹ , and the general formula (a5- Those represented by r-1) are preferred.
Examples of the substituent that R ^{201 to} R ²⁰⁷ and R ^{210 to} R ²¹² may have include, for example, an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, Examples include the substituents represented by (ca-r-1) to (ca-r-7).

［式中、Ｒ’^２０１はそれぞれ独立に、水素原子、置換基を有していてもよい環式基、鎖状のアルキル基、または鎖状のアルケニル基である。］

[Wherein, R ′ ²⁰¹ each independently represents a hydrogen atom, an optionally substituted cyclic group, a chain alkyl group, or a chain alkenyl group. ]

The cyclic group, chain alkyl group, or chain alkenyl group which may have a substituent for R ′ ²⁰¹ may be the same as those described above for R ¹⁰¹ , or may have a substituent. Examples of the chain-like alkyl group that may have a cyclic group or a substituent may include the same groups as those in the above formula (a1-r-2).

^{R 201 ~R 203, R 206 ~R} 207, R 211 ~R 212 , when bonded to each other to form a ring with the sulfur atom, a sulfur atom, an oxygen atom, or a hetero atom such as nitrogen atom, carbonyl _{group, -SO -, - SO 2 -} , - SO 3 -, - COO -, - CONH- , or -N _(R N) - (. the _{R N} is an alkyl group having 1 to 5 carbon atoms), etc. You may couple | bond through the functional group of.
As the ring to be formed, one ring containing a sulfur atom in the ring skeleton in the formula is preferably a 3- to 10-membered ring, particularly a 5- to 7-membered ring, including the sulfur atom. preferable.
Specific examples of the ring formed include, for example, thiophene ring, thiazole ring, benzothiophene ring, thianthrene ring, benzothiophene ring, dibenzothiophene ring, 9H-thioxanthene ring, thioxanthone ring, thianthrene ring, phenoxathiin ring, tetrahydro A thiophenium ring, a tetrahydrothiopyranium ring, etc. are mentioned.

In the formula (ca-4), x is 1 or 2.
W ²⁰¹ is a (x + 1) valent, that is, a divalent or trivalent linking group.
The divalent linking group in W ²⁰¹ is preferably a divalent hydrocarbon group which may have a substituent, and examples thereof include the same hydrocarbon groups as Ya ²¹ in the general formula (a2). The divalent linking group in W ²⁰¹ may be linear, branched or cyclic, and is preferably cyclic. Of these, a group in which two carbonyl groups are combined at both ends of the arylene group is preferable. Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferable.
^Examples of the trivalent linking group in W ²⁰¹ include a group in which one hydrogen atom has been removed from the divalent linking group, a group in which the divalent linking group is further bonded to the divalent linking group, and the like. . The trivalent linking group in W ²⁰¹ is preferably a group in which three carbonyl groups are combined with an arylene group.

  Specific examples of suitable cations of the formula (ca-1) include cations represented by the following formulas (ca-1-1) to (ca-1-63).

［式中、ｇ１、ｇ２、ｇ３は繰返し数を示し、ｇ１は１〜５の整数であり、ｇ２は０〜２０の整数であり、ｇ３は０〜２０の整数である。］

[Wherein, g1, g2, and g3 represent the number of repetitions, g1 is an integer of 1 to 5, g2 is an integer of 0 to 20, and g3 is an integer of 0 to 20. ]

［式中、Ｒ”^２０１は水素原子又は置換基であって、置換基としては前記Ｒ^２０１〜Ｒ^２０７、およびＲ^２１０〜Ｒ^２１２が有していてもよい置換基として挙げたものと同様である。］

[Wherein R ″ ²⁰¹ is a hydrogen atom or a substituent, and the substituent is the same as the substituents that R ^{201 to} R ²⁰⁷ and R ^{210 to} R ²¹² may have. is there.]

  Specific examples of suitable cations of the formula (ca-3) include the following formulas (ca-3-1) to (ca-3-6).

  Specific examples of suitable cations of the formula (ca-4) include the following formulas (ca-4-1) to (ca-4-2).

(B) A component may be used individually by 1 type and may be used in combination of 2 or more type.
0.5-60 mass parts is preferable with respect to 100 mass parts of (A) component, as for content of (B) component in a resist composition, 1-50 mass parts is more preferable, and 1-40 mass parts is further. preferable. By setting it as the said range, pattern formation is fully performed. Moreover, when each component of a resist composition is melt | dissolved in the organic solvent, since a uniform solution is obtained and storage stability becomes favorable, it is preferable.

<Other optional components>
[(D) component]
In addition to the component (A) or the components (A) and (B), the resist composition of the present invention further includes an acid diffusion controller component (hereinafter also referred to as “component (D)”). You may contain.
The component (D) acts as a quencher (acid diffusion controller) that traps acid generated by exposure from the component (B) and the like.
The component (D) in the present invention may be a photodegradable base (D1) (hereinafter referred to as “(D1) component”) that is decomposed by exposure and loses acid diffusion controllability. A non-corresponding nitrogen-containing organic compound (D2) (hereinafter referred to as “component (D2)”) may be used.

((D1) component)
By forming the resist composition containing the component (D1), the contrast between the exposed portion and the non-exposed portion can be improved when forming a resist pattern.
The component (D1) is not particularly limited as long as it is decomposed by exposure and loses acid diffusion controllability, and is a compound represented by the following general formula (d1-1) (hereinafter referred to as “(d1-1) component”). ), A compound represented by the following general formula (d1-2) (hereinafter referred to as “(d1-2) component”) and a compound represented by the following general formula (d1-3) (hereinafter referred to as “(d1- One or more compounds selected from the group consisting of “3) component”) are preferred.
The components (d1-1) to (d1-3) are decomposed in the exposed portion and lose acid diffusion controllability (basicity), and thus do not act as a quencher, and act as a quencher in an unexposed portion.

［式中、Ｒｄ^１〜Ｒｄ^４は置換基を有していてもよい置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、または置換基を有していてもよい鎖状のアルケニル基である。ただし、式（ｄ１−２）中のＲｄ^２における、Ｓ原子に隣接する炭素原子にはフッ素原子は結合していないものとする。Ｙｄ^１は単結合、または２価の連結基である。Ｍ^ｍ＋はそれぞれ独立にｍ価の有機カチオンである。］

[Wherein, Rd ^{1 to} Rd ⁴ are a cyclic group that may have a substituent that may have a substituent, a chain alkyl group that may have a substituent, or a substituent. A chain-like alkenyl group which may have However, a fluorine atom is not bonded to a carbon atom adjacent to the S atom in Rd ² in the formula (d1-2). Yd ¹ is a single bond or a divalent linking group. M ^{m +} is each independently an m-valent organic cation. ]

{(D1-1) component}
During Anion formula (d1-1), Rd ¹ is have an optionally substituted cyclic group which may have a substituent chain alkyl group or a substituted group, Or a similar chain alkenyl group to the same as R ¹⁰¹ .
Among these, Rd ¹ may have an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a substituent. A chain hydrocarbon group is preferred. The substituent that these groups may have is preferably a hydroxyl group, a fluorine atom or a fluorinated alkyl group.
The aromatic hydrocarbon group is more preferably a phenyl group or a naphthyl group.
The aliphatic cyclic group is more preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.
As the chain hydrocarbon group, a chain alkyl group is preferable. The chain alkyl group preferably has 1 to 10 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. A linear alkyl group such as a group or decyl group; 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group And branched chain alkyl groups such as 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, and the like.

The chain alkyl group is preferably a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent. 1-11 are preferable, as for carbon number of the fluorinated alkyl group which has a fluorine atom or a fluorinated alkyl group as a substituent, 1-8 are more preferable, and 1-4 are more preferable. The fluorinated alkyl group may contain an atom other than a fluorine atom. Examples of atoms other than fluorine atoms include oxygen atoms, carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms.
Rd ¹ is preferably a fluorinated alkyl group in which some or all of the hydrogen atoms constituting the linear alkyl group are substituted by fluorine atoms, and the hydrogen atom constituting the linear alkyl group It is preferable that all are fluorinated alkyl groups (linear perfluoroalkyl groups) substituted with fluorine atoms.

  Preferred specific examples of the anion moiety of the component (d1-1) are shown below.

-Cation part In formula (d1-1), Mm ⁺ is an m-valent organic cation.
The organic cation of M ^{m +} is not particularly limited, and examples thereof include those similar to the cations represented by the general formulas (ca-1) to (ca-4), respectively, and the formula (ca-1- Cations represented by 1) to (ca-1-63) are preferable.
As the component (d1-1), one type may be used alone, or two or more types may be used in combination.

{(D1-2) component}
· During anion formula (d1-2), Rd ² is has an optionally substituted cyclic group which may have a substituent chain alkyl group or a substituted group, A chain alkenyl group which may be the same as R ¹⁰¹ .
However, a fluorine atom is not bonded to a carbon atom adjacent to the S atom in Rd ² (not fluorine-substituted). Thereby, the anion of (d1-2) component turns into a moderate weak acid anion, and the quenching ability of (D) component improves.
Rd ² is preferably an aliphatic cyclic group which may have a substituent, and a group in which one or more hydrogen atoms have been removed from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane or the like. (It may have a substituent); it is more preferably a group obtained by removing one or more hydrogen atoms from camphor or the like.
The hydrocarbon group of Rd ² may have a substituent, and examples of the substituent include a hydrocarbon group (aromatic hydrocarbon group, aliphatic hydrocarbon group) in Rd ¹ of the formula (d1-1). The same thing as the substituent which may have is mentioned.

  Preferred specific examples of the anion moiety of the component (d1-2) are shown below.

-Cation part In formula (d1-2), Mm ⁺ is an m-valent organic cation, and is the same as Mm ⁺ in formula (d1-1).
As the component (d1-2), one type may be used alone, or two or more types may be used in combination.

{(D1-3) component}
During Anion formula (d1-3), Rd ³ is have an optionally substituted cyclic group which may have a substituent chain alkyl group or a substituted group, A chain alkenyl group that may be the same as R ^101, and is preferably a cyclic group containing a fluorine atom, a chain alkyl group, or a chain alkenyl group. Among them, a fluorinated alkyl group is preferable, and the same as the fluorinated alkyl group for Rd ¹ is more preferable.

In formula (d1-3), Rd ⁴ may have a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. Examples of the chain alkenyl group include those similar to R ¹⁰¹ . Among these, an alkyl group, an alkoxy group, an alkenyl group, or a cyclic group which may have a substituent is preferable.
The alkyl group in Rd ⁴ is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group. Tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. A part of the hydrogen atoms of the alkyl group of Rd ⁴ may be substituted with a hydroxyl group, a cyano group, or the like.
The alkoxy group in Rd ⁴ is preferably an alkoxy group having 1 to 5 carbon atoms. Specific examples of the alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n- Examples include butoxy group and tert-butoxy group. Of these, a methoxy group and an ethoxy group are preferable.
Examples of the alkenyl group in Rd ⁴ include those similar to R ¹⁰¹ described above, and a vinyl group, a propenyl group (allyl group), a 1-methylpropenyl group, and a 2-methylpropenyl group are preferable. These groups may further have, as a substituent, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.
Examples of the cyclic group for Rd ⁴ include the same groups as those described above for R ^101, and one or more hydrogen atoms are removed from a cycloalkane such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. An alicyclic group or an aromatic group such as a phenyl group or a naphthyl group is preferred. When Rd ⁴ is an alicyclic group, the resist composition is well dissolved in an organic solvent, whereby the lithography properties are improved. In addition, when Rd ⁴ is an aromatic group, in lithography using EUV or the like as an exposure light source, the resist composition is excellent in light absorption efficiency, and sensitivity and lithography characteristics are good.

In formula (d1-3), Yd ¹ represents a single bond or a divalent linking group.
The divalent linking group in Yd ¹ is not particularly limited, but may be a divalent hydrocarbon group (aliphatic hydrocarbon group or aromatic hydrocarbon group) which may have a substituent, or a hetero atom containing 2 Valent linking groups and the like. These may be the same as those exemplified in the description of the divalent linking group of Ya ²¹ in the formula (a2-1).
Yd ¹ is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof. The alkylene group is preferably a linear or branched alkylene group, and more preferably a methylene group or an ethylene group.

  Preferred specific examples of the anion moiety of the component (d1-3) are shown below.

-Cation part In formula (d1-3), Mm ⁺ is an m-valent organic cation, and is the same as Mm ⁺ in formula (d1-1).
As the component (d1-3), one type may be used alone, or two or more types may be used in combination.

As the component (D1), only one of the above components (d1-1) to (d1-3) may be used, or two or more may be used in combination.
The content of the component (D1) is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, with respect to 100 parts by mass of the component (A). More preferably, it is part by mass.
When the content of the component (D1) is not less than the preferable lower limit value, particularly good lithography characteristics and a resist pattern shape can be obtained. On the other hand, when it is not more than the upper limit value, the sensitivity can be maintained well and the throughput is also excellent.

{(D1) Component Production Method}
The manufacturing method of said (d1-1) component and (d1-2) component is not specifically limited, It can manufacture by a well-known method.
Further, (d1-3) component manufacturing method is not particularly limited, for example, if the formula (d1-3) Rd ⁴ in is a group having an oxygen atom at the terminal which binds to Yd ^1, below By reacting the compound (i-1) represented by the general formula (i-1) with the compound (i-2) represented by the following general formula (i-2), the following general formula (i- 3) The compound (i-3) represented by 3) is obtained, and the compound (i-3) is reacted with Z ⁻ (M ^{m +} ) _{1 / m} (i-4) having a desired cation M ^{m +.} Thus, the compound (d1-3) represented by the general formula (d1-3) is produced.

［式中、Ｒｄ^４、Ｙｄ^１、Ｒｄ^３、Ｍ^ｍ＋は、それぞれ、前記一般式（ｄ１−３）中のＲｄ^４、Ｙｄ^１、Ｒｄ^３、Ｍ^ｍ＋と同じである。Ｒｄ^４ａはＲｄ^４から末端の酸素原子を除いた基であり、Ｚ⁻は対アニオンである。］

^{Wherein, Rd 4, Yd 1, Rd} 3, M m + , respectively, the general formula (d1-3) ^Rd 4 ^in, Yd ^1, Rd 3, the same as the ^{M m +.} Rd ^4a is a group obtained by removing the terminal oxygen atom from Rd ⁴ , and Z ⁻ is a counter anion. ]

First, compound (i-1) and compound (i-2) are reacted to obtain compound (i-3).
In formula (i-1), Rd ^4a is a group obtained by removing a terminal oxygen atom from Rd ⁴ . In formula (i-2), Yd ¹ and Rd ³ are the same as described above.
As compound (i-1) and compound (i-2), commercially available compounds may be used or synthesized.
The method for obtaining compound (i-3) by reacting compound (i-1) with compound (i-2) is not particularly limited. For example, compound (i-) can be obtained in the presence of an appropriate acid catalyst. After reacting 2) and compound (i-1) in an organic solvent, the reaction mixture can be washed and recovered.

The acid catalyst in the said reaction is not specifically limited, For example, toluenesulfonic acid etc. are mentioned, The usage-amount is about 0.05-5 mol with respect to 1 mol of compounds (i-2).
The organic solvent in the above reaction may be any material that can dissolve the compound (i-1) and the compound (i-2) as raw materials, and specifically includes toluene and the like. It is preferable that it is 0.5-100 mass parts with respect to (i-1), and it is more preferable that it is 0.5-20 mass parts. A solvent may be used individually by 1 type and may use 2 or more types together.
The amount of compound (i-2) used in the above reaction is usually preferably about 0.5 to 5 mol, more preferably about 0.8 to 4 mol, per 1 mol of compound (i-1).

The reaction time in the above reaction varies depending on the reactivity between the compound (i-1) and the compound (i-2), the reaction temperature, etc., but is usually preferably 1 to 80 hours, more preferably 3 to 60 hours. .
The reaction temperature in the above reaction is preferably 20 ° C to 200 ° C, more preferably about 20 ° C to 150 ° C.

Subsequently, the obtained compound (i-3) and the compound (i-4) are reacted to obtain the compound (d1-3).
In formula (i-4), M ^{m +} is the same as described above, and Z ⁻ is a counter anion. Z ^- is not particularly limited, a known product can be used for.
The method of reacting compound (i-3) and compound (i-4) to obtain compound (d1-3) is not particularly limited. For example, the compound is obtained in the presence of a suitable alkali metal hydroxide. It can be carried out by dissolving (i-3) in a suitable organic solvent and water, adding compound (i-4) and reacting with stirring.

The alkali metal hydroxide in the above reaction is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide and the like, and the amount used is 0.3 to 1 mol per 1 mol of compound (i-3). About 3 mol is preferable.
Examples of the organic solvent in the above reaction include solvents such as dichloromethane, chloroform, and ethyl acetate, and the amount used is preferably 0.5 to 100 parts by mass with respect to compound (i-3). More preferably, it is 5-20 mass parts. A solvent may be used individually by 1 type and may use 2 or more types together.
The amount of compound (i-4) used in the above reaction is usually preferably about 0.5 to 5 mol, more preferably about 0.8 to 4 mol, relative to 1 mol of compound (i-3).

The reaction time in the above reaction varies depending on the reactivity between the compound (i-3) and the compound (i-4), the reaction temperature, etc., but is usually preferably 1 to 80 hours, more preferably 3 to 60 hours. .
The reaction temperature in the above reaction is preferably 20 ° C to 200 ° C, more preferably about 20 ° C to 150 ° C.
After completion of the reaction, the compound (d1-3) in the reaction solution may be isolated and purified. For isolation and purification, conventionally known methods can be used. For example, concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, etc. can be used alone or in combination of two or more thereof. it can.

The structure of the compound (d1-3) obtained as described above is as follows: ¹ H-nuclear magnetic resonance (NMR) spectrum method, ¹³ C-NMR spectrum method, ¹⁹ F-NMR spectrum method, infrared absorption (IR) spectrum method. It can be confirmed by a general organic analysis method such as mass spectrometry (MS) method, elemental analysis method, X-ray crystal diffraction method.

  The content of the component (D1) is preferably 0.5 to 10.0 parts by mass and more preferably 0.5 to 8.0 parts by mass with respect to 100 parts by mass of the component (A). 1.0 to 8.0 parts by mass is even more preferable. When it is at least the lower limit of the above range, particularly good lithography properties and resist pattern shape can be obtained. When it is not more than the upper limit of the above range, the sensitivity can be maintained satisfactorily and the throughput is excellent.

((D2) component)
(D) component may contain the nitrogen-containing organic compound component (henceforth (D2) component) which does not correspond to the said (D1) component.
The component (D2) is not particularly limited as long as it functions as an acid diffusion control agent and does not correspond to the component (D1), and any known component may be used. Of these, aliphatic amines, particularly secondary aliphatic amines and tertiary aliphatic amines are preferred.
An aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic groups preferably have 1 to 12 carbon atoms.
Examples of the aliphatic amine include an amine (alkyl amine or alkyl alcohol amine) or a cyclic amine in which at least one hydrogen atom of ammonia NH ₃ is substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms.
Specific examples of alkylamines and alkyl alcohol amines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; diethylamine, di-n-propylamine, di- -Dialkylamines such as n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine , Trialkylamines such as tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, Li isopropanolamine, di -n- octanol amines, alkyl alcohol amines tri -n- octanol amine. Among these, a trialkylamine having 5 to 10 carbon atoms is more preferable, and tri-n-pentylamine or tri-n-octylamine is particularly preferable.

Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a hetero atom. The heterocyclic compound may be monocyclic (aliphatic monocyclic amine) or polycyclic (aliphatic polycyclic amine).
Specific examples of the aliphatic monocyclic amine include piperidine and piperazine.
As the aliphatic polycyclic amine, those having 6 to 10 carbon atoms are preferable. Specifically, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5. 4.0] -7-undecene, hexamethylenetetramine, 1,4-diazabicyclo [2.2.2] octane, and the like.

  Other aliphatic amines include tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2 -(1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2- {2- (2-hydroxy Ethoxy) ethoxy} ethyl] amine, triethanolamine triacetate and the like, and triethanolamine triacetate is preferable.

As the component (D2), an aromatic amine may be used.
Aromatic amines include aniline, pyridine, 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, diphenylamine, triphenylamine, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxy. And carbonylpyrrolidine.

(D2) A component may be used independently and may be used in combination of 2 or more type.
(D2) A component is normally used in 0.01-5.0 mass parts with respect to 100 mass parts of (A) component. By setting the content in the above range, the resist pattern shape, the stability over time, and the like are improved.

(D) A component may be used individually by 1 type and may be used in combination of 2 or more type.
When the resist composition of this invention contains (D) component, it is preferable that (D) component is 0.1-15 mass parts with respect to 100 mass parts of (A) component, 0.3- More preferably, it is 12 mass parts, and it is still more preferable that it is 0.5-12 mass parts. When it is at least the lower limit of the above range, lithography properties such as roughness are further improved when a resist composition is obtained. Further, a better resist pattern shape can be obtained. When the amount is not more than the upper limit of the above range, the sensitivity can be maintained satisfactorily and the throughput is excellent.

[(E) component]
The resist composition of the present invention comprises, as optional components, an organic carboxylic acid, a phosphorus oxo acid, and derivatives thereof for the purpose of preventing sensitivity deterioration and improving the resist pattern shape, retention stability over time, and the like. At least one compound (E) selected from the group (hereinafter referred to as component (E)) can be contained.
As the organic carboxylic acid, for example, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
Examples of phosphorus oxo acids include phosphoric acid, phosphonic acid, and phosphinic acid. Among these, phosphonic acid is particularly preferable.
Examples of the oxo acid derivative of phosphorus include esters in which the hydrogen atom of the oxo acid is substituted with a hydrocarbon group, and the hydrocarbon group includes an alkyl group having 1 to 5 carbon atoms and 6 to 6 carbon atoms. 15 aryl groups and the like.
Examples of phosphoric acid derivatives include phosphoric acid esters such as di-n-butyl phosphate and diphenyl phosphate.
Examples of phosphonic acid derivatives include phosphonic acid esters such as phosphonic acid dimethyl ester, phosphonic acid-di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, and phosphonic acid dibenzyl ester.
Examples of phosphinic acid derivatives include phosphinic acid esters and phenylphosphinic acid.
(E) A component may be used individually by 1 type and may use 2 or more types together.
(E) A component is normally used in 0.01-5.0 mass parts with respect to 100 mass parts of (A) component.

[(F) component]
The resist composition of the present invention may contain a fluorine additive (hereinafter referred to as “component (F)”) in order to impart water repellency to the resist film.
Examples of the component (F) include those described in JP 2010-002870 A, JP 2010-032994 A, JP 2010-277043 A, JP 2011-13569 A, and JP 2011-128226 A. These fluorine-containing polymer compounds can be used.
More specifically, examples of the component (F) include a polymer having a structural unit (f1) represented by the following formula (f1-1). As the polymer, a polymer (homopolymer) consisting only of the structural unit (f1) represented by the following formula (f1-1); a structural unit (f1) represented by the following formula (f1-1); A copolymer with the structural unit (a1); a structural unit (f1) represented by the following formula (f1-1); a structural unit derived from acrylic acid or methacrylic acid; and the structural unit (a1) It is preferable that it is a copolymer. Here, as the structural unit (a1) copolymerized with the structural unit (f1) represented by the following formula (f1-1), 1-ethyl-1-cyclooctyl (meth) acrylate or the formula (a1) -2-01) is preferred.

［式中、Ｒは前記と同様であり、Ｒｆ^１０２およびＲｆ^１０３はそれぞれ独立して水素原子、ハロゲン原子、炭素数１〜５のアルキル基、又は炭素数１〜５のハロゲン化アルキル基を表し、Ｒｆ^１０２およびＲｆ^１０３は同じであっても異なっていてもよい。ｎｆ^１は１〜５の整数であり、Ｒｆ^１０１はフッ素原子を含む有機基である。］

[Wherein, R is as defined above, and Rf ¹⁰² and Rf ¹⁰³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. , Rf ¹⁰² and Rf ¹⁰³ may be the same or different. nf ¹ is an integer of ¹ to 5, and Rf ¹⁰¹ is an organic group containing a fluorine atom. ]

In formula (f1-1), R bonded to the α-position carbon atom is the same as described above. R is preferably a hydrogen atom or a methyl group.
In formula (f1-1), examples of the halogen atom for Rf ¹⁰² and Rf ¹⁰³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. Examples of the alkyl group having 1 to 5 carbon atoms of Rf ¹⁰² and Rf ¹⁰³ include the same as the alkyl group having 1 to 5 carbon atoms of R, and a methyl group or an ethyl group is preferable. Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms of Rf ¹⁰² and Rf ¹⁰³ include a group in which part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with a halogen atom. Can be mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. The inter alia ^{Rf 102} and ^{Rf 103,} a hydrogen atom, a fluorine atom, or an alkyl group of 1 to 5 carbon atoms is preferable, a hydrogen atom, a fluorine atom, a methyl group or an ethyl group, preferred.
In formula (f1-1), nf ¹ is an integer of ¹ to 5, preferably an integer of 1 to 3, and more preferably 1 or 2.

In formula (f1-1), Rf ¹⁰¹ is an organic group containing a fluorine atom, and is preferably a hydrocarbon group containing a fluorine atom.
The hydrocarbon group containing a fluorine atom may be linear, branched or cyclic, and preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms. The carbon number of 1 to 10 is particularly preferable.
The hydrocarbon group containing a fluorine atom preferably has 25% or more of the hydrogen atoms in the hydrocarbon group fluorinated, more preferably 50% or more fluorinated, and 60% or more. Fluorination is particularly preferable because the hydrophobicity of the resist film during immersion exposure is increased.
Among ^these, as ^{Rf 101,} particularly preferably a fluorinated hydrocarbon group having 1 to 5 carbon atoms, a trifluoromethyl _{group, -CH 2 -CF 3, -CH 2} -CF 2 -CF 3, -CH 2 -CH _{2 -CF 3, -CH (CF 3} ) 2, -CH 2 -CH 2 -CF 3, and most preferably _{-CH 2 -CH 2 -CF 2 -CF 2} -CF 2 -CF 3.

(F) As for the mass mean molecular weight (Mw) (polystyrene conversion reference | standard by gel permeation chromatography), 1000-50000 are preferable, 5000-40000 are more preferable, and 10000-30000 are the most preferable. If it is below the upper limit of this range, it has sufficient solubility in a resist solvent to be used as a resist, and if it is above the lower limit of this range, dry etching resistance and resist pattern cross-sectional shape are good.
The dispersity (Mw / Mn) of the component (F) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.2 to 2.5.

(F) A component may be used individually by 1 type and may use 2 or more types together.
(F) A component is used in the ratio of 0.5-10 mass parts with respect to 100 mass parts of (A) component.

[Other additives]
The resist composition of the present invention further contains, if desired, miscible additives such as additional resins for improving the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, A dye or the like can be appropriately added and contained.

[(S) component]
The resist composition of the present invention can be produced by dissolving the material in an organic solvent (hereinafter sometimes referred to as (S) component).
As the component (S), any component can be used as long as it can dissolve each component to be used to form a uniform solution. Conventionally, any one of known solvents for chemically amplified resists can be used. Two or more types can be appropriately selected and used.
For example, lactones such as γ-butyrolactone (GBL); ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone; ethylene glycol, diethylene glycol, propylene glycol, Polyhydric alcohols such as dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, the polyhydric alcohols or compounds having the ester bond Monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl Derivatives of polyhydric alcohols such as compounds having an ether bond such as ether [in these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane And esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethyl benzyl ether, cresyl Methyl ether, diphenyl ether, dibenzyl ether, phenetol, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesi An aromatic organic solvent such as tylene, dimethyl sulfoxide (DMSO) and the like can be mentioned.
These organic solvents may be used independently and may be used as 2 or more types of mixed solvents.
Of these, PGMEA, PGME, γ-butyrolactone, and EL are preferable.
Moreover, the mixed solvent which mixed PGMEA and the polar solvent is also preferable. The blending ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. It is preferable to be within the range.
More specifically, when EL or cyclohexanone is blended as the polar solvent, the mass ratio of PGMEA: EL or cyclohexanone is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. . Moreover, when mix | blending PGME as a polar solvent, the mass ratio of PGMEA: PGME becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8: 2, More preferably, it is 3: 7-7: 3.
In addition, as the component (S), a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone is also preferable. In this case, the mixing ratio of the former and the latter is preferably 70:30 to 95: 5.
(S) The usage-amount of a component is not specifically limited, It is a density | concentration which can be apply | coated to a board | substrate etc., and is suitably set according to a coating film thickness. Generally, it is used so that the solid content concentration of the resist composition is in the range of 1 to 20% by mass, preferably 2 to 15% by mass.

Since the resist composition of the present invention contains the component (A1) having the structural unit (a0), lithography characteristics are improved in pattern formation of a resist film using the resist composition. For example, LWR (line width roughness), EL (exposure margin), MEEF (mask error factor), etc. are improved. Further, a reduction in film thickness (film shrinkage) after post-exposure baking (PEB) or after development is suppressed, and a negative pattern can be formed with a high residual film rate even in a solvent development process, for example.
As described above, the effect is that the structural unit (a0) has R ¹ (lactone-containing cyclic group, —SO ₂ — containing cyclic group or carbonate-containing cyclic group) at the end, and W ² and By having the structure “—O-specific lactone-containing cyclic group —C (═O) —O—” between R ¹ and R ¹ , it is considered to be due to having steric bulk and high polarity.
The resist composition of the present invention may be used for either an alkali development process or a solvent development process. For example, when the component (A) is the component (A-1), it may be used in a method for forming a positive resist pattern in an alkali development process, or a method for forming a negative resist pattern in a solvent development process You may use for.
The resist composition of the present invention is particularly suitably used for a method for forming a negative resist pattern in a solvent development process. When a negative resist pattern is formed by a solvent development process, since the exposed portion remains as a resist pattern, it is highly useful that film shrinkage in the exposed portion can be suppressed.

≪Resist pattern formation method≫
The resist pattern forming method of the present invention includes a step of forming a resist film on a support using the resist composition of the present invention, a step of exposing the resist film, and developing the resist film to form a resist pattern. Forming.
The resist pattern forming method of the present invention can be performed, for example, as follows.
First, the resist composition is applied onto a support with a spinner or the like, and a baking (post-apply bake (PAB)) treatment is performed, for example, at a temperature of 80 to 150 ° C. for 40 to 120 seconds, preferably 60 to 90 seconds. To form a resist film.
Next, exposure or a mask pattern is performed on the resist film through a mask (mask pattern) on which a predetermined pattern is formed using an exposure apparatus such as an ArF exposure apparatus, an electron beam drawing apparatus, or an EUV exposure apparatus. After performing selective exposure by drawing or the like by direct irradiation of an electron beam without passing through, baking (post-exposure baking (PEB)) treatment is performed, for example, at a temperature of 80 to 150 ° C. for 40 to 120 seconds, preferably 60 to Apply for 90 seconds.
Next, the resist film is developed. The development treatment is performed using an alkaline developer in the case of an alkali development process, and using a developer (organic developer) containing an organic solvent in the case of a solvent development process.
A rinsing treatment is preferably performed after the development treatment. The rinse treatment is preferably a water rinse using pure water in the case of an alkali development process, and is preferably a rinse solution containing an organic solvent in the case of a solvent development process.
In the case of a solvent development process, after the development process or the rinse process, a process of removing the developer or rinse liquid adhering to the pattern with a supercritical fluid may be performed.
Drying is performed after development or rinsing. In some cases, a baking process (post-bake) may be performed after the development process. In this way, a resist pattern can be obtained.

The support is not particularly limited, and a conventionally known one can be used, and examples thereof include a substrate for electronic components and a substrate on which a predetermined wiring pattern is formed. More specifically, a silicon substrate, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. As a material for the wiring pattern, for example, copper, aluminum, nickel, gold or the like can be used.
Further, the support may be a substrate in which an inorganic and / or organic film is provided on the above-described substrate. An inorganic antireflection film (inorganic BARC) is an example of the inorganic film. Examples of the organic film include organic films such as an organic antireflection film (organic BARC) and a lower organic film in a multilayer resist method.
Here, the multilayer resist method is a method in which at least one organic film (lower organic film) and at least one resist film (upper resist film) are provided on a substrate, and the resist pattern formed on the upper resist film is used as a mask. This is a method of patterning a lower organic film, and it is said that a pattern with a high aspect ratio can be formed. That is, according to the multilayer resist method, the required thickness can be secured by the lower organic film, so that the resist film can be thinned and a fine pattern with a high aspect ratio can be formed.
In the multilayer resist method, basically, a method having a two-layer structure of an upper layer resist film and a lower layer organic film (two layer resist method), and one or more intermediate layers between the upper layer resist film and the lower layer organic film And a method of forming a multilayer structure of three or more layers (metal thin film etc.) (three-layer resist method).

The wavelength used for the exposure is not particularly limited, and ArF excimer laser, KrF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray, etc. Can be done using radiation. The resist composition is highly useful for KrF excimer laser, ArF excimer laser, EB or EUV, and is particularly useful for ArF excimer laser, EB or EUV.

The exposure method of the resist film may be normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or may be immersion exposure (Liquid Immersion Lithography).
In immersion exposure, the space between the resist film and the lens at the lowest position of the exposure apparatus is previously filled with a solvent (immersion medium) having a refractive index larger than that of air, and exposure (immersion exposure) is performed in that state. It is an exposure method.
As the immersion medium, a solvent having a refractive index larger than the refractive index of air and smaller than the refractive index of the resist film to be exposed is preferable. The refractive index of such a solvent is not particularly limited as long as it is within the above range.
Examples of the solvent having a refractive index larger than the refractive index of air and smaller than the refractive index of the resist film include water, a fluorine-based inert liquid, a silicon-based solvent, and a hydrocarbon-based solvent.
Specific examples of the fluorine-based inert liquid include a fluorine-based compound such as C ₃ HCl ₂ F ₅ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , and C ₅ H ₃ F ₇ as a main component. Examples thereof include liquids, and those having a boiling point of 70 to 180 ° C are preferable, and those having a boiling point of 80 to 160 ° C are more preferable. It is preferable that the fluorine-based inert liquid has a boiling point in the above range since the medium used for immersion can be removed by a simple method after the exposure is completed.
As the fluorine-based inert liquid, a perfluoroalkyl compound in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms is particularly preferable. Specific examples of the perfluoroalkyl compound include a perfluoroalkyl ether compound and a perfluoroalkylamine compound.
More specifically, examples of the perfluoroalkyl ether compound include perfluoro (2-butyl-tetrahydrofuran) (boiling point: 102 ° C.). Examples of the perfluoroalkylamine compound include perfluorotributylamine ( Boiling point of 174 ° C.).
As the immersion medium, water is preferably used from the viewpoints of cost, safety, environmental problems, versatility, and the like.

Examples of the alkali developer used for the development treatment in the alkali development process include a 0.1 to 10% by mass tetramethylammonium hydroxide (TMAH) aqueous solution.
The organic solvent contained in the organic developer used in the development process in the solvent development process is not particularly limited as long as it can dissolve the component (A) (component (A) before exposure). It can be selected as appropriate. Specific examples include ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, ether solvents, and other polar solvents, hydrocarbon solvents, and the like.
The ketone solvent is an organic solvent containing C—C (═O) —C in the structure. The ester solvent is an organic solvent containing C—C (═O) —O—C in the structure. The alcohol solvent is an organic solvent containing an alcoholic hydroxyl group in the structure, and “alcoholic hydroxyl group” means a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group. A nitrile solvent is an organic solvent containing a nitrile group in its structure. The amide solvent is an organic solvent containing an amide group in the structure. The ether solvent is an organic solvent containing C—O—C in the structure.
Among organic solvents, there are organic solvents that contain multiple types of functional groups that characterize each of the above solvents in the structure, but in that case, any of the solvent types that contain the functional groups of the organic solvent is applicable. Shall. For example, diethylene glycol monomethyl ether corresponds to both alcohol solvents and ether solvents in the above classification.
The hydrocarbon solvent is a hydrocarbon solvent made of a hydrocarbon which may be halogenated and having no substituent other than a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
Among the above, the organic solvent contained in the organic developer is preferably a polar solvent, and is preferably a ketone solvent, an ester solvent, a nitrile solvent, or the like.

Specific examples of each solvent include ketone solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, cyclohexanone, Methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, γ-butyrolactone, methylamylketone (2- Heptanone) and the like.
As the ketone solvent, methyl amyl ketone (2-heptanone) is preferable.

Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono Propyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene Recall monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxy Nethyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, pyrubin Methyl acid, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, 2-hydroxypropionate Examples include ethyl acid, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, and propyl-3-methoxypropionate.
As the ester solvent, butyl acetate is preferred.

  Examples of the nitrile solvent include acetonitrile, propionitryl, valeronitrile, butyronitryl and the like.

A known additive can be blended in the organic developer as required. Examples of the additive include a surfactant. The surfactant is not particularly limited. For example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. As the surfactant, a nonionic surfactant is preferable, and a fluorine-based surfactant or a silicon-based surfactant is more preferable.
When the surfactant is blended, the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and 0.01 to 0. 0% with respect to the total amount of the organic developer. 5 mass% is more preferable.

  The development process can be performed by a known development method. For example, a method in which a support is immersed in a developer for a certain period of time (dip method), a developer is raised on the surface of the support by surface tension, and is left for a certain period of time. (Paddle method), spraying developer on the surface of the support (spray method), coating the developer while scanning the developer coating nozzle at a constant speed on the support rotating at a constant speed The method to continue (dynamic dispensing method) etc. are mentioned.

As the organic solvent contained in the rinsing liquid used for the rinsing process after the development process in the solvent developing process, for example, an organic solvent that is difficult to dissolve the resist pattern is selected as appropriate from the organic solvents used as the organic solvent used in the organic developer. Can be used. Usually, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. Among these, at least one selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents and amide solvents is preferable, and at least one selected from alcohol solvents and ester solvents is preferable. More preferred are alcohol solvents.
The alcohol solvent used for the rinse liquid is preferably a monohydric alcohol having 6 to 8 carbon atoms, and the monohydric alcohol may be linear, branched or cyclic. Specific examples include 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. It is done. Among these, 1-hexanol, 2-heptanol, and 2-hexanol are preferable, and 1-hexanol or 2-hexanol is more preferable.
Any one of these organic solvents may be used alone, or two or more thereof may be mixed and used. Moreover, you may mix and use organic solvents and water other than the above. However, in consideration of development characteristics, the blending amount of water in the rinsing liquid is preferably 30% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, more preferably 3% by mass or less based on the total amount of the rinsing liquid. Is particularly preferred.
A well-known additive can be mix | blended with a rinse liquid as needed. Examples of the additive include a surfactant. Examples of the surfactant include those described above, and nonionic surfactants are preferable, and fluorine-based surfactants or silicon-based surfactants are more preferable.
When the surfactant is blended, the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and 0.01 to 0.5% by mass with respect to the total amount of the rinse liquid. % Is more preferable.

  The rinse treatment (washing treatment) using the rinse liquid can be performed by a known rinse method. Examples of the method include a method of continuously applying a rinsing liquid on a support rotating at a constant speed (rotary coating method), a method of immersing the support in a rinsing liquid for a predetermined time (dip method), and the surface of the support. And a method of spraying a rinse liquid (spray method).

≪Polymer compound≫
The polymer compound of the present invention has a structural unit (a0) represented by the following general formula (a0).
The description of the polymer compound of the present invention is the same as the description of the component (A1) in the resist composition of the present invention.

［式中、Ａ”は、酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、Ｒ^１は、ラクトン含有環式基、−ＳＯ_２−含有環式基またはカーボネート含有環式基であり、Ｗ^２は、重合性基を含む基から重合反応により形成される基である。］

[Wherein, A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and R ¹ represents a lactone-containing cyclic group, —SO ₂ — Containing cyclic group or carbonate-containing cyclic group, and W ² is a group formed by a polymerization reaction from a group containing a polymerizable group.]

<< compound of the fourth aspect >>
The compound of the 4th aspect of this invention is a compound (henceforth a compound (I)) represented by the following general formula (I).
Compound (I) is useful as a raw material for the polymer compound of the present invention. By using the compound (I) as a monomer, a polymer compound having a structural unit represented by the general formula (a0) can be obtained.

［式中、Ａ”は、酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、Ｒ^１は、ラクトン含有環式基、−ＳＯ_２−含有環式基またはカーボネート含有環式基であり、Ｒ^２は、重合性基を含む基である。］

[Wherein, A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and R ¹ represents a lactone-containing cyclic group, —SO ₂ — Containing cyclic group or carbonate-containing cyclic group, and R ² is a group containing a polymerizable group.]

A in formula (I) ", ^{R 1,} respectively, A in the general formula (a0)", is the same as ^{R 1.}
Examples of the “group containing a polymerizable group” in R ² include the same “groups containing a polymerizable group” mentioned in the description of W ^{2 in} the general formula (a0).

<Method for Producing Compound (I)>
The production method of compound (I) is not particularly limited, and can be produced using a known method.
For example, a compound (01) represented by the following general formula (01) and a compound (02) represented by the following general formula (02) are dissolved in a solvent and reacted in the presence of a base to produce the following general formula A first step of obtaining a compound (03) represented by the formula (03);
A second step of obtaining a compound (II) represented by the following general formula (II) by an oxidation / cyclization reaction of the obtained compound (03);
The compound (I) can be produced by a production method comprising the third step of introducing R ² (group containing a polymerizable group) into the hydroxyl group of the obtained compound (II).

As the compounds (01) and (02), commercially available products may be used, or those synthesized by a known production method may be used.
The solvent used in the first step is not particularly limited as long as the compounds (01) and (02) to be used are soluble and do not react with them. For example, dichloromethane, dichloroethane, chloroform, tetrahydrofuran, N, N-dimethyl Examples include formamide, acetonitrile, propionitrile and the like.
Examples of the base include inorganic bases such as sodium hydride, K ₂ CO ₃ and Cs ₂ CO ₃ ; organic bases such as triethylamine, N, N-dimethylaminopyridine and pyridine.
The oxidation / cyclization reaction in the second step can be performed by a method using an oxidizing agent such as formic acid, peracetic acid, m-chlorobenzoic acid, which is a known method.
For the introduction of R ² in the third step, conventionally known methods can be used as a method for introducing a group containing a polymerizable group into the hydroxyl group of an alcohol. The third step may be performed in one step or may be performed in multiple steps.
For example, as ^{R 2,} when introducing the compound (II) a group having a carbonyl group at the end of the oxygen atom side of the hydroxyl groups of ((meth) acryloyl group), and compound ^(II), R 2 -X (X is And a halogen atom such as a chlorine atom or a hydroxyl group) can be reacted with each other to obtain a target compound.
After completion of the reaction, the compound in the reaction solution may be isolated and purified. For isolation and purification, conventionally known methods can be used. For example, concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, etc. can be used alone or in combination of two or more thereof. it can.
The structure of the compound obtained as described above includes ¹ H-nuclear magnetic resonance (NMR) spectrum method, ¹³ C-NMR spectrum method, ¹⁹ F-NMR spectrum method, infrared absorption (IR) spectrum method, mass spectrometry (MS ) Method, elemental analysis method, X-ray crystal diffraction method, etc.

<< Compound of the fifth aspect >>
The compound of the fifth aspect of the present invention is a compound represented by the following general formula (II) (hereinafter referred to as compound (II)).

［式中、Ａ”は、酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、Ｒ^１は、ラクトン含有環式基、−ＳＯ_２−含有環式基またはカーボネート含有環式基である。］

[Wherein A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and R ¹ is a lactone-containing cyclic group, —SO ₂ — Containing cyclic group or carbonate-containing cyclic group.]

A in formula (II) ", ^{R 1,} respectively, A in the general formula (a0)", is the same as ^{R 1.}
Compound (II) is useful as a raw material (intermediate) of the compound (I). As described above, compound (I) can be obtained by introducing R ² (group containing a polymerizable group) into the hydroxyl group of compound (II).

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited by these examples.
In the following, the compound represented by Formula 1 is referred to as Compound 1, and the same applies to compounds represented by other chemical formulas.
In the analysis by NMR, the internal standard of ¹ H-NMR and ¹³ C-NMR is tetramethylsilane (TMS).

<Synthesis Example 1: Synthesis of Compound H-1>
Alcohol 1 (46.8 g) and N, N-dimethylaminopyridine (40.3 g) were dissolved in dichloromethane (490 g) and cooled with ice. A solution of hymic anhydride (49.3 g) in dichloromethane was added dropwise to the solution. Then, after heating up to 25 degreeC and reacting for 12 hours, it ice-cooled and diluted hydrochloric acid (490g) was added, and reaction was stopped. Subsequently, washing was performed three times with pure water, and 61 g of Compound H-1 was obtained by adding hexane (4900 g).
The obtained compound was subjected to NMR measurement, and the structure was identified from the following results.
¹ H-NMR (400 MHz, DMSO-d6): δ (ppm) = 11.97 (1H, OH), 6.19-6.24 (1H, C═CH), 6.04-6.06 (1H , C = CH), 5.36-5.41 (1H, CH), 4.56-4.63 (3H, CH), 3.22-3.37 (2H, CH), 3.06 (2H , CH), 2.65-2.70 (1H, CH), 1.99-2.11 (2H, CH), 1.28-1.36 (2H, CH 2).

<Synthesis Example 2: Synthesis of Compound H-2>
Compound H-1 (6.4 g) and 88% formic acid (15.9 g) were added and heated to 45 ° C. 35% hydrogen peroxide (2.5 g) was added dropwise to the solution over 1 hour. After reacting at 45 ° C. for 12 hours, the mixture was cooled on ice and sodium hydrogen sulfite (1.5 g) was added to quench excess peroxide. Pure water (6.5 g) and sodium chloride (3.5 g) were added, and extraction was performed 5 times with dichloromethane (34 g). The dichloromethane phase was mixed, washed with an aqueous sodium hydrogen carbonate solution and further washed with pure water, and then the solvent was distilled off under reduced pressure to obtain 2.2 g of compound H-2.
The obtained compound was subjected to NMR measurement, and the structure was identified from the following results.
¹ H-NMR (400 MHz, DMSO-d6): δ (ppm) = 5.43-5.46 (1H, CH), 5.27-5.29 (1H, CH), 4.77 (1H, CH ), 4.52-4.66 (2H, CH), 4.35-4.37 (1H, CH), 4.04-4.08 (1H, CH), 3.15-3.24 (2H) , CH), 2.69-2.79 (2H, CH), 2.45-2.50 (1H, CH), 2.08-2.11 (2H, CH), 1.99 (1H, CH _{2), 1.55 (1H, CH} 2).

<Synthesis Example 3: Synthesis of Compound L-1>
Compound H-2 (14 g) and dichloromethane (140 g) were added and ice-cooled. Triethylamine (5.3 g) was added dropwise thereto, and further a dichloromethane solution of methacrylic acid chloride (4.6 g) was slowly added dropwise. The reaction was continued for 3 hours, and pure water was added to the reaction solution to stop the reaction. Liquid separation was performed, and the dichloromethane phase was washed with dilute hydrochloric acid, and then washed with pure water three times. The solution was added dropwise to diisopropyl ether (1400 g) to obtain 13 g of Compound L-1.
The obtained compound was subjected to NMR measurement, and the structure was identified from the following results.
¹ H-NMR (400 MHz, DMSO-d6): δ (ppm) = 6.07 (1H, C═CH), 5.73 (1H, C═CH), 5.41 (1H, CH), 5. 17 (1H, CH), 4.80 (1H, CH), 4.52-4.68 (3H, CH), 3.28-3.40 (2H, CH), 2.85-2.91 ( _{1H, CH), 2.69-2.73 (2H} , CH), 2.08-2.14 (2H, CH 2), 1.95 (1H, CH 2), 1.89 (3H, CH 3 ), 1.73 (1H, CH ₂ ).

<Synthesis Example 4: Synthesis of Compound L-2>
Methacrylic acid chloride _{(4.6g), CH 2 = C} (CH 3) equimolar amounts of _{C (= O) OCH 2 C} (= O) was changed to Cl in the same manner as in Synthesis Example 4 Compound L- 12 g of 2 was obtained.
The obtained compound was subjected to NMR measurement, and the structure was identified from the following results.
¹ H-NMR (400 MHz, DMSO-d6): δ (ppm) = 6.13 (1H, C═CH), 5.81 (1H, C═CH), 5.45 (1H, CH), 5. 17 (1H, CH), 4.78-4.81 (3H, CH + CH ₂ O), 4.52-4.68 (3H, CH), 3.28-3.40 (2H, CH), 2. 85-2.91 (1H, CH), 2.69-2.73 (2H, CH), 2.08-2.14 (2H, CH 2), 1.95 (1H, CH 2), 1. _{89 (3H, CH 3),} 1.73 (1H, CH 2).

<Synthesis Example 5: Synthesis of Compounds L-3 to L-6 and Compound (3)>
Compounds L-3 to L-6 and Compound (3) are obtained in the same manner as Compound L-1 or L-2, except that the hymic anhydride or alcohol 1 is changed to the corresponding carboxylic anhydride or alcohol. It was.

<Synthesis Example 6: Synthesis of Polymer-2>
Under a nitrogen atmosphere, 7.6 g of γ-butyrolactone (GBL) was placed in a flask connected with a thermometer, a reflux tube, a stirrer, and an N ₂ introduction tube, and the internal temperature was raised to 85 ° C. while stirring.
8.1 g (17.6 mmol) of compound L-2 and 4.5 g (22.9 mmol) of PcpMA were dissolved in 33 g of γ-butyrolactone (GBL). To this solution, 0.56 g of V-601 as a polymerization initiator was added and dissolved.
This mixed solution was dropped into the flask at a constant rate over 4 hours, and then heated and stirred for 1 hour to cool the reaction solution to room temperature.
The obtained reaction polymerization solution was dropped into a large amount of methanol / water mixed solution to precipitate a polymer, and the precipitated white powder was filtered, washed with a methanol / water mixed solution, and then dried under reduced pressure. As a result, 6.2 g of a polymer compound (Polymer-2) as a target product was obtained.
The weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement for this polymer compound was 7,600, and the molecular weight dispersity (PDI (Mw / Mn)) was 1.71. Moreover, the composition ratio (ratio (molar ratio) of each structural unit in the structural formula) of the copolymer determined by ¹³ C-NMR was L-2 / PcpMA = 49/51.

<Synthesis Examples 7 to 20: Synthesis of Polymer-1, 3 to 7, R1 to R6, and F1 to F2>
Polymer-1, 3, 7 and 11-18 were obtained in the same manner as in Synthesis Example 6 except that the type and amount of the monomer used were changed. Mw, PDI, and composition ratio (ratio of each structural unit in the structural formula (molar ratio)) of each polymer compound were measured in the same manner as described above.
The structural formulas of monomers used for the synthesis of Polymer-1 to 7, R1 to R6, and F1 to F2, and the measurement results of Mw, PDI, and composition ratio are shown below. “K” in Mw means × 10 ³ , for example, 7.5K indicates that Mw is 7500.

<Comparative example 1, Example 1, Comparative example 2, Examples 2-4>
Each component shown in Table 1 below was mixed and dissolved to prepare a resist composition.

In Table 1, the numerical value in [] is the blending amount (part by mass). Each abbreviation has the following meaning.
(A) -1 to (A) -4: Polymer-1 to Polymer-4, respectively.
(A) -R1 to (A) -R2: Polymer-R1 to Polymer-R2, respectively.
(B) -1: a compound represented by the following structural formula (B) -1.
(D) -1: A compound represented by the following structural formula (D) -1.
(F) -1: Polymer-F1.
(S) -1: γ-butyrolactone.
(S) -2: Mixed solvent of PGMEA / PGME / cyclohexanone = 45/30/25 (mass ratio).

The following evaluation was performed using the obtained resist composition.
[Formation of resist pattern 1]
An organic antireflection film composition “ARC29” (trade name, manufactured by Brewer Science Co., Ltd.) is applied onto a 12-inch silicon wafer using a spinner, and baked on a hot plate at 205 ° C. for 60 seconds to be dried. Thereby, an organic antireflection film having a film thickness of 89 nm was formed.
On this antireflection film, a resist composition is applied using a spinner, subjected to a pre-bake (PAB) treatment for 60 seconds at a temperature shown in Table 2 on a hot plate, and dried to obtain a film having a thickness of 80 nm. A resist film was formed.
Next, immersion ArF exposure apparatus NSR-S609B [manufactured by Nikon; NA (numerical aperture) = 1.07, Dipole 0.97 / 0.78 w / Polano, immersion medium: water ], An ArF excimer laser (193 nm) was selectively irradiated through a photomask (6% halftone). Thereafter, PEB treatment was performed at the temperatures shown in Table 2 for 60 seconds.
Next, alkaline development is performed for 10 seconds with a 2.38 mass% TMAH aqueous solution (trade name: NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C., and then 30 seconds of water using pure water. Rinse and shake-off drying.
As a result, in each example, a line and space (LS) pattern having a line width of 50 nm and a pitch of 100 nm was formed.

[Evaluation of exposure margin (EL)]
The exposure amount when the line of the LS pattern formed in the above [Resist pattern formation 1] is formed within the range of ± 5% (47.5 nm, 52.5 nm) of the target dimension is obtained. (Unit:%) was determined. The results are shown in Table 2 as “5% EL”. Note that EL indicates that the larger the value, the smaller the change in pattern size that accompanies the variation in exposure.
EL (%) = (| E1-E2 | / Eop) × 100
In the above formula, E1 is an exposure amount when an LS pattern having a line width of 47.5 nm is formed (mJ / cm ² ), and E2 is an exposure amount when an LS pattern having a line width of 52.5 nm is formed ( mJ / cm ² ), Eop indicates the optimum exposure amount for forming an LS pattern having a line width of 50 nm and a pitch of 100 nm. Eop was determined by a conventional method.

[Evaluation of LWR (Line Width Roughness)]
The space width of the LS pattern formed in the above [Resist pattern formation 1] was measured using a length measurement SEM (scanning electron microscope, acceleration voltage 300 V, trade name: S-9380, manufactured by Hitachi High-Technologies Corporation). 400 points were measured in the direction, and a value (3s) three times the standard deviation (s) was obtained from the result, and a value averaged over 3s at 400 points was calculated as a scale indicating LWR. The results are shown in Table 2. A smaller value of 3s means that the roughness of the line width is smaller, and an LS pattern having a more uniform width is obtained.

[Evaluation of mask error factor (MEEF)]
In accordance with the same procedure as the formation of the LS pattern formed in the above [Resist pattern formation 1], the mask pattern having a line pattern target size of 45 to 54 nm (10 nm increments in total of 1 point) at the same exposure amount, respectively. An LS pattern having a pitch of 100 nm was formed. At this time, the slope of the straight line when the target size (nm) was plotted on the horizontal axis and the size (nm) of the line pattern formed on the resist film using each mask pattern was plotted on the vertical axis was calculated as MEEF. The results are shown in Table 2. MEEF (straight line) means that the closer the value is to 1, the better the mask reproducibility.

As shown in the above results, the resist composition of Example 1 is 5% EL in comparison with Comparative Example 1 having the same composition except that the “constituent unit having a lactone-containing cyclic group” included in the component (A) is different. , LWR and MEEF were improved.
Similarly, the resist compositions of Examples 2 to 4 have 5% EL as compared with Comparative Example 2 having the same composition except that the “structural unit having a lactone-containing cyclic group” included in the component (A) is different. Lithography characteristics such as LWR and MEEF were improved.

<Comparative Examples 3-6, Examples 5-9, Comparative Example 7, Example 10>
Each component shown in Table 3 below was mixed and dissolved to prepare a resist composition.

In Table 3, the numerical value in [] is a blending amount (part by mass). Each abbreviation has the following meaning.
(A) -2 to (A) -7: Polymer-2 to Polymer-7, respectively.
(A) -R2 to (A) -R6: Polymer-R2 to Polymer-R6, respectively.
(B) -1: a compound represented by the structural formula (B) -1.
(B) -2 to (B) -3: Compounds represented by the following structural formulas (B) -2 to (B) -3, respectively.
(D) -2: A compound represented by the following structural formula (D) -2.
(F) -2: Polymer-F2.
(S) -1: γ-butyrolactone.
(S) -3: PGMEA / cyclohexanone = 90/10 (mass ratio) mixed solvent.

The following evaluation and measurement were performed using the obtained resist composition.
[Resist pattern formation 2]
An organic antireflection film composition “ARC29” (trade name, manufactured by Brewer Science Co., Ltd.) is applied onto a 12-inch silicon wafer using a spinner, and baked on a hot plate at 205 ° C. for 60 seconds to be dried. Thereby, an organic antireflection film having a film thickness of 89 nm was formed.
On this antireflection film, a resist composition is applied using a spinner, subjected to a pre-bake (PAB) treatment for 60 seconds at a temperature shown in Table 4 on a hot plate, and dried to have a film thickness of 100 nm. A resist film was formed.
Next, an immersion ArF exposure apparatus NSR-S609B [manufactured by Nikon; NA (numerical aperture) = 1.07, Annual 0.97 / 0.78 w / Polano, immersion medium: water for the resist film. ], An ArF excimer laser (193 nm) was selectively irradiated through a photomask (6% halftone). Thereafter, PEB treatment was performed at the temperature shown in Table 4 for 60 seconds.
Next, solvent development was performed for 13 seconds with methyl amyl ketone (MAK) 2-heptanone at 23 ° C., and then shaken off and dried.
As a result, in each example, a contact hole (CH) pattern in which holes having a hole diameter of 55 nm were arranged at equal intervals (pitch 110 nm) was formed.

[EL evaluation]
The exposure amount when the hole of the CH pattern formed in [Resist pattern formation 2] is formed within a range of ± 5% (53 nm, 58 nm) of the target dimension is obtained, and EL (unit:%) is obtained by the following formula. ) The results are shown in Table 4 as “5% EL”.
EL (%) = (| E1-E2 | / Eop) × 100
In the above formula, E1 is the exposure amount when a CH pattern with a hole diameter of 53 nm is formed (mJ / cm ² ), and E2 is the exposure amount when a CH pattern with a hole diameter of 58 nm is formed (mJ / cm ^2). ), Eop indicates an optimum exposure amount at which a CH pattern having a hole diameter of 55 nm is formed. Eop was determined by a conventional method.

[Evaluation of Circularity]
The 25 holes in the CH pattern formed in [Resist pattern formation 2] above are measured with a length measurement SEM (scanning electron microscope, acceleration voltage 300 V, trade name: S-9380, manufactured by Hitachi High-Technologies Corporation). The distance from the center of each hole to the outer edge was measured in 24 directions. A triple value (3σ) of the standard deviation (σ) calculated from the measurement result was obtained. The results are shown in Table 4. The 3σ obtained in this way means that the smaller the value, the higher the roundness of the hole.

[Evaluation of in-plane uniformity of pattern dimensions (CDU)]
100 holes in the CH pattern formed in [Resist pattern formation 2] above are measured with a length measurement SEM (scanning electron microscope, acceleration voltage 300 V, trade name: S-9380, manufactured by Hitachi High-Technologies Corporation). The hole diameter (nm) of each hole was measured. A triple value (3σ) of the standard deviation (σ) calculated from the measurement result was obtained. The results are shown in Table 4 as “CDU”. 3σ obtained in this way means that the smaller the value, the higher the dimension (CD) uniformity of the plurality of holes formed in the resist film.

[Measurement of remaining film ratio]
From the film thickness of the CH pattern formed using each resist composition (film thickness of the exposed area after solvent development) formed in [Resist pattern formation 2] above, the remaining film ratio (unit:%) by the following formula: Asked. The results are shown in Table 4.
Residual film rate (%) = (FT2 / FT1) × 100
In the above formula, FT1 represents the resist film thickness (nm) before exposure, and FT2 represents the film thickness (nm) of the CH pattern.
The film thickness was measured with Nanospec 6100A (manufactured by Nanometrics).

As shown in the above results, the resist compositions of Examples 5 to 9 are different from Comparative Examples 3 to 6 having the same composition except that the “structural unit having a lactone-containing cyclic group” included in the component (A) is different. Lithographic properties such as 5% EL, roundness and CDU were improved. Moreover, the remaining film rate of the exposed part was high, and film shrinkage was suppressed.
Similarly, the resist composition of Example 10 has 5% EL, perfect circle as compared with Comparative Example 7 having the same composition except that the “A structural unit having a lactone-containing cyclic group” included in the component (A) is different. And lithography properties such as CDU were improved. Moreover, the remaining film rate of the exposed part was high, and film shrinkage was suppressed.

[Example of polymer synthesis]
Polymer compounds 8 to 15 were synthesized in the same manner as in Synthesis Example 6 using the following monomers (1) to (9) for deriving structural units constituting each polymer compound. About the obtained high molecular compound, the copolymer composition ratio (ratio (molar ratio) of each structural unit in structural formula) calculated | required by the carbon 13 nuclear magnetic resonance spectrum (600MHz-13C-NMR, internal standard: tetramethylsilane). ) And mass average molecular weight (Mw) and molecular weight dispersity (Mw / Mn) in terms of standard polystyrene determined by GPC measurement are shown in Tables 5 and 6, respectively.

  Using the obtained polymer compound, resist compositions (Examples 11 to 22 and Comparative Examples 8 to 10) were prepared by blending each component at the blending ratio shown in Table 7 below.

In Table 7, each symbol has the following meaning, and the numerical value in [] is the blending amount (part by mass).
-(A) -8 to (A) -15: the polymer compounds 8 to 15, respectively.
-(B) -4 to (B) -8: The following compounds (B) -4 to (B) -8.
-(D) -1: The compound (D) -1.
-(D) -3 to (D) -4: The following compounds (D) -3 to (D) -4.
(F) -1: Polymer-F1.
-(F) -3: The following compound (F) -3 (Mw: 20000, PDI: 1.44, molar ratio: 1 / m = 22/78).
(S) -4: PGMEA.
(S) -5: PGME.
-(S) -6: cyclohexanone.

The following evaluation was performed using the obtained resist composition.
[Formation of resist pattern 3]
An organic antireflective coating composition “ARC95” (trade name, manufactured by Brewer Science) is applied onto a 12-inch silicon wafer using a spinner and baked on a hot plate at 205 ° C. for 60 seconds to be dried. Thereby, an organic antireflection film having a thickness of 90 nm was formed.
And
Each of the resist compositions shown in Table 7 (Examples 11 to 22 and Comparative Examples 8 to 10) was applied onto the antireflection film using a coater / developer Lithius (manufactured by Tokyo Electron Ltd.). A pre-baking (PAB) treatment for 60 seconds at a temperature was performed, followed by drying to form a resist film having a thickness of 90 nm.
Next, an immersion ArF exposure apparatus NSR-S609B [manufactured by Nikon; NA (numerical aperture) = 1.07, Dipole (in / out = 0.78 / 0.97) with Polano, An immersion medium: water] was selectively irradiated with an ArF excimer laser (193 nm) through a transmission type phase shift mask.
Thereafter, PEB treatment was performed at 95 ° C. for 60 seconds.
Next, using a coater / developer Lithius (manufactured by Tokyo Electron), alkali development for 10 seconds with a 2.38% by mass TMAH aqueous solution (trade name: NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. After that, water rinsing was performed for 30 seconds using pure water, followed by shaking off and drying.
As a result, in each example, a 1: 1 line and space (LS) pattern having a line width of 50 nm and a pitch of 100 nm was formed.

3σ, which is a measure of LWR, was determined for the LS pattern formed in [Resist pattern formation 3].
“3σ” is a standard obtained from a measurement result obtained by measuring 400 line widths in the longitudinal direction of a line with a scanning electron microscope (acceleration voltage 800 V, trade name: S-9220, manufactured by Hitachi High-Technologies Corporation). The triple value (3 s) (unit: nm) of the deviation (σ) is shown. The smaller the value of 3s, the smaller the roughness of the line side wall, which means that an LS pattern having a more uniform width was obtained. The results are shown in Table 8 as “LWR (nm)”.

[Measurement of pattern height]
The height of the LS pattern formed by the [resist pattern formation 3] was measured using a U-wafer shape / characteristic measuring device (trade name: SCD-XT, manufactured by KLA Tencor). The results are shown in Table 8.

  As shown in the above results, it was confirmed that the resist compositions of Examples 11 to 22 had LWR and pattern height equivalent or higher than those of Comparative Examples 8 to 10.

Claims (4)

The high molecular compound which has a structural unit (a0) represented by the following general formula (a0).

[Wherein, A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and R ¹ represents the following general formula (a2-r-4) , (A2-r-5) or (a2-r-7), a lactone-containing cyclic group, an —SO ₂ -containing cyclic group, or a carbonate-containing cyclic group, and W ² is A group formed by a polymerization reaction from a group represented by R ² ′ -L ¹ —, wherein R ² ′ is an optionally substituted hydrocarbon group containing an ethylenic double bond; And L ¹ is a divalent linking group containing a hetero atom or a single bond. ]

[Wherein, Ra ′ ²¹ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR ″, —OC (═O) R ″, a hydroxyalkyl group or a cyano group. Yes; R ″ is a hydrogen atom or an alkyl group; A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and m ′ is 0 or 1 It is. ] Furthermore, an acid dissociable group represented by the following general formula (a1-r-1), an acid dissociable group represented by the general formula (a1-r-2), or a general formula (a1-r-3) The high molecular compound of Claim 1 which has a structural unit (a1) containing the acid dissociable group represented .

[Wherein, Ra ′ ¹ and Ra ′ ² are a hydrogen atom or an alkyl group, Ra ′ ³ is a hydrocarbon group, and Ra ′ ³ is bonded to either Ra ′ ¹ or Ra ′ ² to form a ring. May be formed. Ra ^'4 ~Ra' ⁶ are each a hydrocarbon group, Ra ^'5, Ra' ⁶ may be bonded to each other to form a ring. Ra ^'7 ~Ra' ⁹ are each an alkyl group. ] The compound represented by the following general formula (I).

[Wherein, A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and R ¹ represents the following general formula (a2-r-4) A lactone-containing cyclic group represented by any one of (a2-r-5) and (a2-r-7), an —SO ₂ -containing cyclic group, or a carbonate-containing cyclic group, and R ² is R ² '-L 1 ^-. a group represented by the R ^2' contains an ethylenic double bond, a hydrocarbon group which may have a substituent group, wherein L ¹ is heteroaryl A divalent linking group containing atoms or a single bond. ]

[Wherein, Ra ′ ²¹ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR ″, —OC (═O) R ″, a hydroxyalkyl group or a cyano group. Yes; R ″ is a hydrogen atom or an alkyl group; A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and m ′ is 0 or 1 It is. ] The compound represented by the following general formula (II).

[Wherein, A ″ represents an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and R ¹ represents the following general formula (a2-r-2) A lactone-containing cyclic group, an —SO ₂ -containing cyclic group, or a carbonate-containing cyclic group represented by any one of (a2-r-7)]

[Wherein, Ra ′ ²¹ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR ″, —OC (═O) R ″, a hydroxyalkyl group or a cyano group. Yes; R ″ is a hydrogen atom or an alkyl group; A ″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and m ′ is 0 or 1 It is. ]