JP2021117264A - Method for forming resist pattern - Google Patents

Abstract

To provide a method for forming a resist pattern having good lithographic characteristics.SOLUTION: A method for forming a resist pattern includes steps of: obtaining a first polymer compound precursor represented by a general formula (Pre-1a); obtaining a polymer compound represented by a general formula (p1); and mixing the polymer compound and an organic solvent to prepare a resist composition. In the formulae, Rp01 and Rp04 are each a hydrogen atom or the like; Vp01 is a single bond or a divalent linking group; Rp02 and Rp03 are each a hydrocarbon group; Rp05 is an alkyl group or the like; Rp06 is an aliphatic hydrocarbon group; n1 is an integer of 0-4; and Ra001, Ra002 and Ra003 are each independently a hydrocarbon group.SELECTED DRAWING: None

Description

The present invention relates to a resist pattern forming method.

In the lithography technology, for example, a resist film made of a resist material is formed on a substrate, the resist film is selectively exposed, and a development process is performed to form a resist pattern having a predetermined shape on the resist film. The process of performing is performed. A resist material whose exposed portion of the resist film changes to a characteristic that dissolves in a developing solution is called a positive type, and a resist material whose exposed portion of a resist film changes to a characteristic that does not dissolve in a developing solution is called a negative type.
In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, pattern miniaturization is rapidly progressing due to advances in lithography technology. As a miniaturization method, generally, the wavelength of the exposure light source is shortened (energy is increased). Specifically, in the past, ultraviolet rays typified by g-rays and i-rays were used, but nowadays, mass production of semiconductor devices using KrF excimer lasers and ArF excimer lasers is being carried out. In addition, EUV (extreme ultraviolet rays), EB (electron beam), X-rays, etc., which have shorter wavelengths (higher energy) than these excimer lasers, are also being studied.

The resist material is required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing a pattern of fine dimensions.
Conventionally, as a resist material satisfying such a requirement, 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 by exposure. Is used.
For example, when the developer is an alkaline developer (alkali development process), the positive chemically amplified resist composition includes a resin component (base resin) whose solubility in the alkaline developer is increased by the action of an acid and acid generation. Those containing an agent component are generally used. When a resist film formed by using such a resist composition is selectively exposed at the time of forming a resist pattern, an acid is generated from an acid generator component in the exposed portion, and the polarity of the base resin is increased by the action of the acid. Then, the exposed portion of the resist film becomes soluble in the alkaline developer. Therefore, alkaline development forms a positive pattern in which the unexposed portion of the resist film remains as a pattern.
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), when the polarity of the base resin increases, the organic developer is relatively developed. Since the solubility in the liquid is lowered, the unexposed portion of the resist film is dissolved and removed by the organic developer, and a negative type resist pattern is formed in which the exposed portion of the resist film remains as a pattern. The solvent development process for forming a negative resist pattern in this way is sometimes called a negative development process.

The base resin used in the chemically amplified resist composition generally has a plurality of structural units in order to improve the lithography characteristics and the like.
For example, in the case of a resin component whose solubility in an alkaline developing solution is increased by the action of an acid, a structural unit containing an acid-degradable group whose polarity is increased by the action of an acid generated from an acid generator or the like is used. In addition, a structural unit containing a lactone-containing cyclic group, a structural unit containing a polar group such as a hydroxyl group, and the like are used in combination.

A wide variety of acid generator components used in the chemically amplified resist composition have been proposed so far. For example, onium salt-based acid generators such as iodonium salt and sulfonium salt, oxime sulfonate-based acid generators, diazomethane-based acid generators, nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, disulfonate-based acid generators, etc. It has been known.
As the onium salt-based acid generator, those having an onium ion such as triphenylsulfonium in the cation portion are mainly used. As the anion portion of the onium salt-based acid generator, a fluorinated alkyl sulfonic acid ion in which a part or all of the hydrogen atom of the alkyl sulfonic acid ion or its alkyl group is replaced with a fluorine atom is generally used. ..

In the formation of the resist pattern, the behavior of the acid generated from the acid generator component by exposure is considered to be one factor that has a great influence on the lithography characteristics.
In particular, when exposing EUV (extreme ultraviolet rays) or EB (electron beam), acid diffusion controllability becomes a problem in the resist material. Conventionally, methods for variously changing the design of polymer compounds have been proposed in order to control acid diffusion.
For example, a resist composition or the like is disclosed in which a polymer compound having a specific acid dissociation functional group is adopted, the reactivity with an acid is improved, and the solubility in a developing solution is improved (for example). , Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2009-114381 Japanese Unexamined Patent Publication No. 2012-220800

With the further progress of lithography technology and the miniaturization of resist patterns, for example, in lithography by EUV and EB, the goal is to form a fine pattern of several tens of nanometers. As the resist pattern size becomes smaller as described above, the resist composition is required to have high sensitivity to an exposure light source and good lithography characteristics such as reduction of roughness.
However, in the conventional resist composition as described above, if the sensitivity is increased with respect to an exposure light source such as EUV, it becomes difficult to obtain a desired resist pattern shape or the like, and all of these characteristics are satisfied. Was difficult.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resist pattern forming method having good lithography characteristics.

In the formation of a resist pattern, particularly when an EUV or EB is exposed to a resist film, it has a structural unit containing a hydroxystyrene skeleton and a structural unit containing an acid-degradable group whose polarity is increased by decomposition by the action of an acid. High molecular weight compounds are useful.
However, according to the study, the present inventors include the polymer compound obtained by randomly copolymerizing a monomer using a conventional radical polymerization method when forming a resist pattern using EUV or EB as an exposure light source. It was confirmed that when the resist composition was used, there was a problem that the lithography characteristics were likely to be adversely affected.
On the other hand, each protective group is obtained by copolymerizing a structural unit whose hydroxystyrene skeleton is protected with a protecting group that can be deprotected with an acid component and a structural unit having a specific imide structure, and then hydrolyzing the constituent units. We have found that the lithography properties can be improved by adopting the polymer compound obtained by deprotection, and have completed the present invention.

That is, in the first aspect of the present invention, the compound represented by the following general formula (m0-1) and the compound represented by the following general formula (m0-2) are copolymerized by living radical polymerization. , The step of obtaining the alternating copolymer represented by the following general formula (p0) and the first polymer compound precursor represented by the following general formula (Pre-1a) by hydrolyzing the alternating copolymer. The step of obtaining the body, the first polymer compound precursor, and the compound represented by the following general formula (Add-1) are reacted and represented by the following general formula (Pre-1b-1). A step of obtaining a second polymer compound precursor, and a step of hydrolyzing the second polymer compound precursor to obtain a polymer compound (A01) represented by the following general formula (p1). A step of preparing a resist composition by mixing the polymer compound (A01) and an organic solvent, a step of forming a resist film using the resist composition on a support, and an exposure of the resist film. This is a resist pattern forming method including a step of developing a resist film after exposure to form a resist pattern.

［式中、Ｒｐ^０１は、水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒｐ^０２及びＲｐ^０３は、それぞれ独立に置換基を有してもよい炭化水素基である。Ｒｐ^０２及びＲｐ^０３は、相互に結合して環を形成していてもよい。Ｒｐ^０４は、水素原子、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である。Ｒｐ^０５は、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、シアノ基又は水酸基である。Ｒｐ^０６は、直鎖状又は分岐鎖状の脂肪族炭化水素基である。ｎ_１は０〜４の整数である。］

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰² and Rp ⁰³ are hydrocarbon groups that may have independent substituents, respectively. Rp ⁰² and Rp ⁰³ may be coupled to each other to form a ring. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. ]

［式中、Ｒｐ^０１は、水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒｐ^０４は、水素原子、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である。Ｒｐ^０５は、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、シアノ基又は水酸基である。Ｒｐ^０６は、直鎖状又は分岐鎖状の脂肪族炭化水素基である。ｎ_１は０〜４の整数である。Ｒａ^００１、Ｒａ^００２及びＲａ^００３は、それぞれ独立に置換基を有してもよい炭化水素基である。Ｒａ^００２及びＲａ^００３は、相互に結合して環を形成していてもよい。］

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. Ra ⁰⁰¹ , Ra ⁰⁰² and Ra ⁰⁰³ are hydrocarbon groups that may each have an independent substituent. Ra ⁰⁰² and Ra ⁰⁰³ may be coupled to each other to form a ring. ]

［式中、Ｒｐ^０１及びＲｐ^０４は、それぞれ独立に水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒａ^００１、Ｒａ^００２及びＲａ^００３は、それぞれ独立に置換基を有してもよい炭化水素基である。Ｒａ^００２及びＲａ^００３は、相互に結合して環を形成していてもよい。Ｒｐ^０５は、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、シアノ基又は水酸基である。ｎ_１は０〜４の整数である。］

[In the formula, Rp ⁰¹ and Rp ⁰⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Ra ⁰⁰¹ , Ra ⁰⁰² and Ra ⁰⁰³ are hydrocarbon groups that may each have an independent substituent. Ra ⁰⁰² and Ra ⁰⁰³ may be coupled to each other to form a ring. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. n ₁ is an integer from 0 to 4. ]

In the second aspect of the present invention, the compound represented by the following general formula (m0-1) and the compound represented by the following general formula (m0-2) are copolymerized by living radical polymerization to be described below. A step of obtaining an alternating copolymer represented by the general formula (p0) and a step of hydrolyzing the alternating copolymer to obtain a first polymer compound precursor represented by the following general formula (Pre-2a). By reacting the obtaining step with the first polymer compound precursor and the compound represented by the following general formula (Add-1), the polymer compound (A01) represented by the following general formula (p1) is reacted. ), The step of mixing the polymer compound (A01) with an organic solvent to prepare a resist composition, and the step of forming a resist film on the support using the resist composition. , A resist pattern forming method including a step of exposing the resist film and a step of developing the resist film after the exposure to form a resist pattern.

［式中、Ｒｐ^０１は、水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒｐ^０２及びＲｐ^０３は、それぞれ独立に置換基を有してもよい炭化水素基である。Ｒｐ^０２及びＲｐ^０３は、相互に結合して環を形成していてもよい。Ｒｐ^０４は、水素原子、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である。Ｒｐ^０５は、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、シアノ基又は水酸基である。Ｒｐ^０６は、直鎖状又は分岐鎖状の脂肪族炭化水素基である。ｎ_１は０〜４の整数である。］

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰² and Rp ⁰³ are hydrocarbon groups that may have independent substituents, respectively. Rp ⁰² and Rp ⁰³ may be coupled to each other to form a ring. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. ]

［式中、Ｒｐ^０１は、水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒｐ^０４は、水素原子、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である。Ｒｐ^０５は、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、シアノ基又は水酸基である。ｎ_１は０〜４の整数である。Ｒａ^００１、Ｒａ^００２及びＲａ^００３は、それぞれ独立に置換基を有してもよい炭化水素基である。Ｒａ^００２及びＲａ^００３は、相互に結合して環を形成していてもよい。］

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. n ₁ is an integer from 0 to 4. Ra ⁰⁰¹ , Ra ⁰⁰² and Ra ⁰⁰³ are hydrocarbon groups that may each have an independent substituent. Ra ⁰⁰² and Ra ⁰⁰³ may be coupled to each other to form a ring. ]

In the third aspect of the present invention, the compound represented by the following general formula (m0-1) and the compound represented by the following general formula (m0-2) are copolymerized by living radical polymerization, and described below. A step of obtaining an alternating copolymer represented by the general formula (p0) and a step of hydrolyzing the alternating copolymer to obtain a first polymer compound precursor represented by the following general formula (Pre-1a). The step of obtaining the polymer compound precursor is reacted with the compound represented by the following general formula (Add-2), and the first polymer compound precursor is reacted and represented by the following general formula (Pre-1b-2). The step of obtaining the polymer compound precursor of No. 2 and the step of hydrolyzing the second polymer compound precursor to obtain the polymer compound (A02) represented by the following general formula (p2), and the above-mentioned high molecular weight compound. A step of preparing a resist composition by mixing a molecular compound (A02) and an organic solvent, a step of forming a resist film on a support using the resist composition, and a step of exposing the resist film. A method for forming a resist pattern, which comprises a step of developing the resist film after the exposure to form a resist pattern.

［式中、Ｒｐ^０１は、水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒｐ^０２及びＲｐ^０３は、それぞれ独立に置換基を有してもよい炭化水素基である。Ｒｐ^０２及びＲｐ^０３は、相互に結合して環を形成していてもよい。Ｒｐ^０４は、水素原子、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である。Ｒｐ^０５は、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、シアノ基又は水酸基である。Ｒｐ^０６は、直鎖状又は分岐鎖状の脂肪族炭化水素基である。ｎ_１は０〜４の整数である。］

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰² and Rp ⁰³ are hydrocarbon groups that may have independent substituents, respectively. Rp ⁰² and Rp ⁰³ may be coupled to each other to form a ring. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. ]

［式中、Ｒｐ^０１は、水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒｐ^０４は、水素原子、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である。Ｒｐ^０５は、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、シアノ基又は水酸基である。Ｒｐ^０６は、直鎖状又は分岐鎖状の脂肪族炭化水素基である。ｎ_１は０〜４の整数である。Ｒａ^００４、Ｒａ^００５は水素原子又はアルキル基である。Ｒａ^００６は炭化水素基であって、Ｒａ^００６は、Ｒａ^００４、Ｒａ^００５のいずれかと結合して環を形成してもよい。Ｘは、ハロゲン原子である。］

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. Ra ⁰⁰⁴ and Ra ⁰⁰⁵ are hydrogen atoms or alkyl groups. Ra ⁰⁰⁶ is a hydrocarbon group, and Ra ⁰⁰⁶ may be bonded to either Ra ⁰⁰⁴ or Ra ^{005 to form a ring.} X is a halogen atom. ]

［式中、Ｒｐ^０１及びＲｐ^０４は、それぞれ独立に水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒａ^００４、Ｒａ^００５は水素原子又はアルキル基である。Ｒａ^００６は炭化水素基であって、Ｒａ^００６は、Ｒａ^００４、Ｒａ^００５のいずれかと結合して環を形成してもよい。Ｒｐ^０５は、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、シアノ基又は水酸基である。ｎ_１は０〜４の整数である。］

[In the formula, Rp ⁰¹ and Rp ⁰⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Ra ⁰⁰⁴ and Ra ⁰⁰⁵ are hydrogen atoms or alkyl groups. Ra ⁰⁰⁶ is a hydrocarbon group, and Ra ⁰⁰⁶ may be bonded to either Ra ⁰⁰⁴ or Ra ^{005 to form a ring.} Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. n ₁ is an integer from 0 to 4. ]

A fourth aspect of the present invention is to copolymerize a compound represented by the following general formula (m0-1) and a compound represented by the following general formula (m0-2) by living radical polymerization, and then carry out the following. A step of obtaining an alternating copolymer represented by the general formula (p0) and a step of hydrolyzing the alternating copolymer to obtain a first polymer compound precursor represented by the following general formula (Pre-2a). By reacting the obtaining step with the first polymer compound precursor and the compound represented by the following general formula (Add-2), the polymer compound (A02) represented by the following general formula (p2) is reacted. ), The step of mixing the polymer compound (A02) with an organic solvent to prepare a resist composition, and the step of forming a resist film on the support using the resist composition. , A resist pattern forming method including a step of exposing the resist film and a step of developing the resist film after the exposure to form a resist pattern.

［式中、Ｒｐ^０１は、水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒｐ^０２及びＲｐ^０３は、それぞれ独立に置換基を有してもよい炭化水素基である。Ｒｐ^０２及びＲｐ^０３は、相互に結合して環を形成していてもよい。Ｒｐ^０４は、水素原子、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である。Ｒｐ^０５は、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、シアノ基又は水酸基である。Ｒｐ^０６は、直鎖状又は分岐鎖状の脂肪族炭化水素基である。ｎ_１は０〜４の整数である。］

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰² and Rp ⁰³ are hydrocarbon groups that may have independent substituents, respectively. Rp ⁰² and Rp ⁰³ may be coupled to each other to form a ring. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. ]

［式中、Ｒｐ^０１は、水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒｐ^０４は、水素原子、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である。Ｒｐ^０５は、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、シアノ基又は水酸基である。ｎ_１は０〜４の整数である。Ｒａ^００４、Ｒａ^００５は水素原子又はアルキル基である。Ｒａ^００６は炭化水素基であって、Ｒａ^００６は、Ｒａ^００４、Ｒａ^００５のいずれかと結合して環を形成してもよい。Ｘは、ハロゲン原子である。］

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. n ₁ is an integer from 0 to 4. Ra ⁰⁰⁴ and Ra ⁰⁰⁵ are hydrogen atoms or alkyl groups. Ra ⁰⁰⁶ is a hydrocarbon group, and Ra ⁰⁰⁶ may be bonded to either Ra ⁰⁰⁴ or Ra ^{005 to form a ring.} X is a halogen atom. ]

According to the resist pattern forming method of the present invention, it is possible to provide a resist pattern forming method having good lithography characteristics.

As used herein and in the claims, "aliphatic" is defined as a relative concept to aromatics, meaning groups, compounds, etc. that do not have aromatic properties.
Unless otherwise specified, the "alkyl group" shall include linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
Unless otherwise specified, the "alkylene group" shall include linear, branched and cyclic divalent saturated hydrocarbon groups.
Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The “constituent unit” means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
When "may have a substituent" is described, a hydrogen atom (-H) is replaced with a monovalent group, and a methylene group (-CH _2- ) is replaced with a divalent group. Including both.
"Exposure" is a concept that includes general irradiation of radiation.

An "acid-degradable group" is a group having an acid-degradable property in which at least a part of the bonds in the structure of the acid-degradable group can be cleaved by the action of an acid.
Examples of the acid-degradable group whose polarity is increased by the action of an acid include a group which is decomposed by the action of an acid to produce a polar group.
Examples of the polar group, such as carboxy group, a hydroxyl group, an amino group, such as a sulfo group _(-SO 3 H) and the like.
More specific examples of the acid-degradable group include a group in which the polar group is protected by an acid-dissociable group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected by an acid-dissociable group).

The "acid dissociative group" is (i) a group having acid dissociation that allows the bond between the acid dissociative group and an atom adjacent to the acid dissociative group to be cleaved by the action of an acid, or a group having acid dissociation. (Ii) A group capable of cleaving a bond between the acid dissociative group and an atom adjacent to the acid dissociative group by causing a decarbonation reaction after a part of the bond is cleaved by the action of an acid. , Both.
The acid dissociable group constituting the acid-degradable group needs to be a group having a lower polarity than the polar group produced by the dissociation of the acid-dissociable group, whereby the acid-dissociable group is affected by the action of the acid. When is dissociated, a polar group having a higher polarity than the acid dissociative group is generated and the polarity is increased. As a result, the polarity of the entire (A1) component increases. As the polarity increases, the solubility in the developer changes relatively, the solubility increases when the developer is an alkaline developer, and the solubility increases when the developer is an organic developer. Decrease.

The "base material component" is an organic compound having a film-forming ability. Organic compounds used as base material components 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 term "small molecule compound" refers to a non-polymer having a molecular weight of 500 or more and less than 4000. As the polymer, a polymer having a molecular weight of 1000 or more is usually used. Hereinafter, the terms "resin", "polymer compound" or "polymer" indicate a polymer having a molecular weight of 1000 or more. As the molecular weight of the polymer, the polystyrene-equivalent weight average molecular weight by GPC (gel permeation chromatography) shall be used.

"Derived building block" means a building block formed by cleavage of multiple bonds between carbon atoms, for example, an ethylenic double bond.
In the "acrylic acid ester", the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. ^{The substituent (R αx} ) that replaces the hydrogen atom bonded to the carbon atom at the α-position is an atom or group other than the hydrogen atom. In addition, ^{an itaconic acid diester in which the substituent (R αx} ) is substituted with a substituent containing an ester bond, ^{and an α-hydroxyacrylic ester in which the substituent (R αx} ) is substituted with a hydroxyalkyl group or a group modified with a hydroxyl group thereof are also available. It shall include. Unless otherwise specified, the carbon atom at the α-position of the acrylic acid ester is a carbon atom to which the carbonyl group of acrylic acid is bonded.
Hereinafter, an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the α-position is substituted with a substituent may be referred to as an α-substituted acrylic acid ester.

The "derivative" is a concept including a compound in which the hydrogen atom at the α-position is substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. As those derivatives, the hydrogen atom at the α-position may be substituted with a substituent. The hydrogen atom of the hydroxyl group of the target compound is substituted with an organic group; even if the hydrogen atom at the α-position is substituted with a substituent. Examples of a good target compound include those to which a substituent other than a hydroxyl group is bonded. The α-position refers to the first carbon atom adjacent to the functional group unless otherwise specified.
^{Examples of} the substituent that replaces the hydrogen atom at the α-position of hydroxystyrene include those similar to R αx.

In the present specification and claims, some structures represented by chemical formulas have asymmetric carbons, and enantiomers and diastereomers may be present. In that case, one chemical formula is used to represent those isomers. These isomers may be used alone or as a mixture.

(Resist pattern forming method)
(First aspect)
The resist pattern forming method according to the first aspect of the present invention is
(Ia) The compound represented by the following general formula (m0-1) and the compound represented by the following general formula (m0-2) are copolymerized by living radical polymerization, and the following general formula (p0) is used. The step of obtaining the represented alternating copolymer (hereinafter, also referred to as step (ia)) and
(Iia) A step of hydrolyzing the alternating copolymer to obtain a first polymer compound precursor represented by the following general formula (Pre-1a) (hereinafter, also referred to as step (ia)).
(Iia) A second polymer compound precursor represented by the following general formula (Pre-1b-1) is reacted by reacting the first polymer compound precursor with a compound represented by the following general formula (Add-1). And the process of obtaining the polymer compound precursor of
(Iva) A step of hydrolyzing the second polymer compound precursor to obtain a polymer compound (A01) represented by the following general formula (p1) (hereinafter, also referred to as step (iva)).
(Va) A step of preparing a resist composition by mixing the polymer compound (A01) with an organic solvent (hereinafter, also referred to as step (va)).
(Via) A step of forming a resist film on the support using the resist composition (hereinafter, also referred to as step (via)).
(Via) A resist pattern forming method including a step of exposing the resist film and a step of developing the exposed resist film to form a resist pattern (hereinafter, also referred to as a step (via)).

［式中、Ｒｐ^０１は、水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒｐ^０２及びＲｐ^０３は、それぞれ独立に置換基を有してもよい炭化水素基である。Ｒｐ^０２及びＲｐ^０３は、相互に結合して環を形成していてもよい。Ｒｐ^０４は、水素原子、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である。Ｒｐ^０５は、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、シアノ基又は水酸基である。Ｒｐ^０６は、直鎖状又は分岐鎖状の脂肪族炭化水素基である。ｎ_１は０〜４の整数である。］

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰² and Rp ⁰³ are hydrocarbon groups that may have independent substituents, respectively. Rp ⁰² and Rp ⁰³ may be coupled to each other to form a ring. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. ]

［式中、Ｒｐ^０１は、水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒｐ^０４は、水素原子、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である。Ｒｐ^０５は、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、シアノ基又は水酸基である。Ｒｐ^０６は、直鎖状又は分岐鎖状の脂肪族炭化水素基である。ｎ_１は０〜４の整数である。Ｒａ^００１、Ｒａ^００２及びＲａ^００３は、それぞれ独立に置換基を有してもよい炭化水素基である。Ｒａ^００２及びＲａ^００３は、相互に結合して環を形成していてもよい。］

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. Ra ⁰⁰¹ , Ra ⁰⁰² and Ra ⁰⁰³ are hydrocarbon groups that may each have an independent substituent. Ra ⁰⁰² and Ra ⁰⁰³ may be coupled to each other to form a ring. ]

［式中、Ｒｐ^０１及びＲｐ^０４は、それぞれ独立に水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒａ^００１、Ｒａ^００２及びＲａ^００３は、それぞれ独立に置換基を有してもよい炭化水素基である。Ｒａ^００２及びＲａ^００３は、相互に結合して環を形成していてもよい。Ｒｐ^０５は、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、シアノ基又は水酸基である。ｎ_１は０〜４の整数である。］

[In the formula, Rp ⁰¹ and Rp ⁰⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Ra ⁰⁰¹ , Ra ⁰⁰² and Ra ⁰⁰³ are hydrocarbon groups that may each have an independent substituent. Ra ⁰⁰² and Ra ⁰⁰³ may be coupled to each other to form a ring. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. n ₁ is an integer from 0 to 4. ]

<Process (ia)>
In the step (ia), the compound represented by the following general formula (m0-1) and the compound represented by the following general formula (m0-2) are copolymerized by living radical polymerization, and the following general formula (m0-1) is used. This is a step of obtaining the alternating copolymer represented by p0).

≪Living radical polymerization≫
Living radical polymerization is a polymerization reaction in which the termination reaction is suppressed to some extent by the equilibrium between the Dormant species and the radical growth species, and the molecular weight can be controlled by a reversible exchange reaction. It is believed that if the exchange reaction occurs much faster than the polymerization reaction, a polymer with a narrow molecular weight distribution can be obtained.
Examples of living radical polymerization include those using a chain transfer agent such as polysulfide, those using a radical trapping agent such as a cobalt porphyrin complex and a nitroxide compound, and atom transfer using an organic halogen compound as an initiator and using a transition metal complex as a catalyst. Examples include radical polymerization. Among them, atom transfer radical polymerization is preferable.

-Atom transfer radical polymerization As the organic halogen compound in the atom transfer radical polymerization, an α-halogenocarbonyl compound, an α-halogenocarboxylic acid ester and the like can be used. Among them, α-halogenocarboxylic acid ester is preferable, and specific examples thereof include ethyl 2-bromo-2-methylpropanoate, 2-hydroxyethyl 2-bromopropionic acid, and 2-chloro-2,4,4-trimethylglutaric acid. Examples thereof include dimethyl and ethyl 2-chloro-2-phenylacetate, and ethyl 2-chloro-2-phenylacetate is more preferable.

The central metals constituting the transition metal complex in the atomic transfer radical polymerization include elements of Group 7 to 11 of the Periodic Table of the Periodic Table such as iron, copper, nickel, rhodium, ruthenium, and renium. (According to the periodic table described in "Revised 4th Edition" (1993)) is preferably mentioned. Among them, ruthenium and copper are more preferable.

Specific examples of the transition metal complex having ruthenium as the central metal include dichlorotris (triphenylphosphine) ruthenium, dichlorotris (tributylphosphine) ruthenium, dichloro (cyclooctadiene) ruthenium, dichlorobenzene ruthenium, and dichlorop-simene ruthenium. Dichloro (norbornadiene) ruthenium, cis-dichlorobis (2,2'-bipyridine) ruthenium, dichlorotris (1,10-phenanthroline) ruthenium, carbonylchlorohydridotris (triphenylphosphine) ruthenium, chlorocyclopentadienylbis (triphenyl) Examples thereof include ruthenium) ruthenium, chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium, and chloroindenylbis (triphenylphosphine) ruthenium. Among them, dichlorotris (triphenylphosphine) ruthenium, chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium (RuCp ^* catalyst), and chloroindenylbis (triphenylphosphine) ruthenium are preferable, and chloropentamethylcyclopenta. Dienylbis (triphenylphosphine) ruthenium (RuCp ^* catalyst) is more preferred.

In the atom transfer radical polymerization, Lewis acid or amine may be used as a co-catalyst.
Examples of Lewis acid include aluminum trialkoxides such as aluminum triisopropoxide and aluminum tri (t-butoxide); bis (2,6-di-t-butylphenoxy) methylaluminum and bis (2,4,6-tri-). Bis (substituted aryloxy) alkylaluminum such as t-butylphenoxy) methylaluminum; tris (substituted aryloxy) aluminum such as tris (2,6-diphenylphenoxy) aluminum; titanium tetraalkoxide such as titanium tetraisopropoxide Can be mentioned. Among them, aluminum trialkoxide is preferable, and aluminum triisopropoxide is more preferable.

Examples of amines include aliphatic primary amines such as methylamine, ethylamine, propylamine, isopropylamine and butylamine; aliphatic secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine and dibutylamine; trimethylamine, Aliphatic amines such as aliphatic tertiary amines such as triethylamine, tripropylamine, triisopropylamine and tributylamine; N, N, N', N'-tetramethylethylenediamine, N, N, N', N'' , N''-Pentamethyldiethylenetriamine, 1,1,4,7,10,10-Hexamethyltriethylenetetraamine and other aliphatic polyamines; aniline, toluidine and other aromatic primary amines; diphenylamine and other aromatics Secondary amines; aromatic amines such as triphenylamines, and aromatic amines such as tertiary amines can be mentioned. Among them, aliphatic amines are preferable, and specifically, butylamine, dibutylamine, and tributylamine are more preferable.

Examples of the solvent used for the atomic transfer radical polymerization include esters such as ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and cellosolves; and alkyl lactones such as γ-butyrolactone. Ethers such as tetrahydrofuran, dimethoxyethane, diethoxyethane; alkyl ketones such as 2-butanone (methyl ethyl ketone), 2-heptanone, methyl isobutyl ketone; cycloalkyl ketones such as cyclohexanone; 2-propanol, propylene glycol monomethyl ether , Alcohols such as isopropyl alcohol; hydrocarbons such as heptane, cyclohexane, cycloheptane, toluene, xylene; aproton polar solvents such as dimethylformamide (DMF), dimethylsulfoxide, dimethylacetamide, hexamethylphosphoroamide; dichloromethane , Dichloroethane, non-polar solvents such as chloroform and the like.
These solvents can be used alone or in admixture of two or more.

The reaction temperature in the atom transfer radical polymerization is usually 40 to 150 ° C, preferably 50 to 130 ° C.
The reaction time in the atom transfer radical polymerization is usually 1 to 96 hours, preferably 1 to 48 hours.

≪Compound (m0-1) ≫
The compound (m0-1) is a compound represented by the following general formula (m0-1).

［式中、Ｒｐ^０１は、水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒｐ^０２及びＲｐ^０３は、それぞれ独立に置換基を有してもよい炭化水素基である。Ｒｐ^０２及びＲｐ^０３は、相互に結合して環を形成していてもよい。］

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰² and Rp ⁰³ are hydrocarbon groups that may have independent substituents, respectively. Rp ⁰² and Rp ⁰³ may be coupled to each other to form a ring. ]

In the above formula (m0-1), Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms.
As ^{the alkyl group having 1 to 5 carbon atoms of Rp 01,} a linear or branched alkyl group having 1 to 5 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, etc. Examples thereof include n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like.
The ^{alkyl halide group having 1 to 5 carbon atoms of Rp 01} is a group in which a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferable.
As Rp ⁰¹ , a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is most preferable from the viewpoint of industrial availability.

In the above formula (m0-1), Vp ⁰¹ is a single bond or a divalent linking group.
As the ^{divalent linking group in Vp 01} , for example, a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a hetero atom are preferable.

A divalent hydrocarbon group that may have a substituent:
When Vp ⁰¹ is a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

· · ^{Aliphatic hydrocarbon group at Vp 01} The 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, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

... Linear or branched aliphatic hydrocarbon group The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Numbers 1 to 4 are more preferable, and carbon numbers 1 to 3 are most preferable.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [−CH ₂ −], an ethylene group [− (CH ₂ ) ₂ −], and a trimethylene group [ − (CH ₂ ) ₃ −], tetramethylene group [− (CH ₂ ) ₄ −], pentamethylene group [− (CH ₂ ) ₅ −] and the like can be mentioned.
The branched-chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, further preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -C (CH ₃ ). Alkylene methylene groups such as _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _{2-, etc.;-} 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) Examples thereof include alkylalkylene groups such as alkyltetramethylene groups such as CH ₂ CH ₂ CH ₂ − and −CH ₂ CH (CH ₃ ) CH ₂ CH _{2 −.} As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

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, a carbonyl group and the like.

... An aliphatic hydrocarbon group containing a ring in the structure As the aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group may contain a substituent containing a hetero atom in the ring structure. (A group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), a group in which the cyclic aliphatic hydrocarbon group is bonded to the terminal of a linear or branched aliphatic hydrocarbon group, the cyclic fat Examples thereof include a group in which the group hydrocarbon group is intervening in the middle of the linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same groups as described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms, specifically. Examples thereof include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

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, an alkyl halide group, a hydroxyl group, a carbonyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group are more preferable. The methoxy group and the ethoxy group are most preferable.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
Examples of the alkyl halide group as the substituent include a group in which a part or all of the hydrogen atom of the alkyl group is substituted with the halogen atom.
The cyclic aliphatic hydrocarbon group may be substituted with a substituent containing a hetero atom as a part of the carbon atom constituting the ring structure. The substituent containing a hetero atom, -O -, - C (= O) -O -, - S -, - S (= O) 2 -, - S (= O) 2 -O- are preferred.

Aromatic hydrocarbon group at Vp ⁰¹ The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be a monocyclic type or a polycyclic type. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 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, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); an aromatic compound containing two or more aromatic rings. A group obtained by removing two hydrogen atoms from (for example, biphenyl, fluorene, etc.); one of the hydrogen atoms of the group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring. Hydrogen from an aryl group in an arylalkyl group such as a group substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group). A group obtained by removing one more atom) and the like. The alkylene group bonded to the aryl group or the heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon number.

In the aromatic hydrocarbon group, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the 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, an alkyl halide group, a hydroxyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
Examples of the alkoxy group, halogen atom and alkyl halide 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 heteroatom:
When Vp ⁰¹ is a divalent linking group containing a heteroatom, the preferred linking groups are -O-, -C (= O) -O-, -C (= O)-, and -OC. (= 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 - ^{C (= O) -O -,} - C (= O) -O-Y 21 -, - [Y 21 -C (= O) -O] m "-Y 22 -, - Y 21 -O-C ( = O) ^{-Y 22} - or _{^{-Y 21 -S (= O) 2}} -O-Y 22 - group represented by ^{wherein, Y 21} and ^{Y 22} have independently substituent It is also a good divalent hydrocarbon group, where O is an oxygen atom and m "is an integer from 0 to 3. ] Etc. can be mentioned.
The divalent linking group containing the hetero atom is -C (= O) -NH-, -C (= O) -NH-C (= O)-, -NH-, -NH-C (= NH). )-, The H may be substituted with a substituent such as an alkyl group or an acyl group. 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 -, - C (= O) -O-Y 21 -, - [Y 21 - _{^{C (= O) -O] m}} "-Y 22 -, - Y 21 -O-C (= O) -Y 22 - or _{^{-Y 21 -S (= O) 2}} -O-Y 22 - in, Y ²¹ and Y ²² are divalent hydrocarbon groups which may independently have a substituent. The divalent hydrocarbon group is mentioned in the description as the divalent linking group. (A divalent hydrocarbon group which may have a substituent) is mentioned.
As Y ²¹ , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or an ethylene group is particularly preferable. preferable.
As Y ²² , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group or an alkyl methylene group is more preferable. 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.
Formula _{^{- [Y 21 -C (= O}} ) -O] m "-Y 22 - In the group represented by, m" is an integer of 0 to 3, preferably an integer of 0 to 2, 0 Or 1 is more preferable, and 1 is particularly preferable. In other words, the formula ^- Examples of the group represented by the formula ^{-Y 21 -C (= O) -O} -Y 22 - - [Y 21 -C (= O) -O] m "-Y 22 represented by group is particularly preferred among them, the formula _{-. (CH 2) a '} -C (= O) -O- (CH 2) b' -. in the group represented by the formula in the formula, a 'is from 1 to 10 Is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably 1 or 2, and most preferably 1. b'is an integer of 1 to 10 and of 1 to 8. An integer is preferable, an integer of 1 to 5 is more preferable, 1 or 2 is more preferable, and 1 is most preferable.

In the above formula (m0-1), Vp ⁰¹ is a single bond, an ester bond [-C (= O) -O-], an ether bond (-O-), -C (= O) -NH. -, A linear or branched alkylene group, or a combination thereof is preferable, and a single bond is more preferable.

In the above formula (m0-1), Rp ⁰² and Rp ⁰³ are hydrocarbon groups that may independently have substituents. The hydrocarbon groups in Rp ⁰² and Rp ⁰³ may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a cyclic hydrocarbon group, or a chain hydrocarbon group, respectively.

Cyclic group which may have a substituent:
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. Aliphatic hydrocarbon groups mean hydrocarbon groups that do not have aromatic properties. Further, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. Further, ^{the cyclic hydrocarbon group in Rp 02} and Rp ⁰³ may contain a hetero atom such as a heterocycle.

The aromatic hydrocarbon group in Rp ⁰² and Rp ⁰³ is a hydrocarbon group having an aromatic ring.
Specifically, as the aromatic ring of the aromatic hydrocarbon group in Rp ⁰² and Rp ⁰³ , benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or a part of the carbon atoms constituting these aromatic rings is a heteroatom. Examples include substituted aromatic heterocycles. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like.
Specific examples of the aromatic hydrocarbon group in Rp ⁰² and Rp ⁰³ include a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), and a hydrogen atom of the aromatic ring. A group in which one is substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.) Can be mentioned.

Examples of the cyclic aliphatic hydrocarbon group in Rp ⁰² and Rp ⁰³ include an aliphatic hydrocarbon group containing a ring in the structure.
As the aliphatic hydrocarbon group containing a ring in this structure, an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from the aliphatic hydrocarbon ring) and an alicyclic hydrocarbon group are linear or branched. Examples thereof include a group bonded to the terminal of a chain-shaped aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. Examples of the monocyclic alicyclic hydrocarbon group include a group obtained by removing one or more hydrogen atoms from a monocycloalkane. Specific examples thereof include cyclopentane and cyclohexane.
Examples of the polycyclic alicyclic hydrocarbon group include a group obtained by removing one or more hydrogen atoms from a polycycloalkane. Specifically, examples of the polycycloalkane include polycycloalkanes having a polycyclic skeleton of a crosslinked ring system such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and cyclic groups having a steroid skeleton. Examples thereof include polycycloalkanes having a polycyclic skeleton of a fused ring system.

Examples of the substituent in the cyclic group of Rp ⁰² and Rp ⁰³ include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a nitro group, a carbonyl group and the like.

Chain-like alkyl group which may have a substituent:
The chain alkyl group of Rp ⁰² and Rp ⁰³ may be either linear or branched.
Specific examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decanyl group, an undecyl group, a dodecyl group and a tridecyl group. Examples thereof include a group, an isotridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group, an icosyl group, a henicosyl group and a docosyl group.
Specific examples of the branched alkyl group include 1-methylethyl group, 1,1-dimethylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3 -Methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group and the like can be mentioned.

Chain alkenyl group which may have a substituent:
The chain alkenyl group of Rp ⁰² and Rp ⁰³ may be either linear or branched chain.
Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), a butynyl group and the like. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, a 2-methylpropenyl group and the like.

Examples of the substituent in the chain alkyl group or alkenyl group of Rp ⁰² and Rp ⁰³ include an alkoxy group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), an alkyl halide group, a hydroxyl group, and a carbonyl group. Examples thereof include a group, a nitro group, an amino group, and the above-mentioned cyclic group.

In the above formula (m0-1), Rp ⁰² and Rp ⁰³ may be bonded to each other to form a ring. That is, Rp ⁰² and Rp ⁰³ may form a cyclic imide together with the imide bond in the formula. The cyclic imide may be a monocyclic type or a polycyclic type, and in the case of the polycyclic type, it may have a crosslinked structure.
Examples of the polycyclic cyclic imide structure include a fused ring of a cyclic imide and an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group.
Specific examples of the cyclic imide include a maleimide ring, a succinimide ring, and a nadiimide ring.
Moreover, the cyclic imide may have a substituent.
Examples of the substituent include a hydrocarbon group. The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a cyclic hydrocarbon group, or a chain hydrocarbon group.

In the above formula (m0-1), ^{it is preferable that Rp 02} and Rp ⁰³ are bonded to each other to form a ring.

The preferred structure of the cyclic imide when Rp ⁰² and Rp ⁰³ are bonded to each other to form a ring is shown below. Note that * indicates a bond with an oxygen atom bonded to a nitrogen atom in the above formula (m0-1).

The compound (m0-1) is more preferably a compound represented by the following general formula (m0-11).

［式中、Ｒｐ^０１は、水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｙｐ^０１は、アルキレン基、アルケニレン基又は２価の環式基である。］

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Yp ⁰¹ is an alkylene group, an alkaneylene group or a divalent cyclic group. ]

In the above formula (m0-11), Rp ⁰¹ and Vp ⁰¹ are the same as those described in the above formula (m0-1).

In the above formula (m0-11), Yp ⁰¹ is an alkylene group, an alkaneylene group or a divalent cyclic group.
Examples ^{of the alkylene group in Yp 01} include a linear alkylene group having 1 to 8 carbon atoms which may have a substituent. Among them, specifically, an ethylene group [-(CH ₂ ) _2- ] which may have a substituent and an n-propylene group [-(CH ₂ ) _3- ] which may have a substituent are used. preferable.
Examples of the substituent include a hydrocarbon group. The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a cyclic hydrocarbon group, or a chain hydrocarbon group. Among them, specifically, a linear hydrocarbon group such as a methyl group or an ethyl group; an aromatic hydrocarbon group such as a phenyl group is preferable.

Examples ^{of the alkenylene group in Yp 01} include a linear alkenylene group having 2 to 6 carbon atoms which may have a substituent. Among them, specifically, an ethenylene group is preferable.
Examples of the substituent include the same substituents that the alkylene group may have.

The ^{divalent cyclic group in Yp 01} may be monocyclic or polycyclic, and in the case of polycyclic, it may have a crosslinked structure. Here, when the ^{divalent cyclic group in Yp 01} is a monocyclic group, it means that it has a monocyclic structure different from that of the cyclic imide in the formula (m0-11). That is, it has a polycyclic cyclic imide structure.
Examples of the polycyclic cyclic imide structure include a fused ring of a cyclic imide and an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group.
The cyclic imide is preferably a 5-membered ring or a 6-membered ring.
The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be a monocyclic type or a polycyclic type. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.

The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group.
As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
As the aliphatic hydrocarbon group which is a polycyclic group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferable, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically. Examples include adamantane, norbornane, norbornene, isobornane, tricyclodecane, tetracyclododecane and the like.

In the above formula (m0-11), Yp ⁰¹ is preferably a divalent cyclic group, more preferably a divalent cyclic aliphatic hydrocarbon group, and is divalent. Aliphatic hydrocarbon groups of polycyclic groups are more preferred. Specifically, a group obtained by removing two hydrogen atoms from norbornane and norbornene is preferable.

A suitable specific example of the compound represented by the above formula (m0-1) is shown below. In each of the following formulas, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

Among the above examples, the compound (m0-1) is preferably at least one selected from the group consisting of the compounds represented by the chemical formulas (m01-1-1) to (m01-1-5), and the chemical formula (m01-1-5) is preferable. The compound represented by m01-1-1) is more preferable.

≪Compound (m0-2) ≫
The compound (m0-2) is a compound represented by the following general formula (m0-2).

［Ｒｐ^０４は、水素原子、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である。Ｒｐ^０５は、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、シアノ基又は水酸基である。Ｒｐ^０６は、直鎖状又は分岐鎖状の脂肪族炭化水素基である。ｎ_１は０〜４の整数である。］

[Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. ]

In the above formula (m0-2), Rp ⁰⁴ may be the same as ^{Rp 01} in the above formula (m0-1).

In the above formula (m0-2), Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group.

As ^{the alkyl group in Rp 05,} an alkyl group having 1 to 5 carbon atoms is preferable, a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are more preferable, and a methyl group is further preferable.
As ^{the alkoxy group in Rp 05,} an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferable, and a methoxy group. Is even more preferable.
Examples of the halogen atom in Rp ⁰⁵ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
As the ^{alkyl halide group in Rp 05,} a part or all of hydrogen atoms such as an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group are the halogens. Examples include atomically substituted groups.

In the above formula (m0-2), n ₁ is an integer of 0 to 4, preferably 0 to 2.

In the above formula (m0-2), Rp ⁰⁵ is preferably an alkyl group, an alkoxy group, or a cyano group.

In the above formula (m0-2), Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group.
The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [−CH ₂ −], an ethylene group [− (CH ₂ ) ₂ −], and a trimethylene group [ − (CH ₂ ) ₃ −], tetramethylene group [− (CH ₂ ) ₄ −] and the like can be mentioned.
The branched-chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, and even more preferably 3 or 4 carbon atoms.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -C (CH ₃ ). Alkylene methylene groups such as _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _{2-, etc.;-} 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) Examples thereof include alkylalkylene groups such as alkyltetramethylene groups such as CH ₂ CH ₂ CH ₂ − and −CH ₂ CH (CH ₃ ) CH ₂ CH _{2 −.}

In the above formula (m0-2), Rp ⁰⁶ is preferably a linear aliphatic hydrocarbon group, preferably a methylene group, an ethylene group, or a trimethylene group, and more preferably a methylene group.

A suitable specific example of the compound represented by the above formula (m0-2) is shown below.

In the above examples, the compound (m0-2) is selected from the group consisting of the compounds represented by the chemical formulas (m02-1-1), (m02-1-6) to (m02-1-10), respectively. At least one is preferable.

<< Alternating copolymer represented by the general formula (p0) >>
The compound represented by the above-mentioned general formula (m0-1) and the compound represented by the above-mentioned general formula (m0-2) are copolymerized by the following general formula (p0) by living radical polymerization. It is an alternating copolymer represented.

［式中、Ｒｐ^０１は、水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒｐ^０２及びＲｐ^０３は、それぞれ独立に置換基を有してもよい炭化水素基である。Ｒｐ^０２及びＲｐ^０３は、相互に結合して環を形成していてもよい。Ｒｐ^０４は、水素原子、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である。Ｒｐ^０５は、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、シアノ基又は水酸基である。Ｒｐ^０６は、直鎖状又は分岐鎖状の脂肪族炭化水素基である。ｎ_１は０〜４の整数である。］

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰² and Rp ⁰³ are hydrocarbon groups that may have independent substituents, respectively. Rp ⁰² and Rp ⁰³ may be coupled to each other to form a ring. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. ]

In the above general formula (p0), Rp ⁰¹ , Vp ⁰¹ , Rp ⁰² , Rp ⁰³ , Rp ⁰⁴ , Rp ⁰⁵ , Rp ⁰⁶ , n ₁ are the above general formulas (m0-1) or (m0-2). It is the same as the contents explained.

The ratio of the structural units derived from the compound represented by the general formula (m0-1) described above is the total (100 mol%) of all the structural units constituting the alternating copolymer represented by the general formula (p0). ), 20 to 80 mol% is preferable, 30 to 70 mol% is more preferable, and 40 to 60 mol% is further preferable.

The ratio of the structural units derived from the compound represented by the general formula (m0-2) described above is the total (100 mol%) of all the structural units constituting the alternating copolymer represented by the general formula (p0). ), 20 to 80 mol% is preferable, 30 to 70 mol% is more preferable, and 40 to 60 mol% is further preferable.

<Process (ia)>
The step (ia) is a step of hydrolyzing the alternating copolymer represented by the above general formula (p0) to obtain a first polymer compound precursor represented by the following general formula (Pre-1a). be.

^{Rp 01} , Vp ⁰¹ , Rp ⁰⁴ , Rp ⁰⁵ , Rp ⁰⁶ , and n ₁ in the above formula (Pre-1a) are the same as those described in the above formula (m0-1) and the above formula (m0-2). be.

The method for hydrolyzing the alternating copolymer can be carried out by adding the alternating copolymer and the acid component to a solvent and mixing them. Examples of the solvent include the same solvents as those used for atom transfer radical polymerization described above.

≪Acid component≫
The acid component is not particularly limited, and may be an inorganic acid or an organic acid.
Examples of such acid components include organic acids such as acetic acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and malonic acid; and inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and hydrobromic acid. Can be mentioned.
In the production method of the present embodiment, one type of acid component may be used alone, or two or more types may be used in combination.

The temperature conditions during the reaction between the alternating copolymer and the acid component are not particularly limited, and are, for example, about 0 to 120 ° C.
The reaction time between the alternating copolymer and the acid component is not particularly limited, and is, for example, about 1 to 72 hours.

<Process (iii)>
In the step (iii), the first polymer compound precursor represented by the above formula (Pre-1a) is reacted with the compound represented by the following general formula (Add-1), and the following general formula is used. This is a step of obtaining a second polymer compound precursor represented by (Pre-1b-1).

［式中、Ｒｐ^０１は、水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒｐ^０４は、水素原子、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である。Ｒｐ^０５は、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、シアノ基又は水酸基である。Ｒｐ^０６は、直鎖状又は分岐鎖状の脂肪族炭化水素基である。ｎ_１は０〜４の整数である。Ｒａ^００１、Ｒａ^００２及びＲａ^００３は、それぞれ独立に置換基を有してもよい炭化水素基である。Ｒａ^００２及びＲａ^００３は、相互に結合して環を形成していてもよい。］

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. Ra ⁰⁰¹ , Ra ⁰⁰² and Ra ⁰⁰³ are hydrocarbon groups that may each have an independent substituent. Ra ⁰⁰² and Ra ⁰⁰³ may be coupled to each other to form a ring. ]

As a method for reacting the first polymer compound precursor with the compound represented by the general formula (Add-1), a method known as esterification can be used. for example,
Carbodiimide-based condensing agent (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC / HCl), etc.) and N, N-dimethyl-4-aminopyridine (DMAP) as a catalyst are used. The method of esterification can be mentioned.

The temperature conditions for reacting the first polymer compound precursor with the compound represented by the general formula (Add-1) are not particularly limited, and are, for example, about 0 to 120 ° C.
The reaction time for reacting the first polymer compound precursor with the compound represented by the general formula (Add-1) is not particularly limited, and is, for example, about 1 to 72 hours.

^{Examples of the hydrocarbon group of Ra 001 in} the above general formula (Add-1) include a linear or branched alkyl group, a chain or cyclic alkenyl group, and a cyclic hydrocarbon group.
The ^{linear alkyl group in Ra 11} preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and the like. Among these, a methyl group, an ethyl group and an n-butyl group are preferable, and a methyl group or an ethyl group is more preferable.

The ^{branched-chain alkyl group in Ra 001} preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, a 2,2-dimethylbutyl group and the like, and an isopropyl group is preferable.

When Ra ⁰⁰¹ is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
As the aliphatic hydrocarbon group which is a polycyclic group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferable, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically. Examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

When ^{the cyclic hydrocarbon group in Ra 001} is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be a monocyclic type or a polycyclic type. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, as the aromatic hydrocarbon group in Ra ^001, a group obtained by removing one hydrogen atom from the above-mentioned aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); two or more aromatic rings. A group obtained by removing one hydrogen atom from an aromatic compound (eg, biphenyl, fluorene, etc.); a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic hetero ring is substituted with an alkylene group (eg, benzyl). Groups, phenethyl groups, 1-naphthylmethyl groups, 2-naphthylmethyl groups, 1-naphthylethyl groups, arylalkyl groups such as 2-naphthylethyl groups, etc.) and the like. The carbon number of the alkylene group bonded to the aromatic hydrocarbon ring or the aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

The cyclic hydrocarbon group in Ra ^{001 may have a substituent.} Examples of this substituent include -R ^P1 , -R ^P2, -O-R ^P1 , -R ^P2, -CO-R ^P1 , -R ^P2, -CO-OR ^P1 , -R ^P2, -O-CO-R ^P1 , and so on. Examples thereof include ^{-R P2-} OH, -R ^P2- CN and -R ^P2-COOH.
Here, ^RP1 is a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a monovalent hydrocarbon group having 6 to 30 carbon atoms. It is an aromatic hydrocarbon group. ^RP2 is a single bond, a divalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent group having 6 to 30 carbon atoms. It is an aromatic hydrocarbon group. However, a chain saturated hydrocarbon group R ^P1 and R ^P2, some or all of the aliphatic cyclic saturated hydrocarbon group and an aromatic hydrogen atom of a hydrocarbon group has may be substituted by a fluorine atom. The aliphatic cyclic saturated hydrocarbon group may have one or more of the above-mentioned substituents alone, or may have one or more of the above-mentioned substituents.
Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms include 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 decyl group. ..
Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group and a cyclododecyl group. Monocyclic aliphatic saturated hydrocarbon group; bicyclo [2.2.2] octanyl group, tricyclo [5.2.1.02,6] decanyl group, tricyclo [3.3.1.13,7] decanyl group , Tetracyclo [6.2.1.13, 6.02,7] Polycyclic aliphatic saturated hydrocarbon groups such as dodecanyl group and adamantyl group can be mentioned.
Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include a group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene.
In R ^P2, a divalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, a divalent aromatic hydrocarbon having 6 to 30 carbon atoms Examples of the group include a group obtained by further removing one hydrogen atom from each of the above-mentioned monovalent hydrocarbon groups.

The ^{chain or cyclic alkenyl group in Ra 001} is preferably an alkenyl group having 2 to 10 carbon atoms.

Examples of the hydrocarbon groups ^{of Ra 002} and Ra ⁰⁰³ in the above formula (Add-1) include those similar to those of ^{Ra 001.}

When Ra ⁰⁰² and Ra ⁰⁰³ are bonded to each other to form a ring, a group represented by the following general formula (a1-r2-1), a group represented by the following general formula (a1-r2-2), the following Groups represented by the general formula (a1-r2-3) are preferably mentioned.
On the other hand, when Ra ⁰⁰² and Ra ⁰⁰³ are not bonded to each other and are independent hydrocarbon groups, the group represented by the following general formula (a1-r2-4) is preferably mentioned.

［式（ａ１−ｒ２−１）中、Ｒａ’^１０は、炭素数１〜１０のアルキル基、又は下記一般式（ａ１−ｒ２−ｒ１）で表される基を示す。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を示す。式（ａ１−ｒ２−２）中、Ｙａは炭素原子である。Ｘａは、Ｙａと共に環状の炭化水素基を形成する基である。この環状の炭化水素基が有する水素原子の一部又は全部は置換されていてもよい。Ｒａ^０１〜Ｒａ^０３は、それぞれ独立して、水素原子、炭素数１〜１０の１価の鎖状飽和炭化水素基又は炭素数３〜２０の１価の脂肪族環状飽和炭化水素基である。この鎖状飽和炭化水素基及び脂肪族環状飽和炭化水素基が有する水素原子の一部又は全部は置換されていてもよい。Ｒａ^０１〜Ｒａ^０３の２つ以上が互いに結合して環状構造を形成していてもよい。式（ａ１−ｒ２−３）中、Ｙａａは炭素原子である。Ｘａａは、Ｙａａと共に脂肪族環式基を形成する基である。Ｒａ^０４は、置換基を有していてもよい芳香族炭化水素基である。式（ａ１−ｒ２−４）中、Ｒａ’^１２及びＲａ’^１３は、それぞれ独立に、炭素数１〜１０の１価の鎖状飽和炭化水素基又は水素原子である。この鎖状飽和炭化水素基が有する水素原子の一部又は全部は置換されていてもよい。Ｒａ’^１４は、置換基を有していてもよい炭化水素基である。＊は結合手を示す（以下同じ）。］

Wherein (a1-r2-1), Ra ' 10 represents a group represented by the alkyl group having 1 to 10 carbon atoms, or the following general formula (a1-r2-r1). Ra ^'11 is Ra' represents a group to form an alicyclic group together with the carbon atom ^{to which 10} is bonded. In the formula (a1-r2-2), Ya is a carbon atom. Xa is a group that forms a cyclic hydrocarbon group together with Ya. A part or all of hydrogen atoms contained in this cyclic hydrocarbon group may be substituted. Ra ^{01 to Ra 03} are independently hydrogen atoms, monovalent chain saturated hydrocarbon groups having 1 to 10 carbon atoms, or monovalent aliphatic cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms. A part or all of the hydrogen atoms contained in the chain saturated hydrocarbon group and the aliphatic cyclic saturated hydrocarbon group may be substituted. Two or more of Ra ^{01 to Ra 03} may be bonded to each other to form an annular structure. In formula (a1-r2-3), Ya is a carbon atom. Xaa is a group that forms an aliphatic cyclic group with Yaa. Ra ⁰⁴ is an aromatic hydrocarbon group which may have a substituent. Wherein (a1-r2-4), Ra ' 12 and Ra' ¹³ each independently represent a monovalent chain-like saturated hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms. A part or all of the hydrogen atoms contained in this chain saturated hydrocarbon group may be substituted. Ra ^'14 is a hydrocarbon group which may have a substituent. * Indicates a bond (the same applies hereinafter). ]

［式中、Ｙａ^０は、第４級炭素原子である。Ｒａ^０３１、Ｒａ^０３２及びＲａ^０３３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。但し、Ｒａ^０３１、Ｒａ^０３２及びＲａ^０３３のうちの１つ以上は、少なくとも一つの極性基を有する炭化水素基である。］

[In the formula, Ya ⁰ is a quaternary carbon atom. Ra ⁰³¹ and Ra ⁰³² and Ra ⁰³³ are hydrocarbon groups that may independently have substituents. However, ^{one or more of Ra 031} and Ra ⁰³² and Ra ⁰³³ are hydrocarbon groups having at least one polar group. ]

In the above formula (a1-r2-1), ^{the alkyl group having 1 to 10} carbon atoms of Ra'10 is preferably a linear or branched alkyl group. Ra ^'10 is preferably an alkyl group having 1 to 5 carbon atoms.

In the above formula (a1-r2-r1), Ya ⁰ is a quaternary carbon atom. That is, there are four adjacent carbon atoms bonded to ^{Ya 0 (carbon atom).}

In the above formula (a1-r2-r1), Ra ⁰³¹ and Ra ⁰³² and Ra ⁰³³ are hydrocarbon groups which may independently have a substituent. Examples of the hydrocarbon group in Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ include a linear or branched alkyl group, a chain or cyclic alkenyl group, and a cyclic hydrocarbon group, respectively.

The ^{linear alkyl group in Ra 031} , Ra ⁰³² and Ra ⁰³³ preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably 1 or 2 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and the like. 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-chain alkyl group in Ra 031} , Ra ⁰³² and Ra ⁰³³ preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, a 2,2-dimethylbutyl group and the like, and an isopropyl group is preferable.
The ^{chain or cyclic alkenyl group in Ra 031} , Ra ⁰³² and Ra ⁰³³ is preferably an alkenyl group having 2 to 10 carbon atoms.

The ^{cyclic hydrocarbon group in Ra 031} , Ra ⁰³² and Ra ⁰³³ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
As the aliphatic hydrocarbon group which is a polycyclic group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferable, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically. Examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The ^{aromatic hydrocarbon group in Ra 031} , Ra ⁰³² and Ra ⁰³³ is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be a monocyclic type or a polycyclic type. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring. Specifically, the aromatic hydrocarbon group is a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); an aromatic containing two or more aromatic rings. A group obtained by removing one hydrogen atom from a compound (for example, biphenyl, fluorene, etc.); a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (for example, a benzyl group or a phenethyl group). , 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-arylalkyl group such as 2-naphthylethyl group, etc.) and the like. The carbon number of the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

When the ^{hydrocarbon group represented by Ra 031} , Ra ⁰³² and Ra ⁰³³ is substituted, examples of the substituent include a hydroxy group, a carboxy group, a halogen atom (fluorine atom, chlorine atom, bromine atom and the like). ), An alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), alkyloxycarbonyl group and the like.

Among the above, the ^{hydrocarbon group which may have a substituent in Ra 031} , Ra ⁰³² and Ra ⁰³³ is preferably a linear or branched alkyl group which may have a substituent. A linear alkyl group is more preferred.

However, ^{one or more of Ra 031} and Ra ⁰³² and Ra ⁰³³ are hydrocarbon groups having at least a polar group.
The "hydrocarbon group having a polar group" is one in which the methylene group (-CH _2- ) constituting the hydrocarbon group is replaced with a polar group, or at least one hydrogen atom constituting the hydrocarbon group is present. Any one substituted with a polar group is included.
As such a "hydrocarbon group having a polar group", a functional group represented by the following general formula (a1-p1) is preferable.

［式中、Ｒａ^０７は、炭素数２〜１２の２価の炭化水素基を表す。Ｒａ^０８は、ヘテロ原子を含む２価の連結基を表す。Ｒａ^０６は、炭素数１〜１２の１価の炭化水素基を表す。ｎ_ｐ０は、１〜６の整数である。］

[In the formula, Ra ⁰⁷ represents a divalent hydrocarbon group having 2 to 12 carbon atoms. Ra ⁰⁸ represents a divalent linking group containing a heteroatom. Ra ⁰⁶ represents a monovalent hydrocarbon group having 1 to 12 carbon atoms. n _p0 is an integer of 1 to 6. ]

In the formula (a1-p1), Ra ⁰⁷ represents a divalent hydrocarbon group having 2 to 12 carbon atoms.
Ra ⁰⁷ has 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 4 carbon atoms, and particularly preferably 2 carbon atoms.
The hydrocarbon group in Ra ⁰⁷ is preferably a chain or cyclic aliphatic hydrocarbon group, and more preferably a chain hydrocarbon group.
Examples of Ra ⁰⁷ include an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, and a heptane-1, 7-Diyl group, octane-1,8-diyl group, nonan-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, etc. Linear alcandiyl group; propane-1,2-diyl group, 1-methylbutane-1,3-diyl group, 2-methylpropane-1,3-diyl group, pentane-1,4-diyl group, 2 -Branched chain arcandyl group such as methylbutane-1,4-diyl group; cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1 , 5-Diyl group and other cycloalkandyl groups; norbornan-1,4-diyl group, norbornan-2,5-diyl group, adamantan-1,5-diyl group, adamantan-2,6-diyl group and the like. Examples thereof include a ring-type divalent alicyclic hydrocarbon group.
Among the above, an alkanediyl group is preferable, and a linear alkanediyl group is more preferable.

In the formula (a1-p1), Ra ⁰⁸ represents a divalent linking group containing a heteroatom.
Examples of Ra ⁰⁸ include -O-, -C (= O) -O-, -C (= O)-, -OC (= O) -O-, and -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 -,- Examples thereof include S (= O) _2- O− and the like.
Among these, -O-, -C (= O) -O-, -C (= O)-, and -OC (= O) -O- are preferable from the viewpoint of solubility in a developing solution. O- and -C (= O)-are particularly preferable.

In the formula (a1-p1), Ra ⁰⁶ represents a monovalent hydrocarbon group having 1 to 12 carbon atoms.
Ra ⁰⁶ has 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms, further preferably 1 to 3 carbon atoms, and more preferably 1 to 2 carbon atoms from the viewpoint of solubility in a developing solution. 1 or 2 is particularly preferable, and 1 is most preferable.

Examples of the hydrocarbon group in Ra ⁰⁶ include a chain hydrocarbon group or a cyclic hydrocarbon group, or a hydrocarbon group in which a chain and a cyclic are combined.
Examples of the chain hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and n. -Heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and the like can be mentioned.

The cyclic hydrocarbon group may be an alicyclic hydrocarbon group or an aromatic hydrocarbon group.
The alicyclic hydrocarbon group may be either a monocyclic group or a polycyclic group, and the monocyclic alicyclic hydrocarbon group may be, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a methyl. Cycloalkyl groups such as cyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cycloheptyl group, cyclodecyl group and the like can be mentioned. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a 2-alkyladamantan-2-yl group, a 1- (adamantan-1-yl) alkane-1-yl group, and a norbornyl group. Examples include a group, a methylnorbornyl group, an isobornyl group and the like.
Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group, a trill group, a xsilyl group, a cumenyl group and a mesityl group. , Biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group and the like.

As Ra ⁰⁶ , a chain hydrocarbon group is preferable, an alkyl group is more preferable, and a linear alkyl group is further preferable, from the viewpoint of solubility in a developing solution.

In the above formula (a1-p1), n _p0 is an integer of 1 to 6, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.

Specific examples of the hydrocarbon group having at least a polar group are shown below.
In the following formula, * is a bond that bonds to the ^{quaternary carbon atom (Ya 0).}

In the above formula (a1-r2-r1), among Ra ⁰³¹ and Ra ⁰³² and Ra ⁰³³ , the number of hydrocarbon groups having at least one polar group is one or more, but the developing solution is used when forming a resist pattern. It may be appropriately determined in consideration of the solubility of, for example, ^{one or two of Ra 031} and Ra ⁰³² and Ra ⁰³³ , and particularly preferably one.

The above-mentioned hydrocarbon group having at least a polar group may have a substituent other than the polar group. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.) and an alkyl halide group having 1 to 5 carbon atoms.

Wherein (a1-r2-1), Ra ' ( aliphatic cyclic ^{group 11} Ra' ¹⁰ is formed together with bonded carbon atoms) is substituted by a monocyclic group ^{Ra 001} in formula (Add-1) or The groups listed as the aliphatic hydrocarbon group which is a polycyclic group are preferable.

In the formula (a1-r2-2), the cyclic hydrocarbon group formed by Xa together with Ya is a cyclic monovalent hydrocarbon group (aliphatic hydrocarbon ^{) in Ra 001 in the above general formula (Add-1).} A group obtained by further removing one or more hydrogen atoms from the group) can be mentioned.
The cyclic hydrocarbon group that Xa forms with Ya may have a substituent. Examples of this substituent include the same substituents that the cyclic hydrocarbon group in ^{Ra 001 in the above general formula (Add-1) may have.}
In the formula (a1-r2-2), examples ^{of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in Ra 01 to Ra 03} include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl. Examples thereof include a group, a hexyl group, a heptyl group, an octyl group, a decyl group and the like.
Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms in Ra ^{01 to Ra 03} include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a cyclodecyl group. Monocyclic aliphatic saturated hydrocarbon groups such as groups and cyclododecyl groups; bicyclo [2.2.2] octanyl group, tricyclo [5.2.1.02,6] decanyl group, tricyclo [3.3.1] Examples thereof include a polycyclic aliphatic saturated hydrocarbon group such as .13,7] decanyl group, tetracyclo [6.2.1.13, 6.02,7] dodecanyl group and adamantyl group.

Examples of the substituent contained ^{in the chain saturated hydrocarbon group represented by Ra 01 to Ra 03} or the aliphatic cyclic saturated hydrocarbon group include the same group as Ra ⁰⁵ described above.

Examples of the group containing a carbon-carbon double bond formed by two or more of Ra ^{01 to Ra 03} bonding to each other to form a cyclic structure include a cyclopentenyl group, a cyclohexenyl group, a methylcyclopentenyl group, and a methyl. Examples thereof include a cyclohexenyl group, a cyclopentylidene ethenyl group, a cyclohexylidene ethenyl group and the like.

In the formula (a1-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is an aliphatic hydrocarbon which is a monocyclic group or a polycyclic group in ^{Ra 001 in the above general formula (Add-1).} The groups listed as hydrogen groups are preferred.
In the formula (a1-r2-3), examples ^{of the aromatic hydrocarbon group in Ra 04} include a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Among them, Ra ⁰⁴ is preferably a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, and more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene or phenanthrene. , Benzene, naphthalene or anthracene with one or more hydrogen atoms removed is more preferred, benzene or naphthalene with one or more hydrogen atoms removed, and benzene with one or more hydrogen atoms removed most. preferable.

^{Examples of the substituent that Ra 04} in the formula (a1-r2-3) may have include a methyl group, an ethyl group, a propyl group, a hydroxyl group, a carboxyl group, and a halogen atom (fluorine atom, chlorine atom, etc.). Bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), alkyloxycarbonyl group, etc. can be mentioned.

Wherein (a1-r2-4), Ra ' 12 and Ra' ¹³ each independently represent a monovalent chain-like saturated hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms. In Ra ^'12 and Ra' ^13, the monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, in the above ^Ra 01 ^{to Ra 03,} monovalent chain saturated hydrocarbon having from 1 to 10 carbon atoms The same as the group can be mentioned. A part or all of the hydrogen atoms contained in this chain saturated hydrocarbon group may be substituted.
Ra ^'12 and Ra' ¹³ is preferably a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, a methyl group, an ethyl group more preferably, in particular a methyl group preferable.
If chain saturated hydrocarbon group represented by Ra ^'12 and Ra' ¹³ is substituted, the substituent, for example, include the same groups as Ra ⁰⁵ described above.

Wherein (a1-r2-4), Ra ' 14 is a hydrocarbon group which may have a substituent. The hydrocarbon group in the ra ^'14, include straight chain or branched chain alkyl group, or a cyclic hydrocarbon group.

Linear alkyl groups in the ra ^'14 is preferably has 1 to 5 carbon atoms, more preferably 1 to 4, 1 or 2 is more preferred. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and the like. 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.

Branched-chain alkyl group in the ra ^'14 is preferably has 3 to 10 carbon atoms, 3-5 is more preferable. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, a 2,2-dimethylbutyl group and the like, and an isopropyl group is preferable.

If Ra ^'14 is cyclic hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group with an aliphatic hydrocarbon group, or may be a monocyclic group or polycyclic group.
As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
As the aliphatic hydrocarbon group which is a polycyclic group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferable, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically. Examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The aromatic hydrocarbon group in Ra ^'14, include the same aromatic hydrocarbon group in Ra ^04. Among them, Ra ^'14 is preferably an aromatic hydrocarbon ring group derived by removing one or more hydrogen atoms from 6 to 15 carbon atoms, more benzene, naphthalene, a group obtained by removing one or more hydrogen atoms from anthracene or phenanthrene Preferably, a group in which one or more hydrogen atoms are removed from benzene, naphthalene or anthracene is more preferable, a group in which one or more hydrogen atoms are removed from naphthalene or anthracene is particularly preferable, and a group in which one or more hydrogen atoms are removed from naphthalene is particularly preferable. Most preferred.
The ra ^'14 substituent which may be possessed are the same as those of the substituent which may be ra ⁰⁴ has had.

If Ra ^'14 in formula (a1-R2-4) is a naphthyl group, a position to bind to the tertiary carbon atoms in the formula (a1-R2-4) are the 1-position or 2-position of the naphthyl group It may be either.
If Ra ^'14 in formula (a1-R2-4) is anthryl group, a position to bind to the tertiary carbon atoms in the formula (a1-R2-4), the 1-position of the anthryl group, 2-position or It may be any of the 9th place.

Specific examples of the groups represented by the above formula (a1-r2-1) are given below.

Specific examples of the groups represented by the above formula (a1-r2-2) are given below.

Specific examples of the groups represented by the above formula (a1-r2-3) are given below.

Specific examples of the groups represented by the above formula (a1-r2-4) are given below.

^{Rp 01} , Vp ⁰¹ , Rp ⁰⁴ , Rp ⁰⁵ , Rp ⁰⁶ , and n ₁ in the above formula (Pre-1b-1) are the contents described in the above formula (m0-1) and the above formula (m0-2). The same is true.

^{Ra 001} , Ra ⁰⁰² and Ra ⁰⁰³ in the above formula (Pre-1b-1) are hydrocarbon groups which may independently have a substituent.
In the above formula (Pre-1b-1), -C (Ra ⁰⁰¹ ) (Ra ⁰⁰² ) (Ra ⁰⁰³ ) is an acid dissociative group (tertiary alkyl ester type acid dissociative group). The "acid dissociative group" is (i) a group having acid dissociation that allows the bond between the acid dissociative group and an atom adjacent to the acid dissociative group to be cleaved by the action of an acid, or a group having acid dissociation. (Ii) A group capable of cleaving a bond between the acid dissociative group and an atom adjacent to the acid dissociative group by causing a decarbonation reaction after a part of the bond is cleaved by the action of an acid. , Both.
^{Specifically, the tertiary carbon atom of -C (Ra 001} ) (Ra ⁰⁰² ) (Ra ⁰⁰³ ) in the above formula (Pre-1b-1) and the oxygen atom adjacent to the tertiary carbon atom The bond between, and -C (Ra ⁰⁰¹ ) (Ra ⁰⁰² ) (Ra ⁰⁰³ ) is dissociated, and a highly polar polar group (carboxy group) is generated to increase the polarity.

^{Ra 001} , Ra ⁰⁰² and Ra ⁰⁰³ in the above formula (Pre-1b-1) are the same as those described as the hydrocarbon group in the above formula (Add-1).

<Process (iva)>
The step (iva) is a step of hydrolyzing the second polymer compound precursor to obtain the polymer compound (A01) represented by the general formula (p1) (hereinafter, also referred to as step (iva)). Is.

The method for hydrolyzing the second polymer compound precursor can be carried out by adding the second polymer compound precursor and the base component to a solvent and mixing them. Examples of the solvent include the same solvents as those used for atom transfer radical polymerization described above.

≪Base component≫
The base component is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, potassium carbonate and the like.
In the production method of the present embodiment, one type of base component may be used alone, or two or more types may be used in combination.

The temperature condition at the time of the reaction between the second polymer compound precursor and the base component is not particularly limited, and is, for example, about 0 to 60 ° C.
The reaction time between the second polymer compound precursor and the base component is not particularly limited, and is, for example, about 1 to 24 hours.

^{Rp 01} , Vp ⁰¹ , Rp ⁰⁴ , Rp ⁰⁵ , and n ₁ in the general formula (p1) are the same as those described in the above formula (m0-1) and the above formula (m0-2).
^{Ra 001} , Ra ⁰⁰² and Ra ⁰⁰³ in the general formula (p1) are the same as those described as the hydrocarbon group in the above formula (Add-1).

<Process (va)>
This is a step of preparing a resist composition by mixing a polymer compound (A01) and an organic solvent.

[Resist composition]
The resist composition in the present embodiment is a base material component in which an acid is generated by exposure and the solubility in a developing solution is changed by the action of the acid, and the solubility in the developing solution is changed by the action of the acid. (A) (hereinafter, also referred to as “component (A)”) is contained. The above-mentioned polymer compound (A01) is contained in the component (A), and the component (A) is a polymer compound (A1) other than the polymer compound (A01) (hereinafter, (A1). ) May be included.

When a resist film is formed using the resist composition of the present embodiment and selective exposure is performed on the resist film, an acid is generated in the exposed portion of the resist film, and the component (A) is generated by the action of the acid. While the solubility of the resist film in the developing solution changes, the solubility of the component (A) in the developing solution does not change in the unexposed portion of the resist film, so that the resist film is developed between the exposed portion and the unexposed portion. There is a difference in solubility in the solution. Therefore, when the resist film is developed, if the resist composition is a positive type, the exposed portion of the resist film is dissolved and removed to form a positive type resist pattern, and if the resist composition is a negative type, the resist film is not formed. The exposed portion is dissolved and removed to form a negative resist pattern.

In the present specification, a resist composition in which a resist film exposed portion is dissolved and removed to form a positive resist pattern is referred to as a positive resist composition, and a negative resist pattern in which a resist film unexposed portion is dissolved and removed is referred to as a negative resist pattern. The resist composition to be formed is called a negative resist composition.
The resist composition in the present embodiment may be a positive resist composition or a negative resist composition.
Further, the resist composition in the present embodiment may be used for an alkaline developing process in which an alkaline developing solution is used for the developing process at the time of forming a resist pattern, and a developing solution (organic developing solution) containing an organic solvent in the developing process. It may be for a solvent developing process using.
That is, the resist composition in the present embodiment is a "positive resist composition for an alkali developing process" that forms a positive resist pattern in an alkali developing process, and a "solvent developing" that forms a negative resist pattern in a solvent developing process. It is a negative resist composition for processing.

The resist composition in the present embodiment has an acid-generating ability to generate an acid by exposure, and the component (A) may generate an acid by exposure, and is added separately from the component (A). The agent component may generate an acid upon exposure.
Specifically, the resist composition may contain (1) an acid generator component (B) that generates an acid upon exposure (hereinafter referred to as "component (B)"); (2). The component (A) may be a component that generates an acid by exposure; the component (3) (A) is a component that generates an acid by exposure and further contains a component (B). May be good.
That is, in the case of the above (2) or (3), the component (A) is "a base material component that generates an acid by exposure and whose solubility in a developing solution changes by the action of the acid".
In the case of (2) or (3), it means that the component (A) contains the component (A1) and the component (A1) contains a component that generates an acid by exposure.
The resist composition in this embodiment is preferably the case of (1) above.

Examples of the resist composition in the present embodiment include a resist composition containing a component (A), a component (B), and a component (S).

<Ingredient (A)>
The component (A) in the resist composition is a base material component whose solubility in a developing solution changes due to the action of an acid, and contains the above-mentioned component (A0). By using the component (A0), the polarity of the base material component changes before and after exposure, so that good development contrast can be obtained not only in the alkali development process but also in the solvent development process.
Further, since the component (A0) is produced by the above-mentioned process, the variation of each structural unit is suppressed, and a resist pattern having good lithography characteristics can be formed.

When the alkaline development process is applied, the base material component containing the component (A0) is sparingly soluble in an alkaline developer before exposure. For example, when an acid is generated from the component (B) by exposure, the acid The polarity is increased by the action of, and the solubility in an alkaline developer is increased. Therefore, in the formation of the resist pattern, when the resist composition is selectively exposed to the resist film obtained by applying the resist composition on the support, the resist film exposed portion changes from poorly soluble to soluble in an alkaline developer. On the other hand, since the unexposed portion of the resist film remains sparingly soluble in alkali, a positive resist pattern is formed by developing with alkali.

On the other hand, when the solvent development process is applied, the base material component containing the component (A0) is highly soluble in an organic developer before exposure, and for example, when acid is generated from the component (B) by exposure. Due to the action of the acid, the polarity is increased and the solubility in an organic developer is reduced. Therefore, in the formation of the resist pattern, when the resist composition is selectively exposed to the resist film obtained by applying the resist composition on the support, the resist film exposed portion becomes soluble to sparingly soluble in an organic developer. While it changes, the unexposed part of the resist film remains soluble and does not change. Therefore, by developing with an organic developer, it is possible to add contrast between the exposed part and the unexposed part, and a negative resist pattern can be obtained. It is formed.

In the resist composition of the present embodiment, the component (A) may be used alone or in combination of two or more.

-Regarding the component (A1) The component (A1) is a polymer compound that does not correspond to the component (A0). A structural unit containing a formula group, a -SO ₂ -containing cyclic group or a carbonate-containing cyclic group (a2), a structural unit containing a polar group-containing aliphatic hydrocarbon group (a3) (provided that the structural unit (a1) or a constitution A polymer having one or more of a unit (excluding those corresponding to the unit (a2)), a structural unit containing a hydroxystyrene skeleton (a10), and a structural unit containing an acid non-dissociable aliphatic cyclic group (a4). Examples include compounds.

<< Structural unit (a1) >>
The structural unit (a1) is a structural unit containing an acid-degradable group whose polarity is increased by the action of an acid.
An "acid-degradable group" is a group having an acid-degradable property in which at least a part of the bonds in the structure of the acid-degradable group can be cleaved by the action of an acid.
Examples of the acid-degradable group whose polarity is increased by the action of an acid include a group which is decomposed by the action of an acid to produce 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, may be referred to as “OH-containing polar group”) is preferable, a carboxy group or a hydroxyl group is more preferable, and a carboxy group is particularly preferable.
More specific examples of the acid-degradable group include a group in which the polar group is protected by an acid-dissociable group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected by an acid-dissociable group).

Here, the "acid dissociative group" is a group having an acid dissociative property (i) in which the bond between the acid dissociative group and an atom adjacent to the acid dissociative group can be cleaved by the action of an acid. Alternatively, after a part of the bond is cleaved by the action of the acid (ii), a decarbonation reaction is further caused, so that the bond between the acid dissociative group and the atom adjacent to the acid dissociative group is cleaved. It refers to both the basis to obtain.
The acid dissociable group constituting the acid-degradable group needs to be a group having a lower polarity than the polar group produced by the dissociation of the acid-dissociable group, whereby the acid-dissociable group is affected by the action of the acid. When is dissociated, a polar group having a higher polarity than the acid dissociative group is generated and the polarity is increased. As a result, the polarity of the entire (A1) component increases. As the polarity increases, the solubility in the developer changes relatively, the solubility increases when the developer is an alkaline developer, and the solubility increases when the developer is an organic developer. Decrease.

Examples of the acid dissociable group include those that have been proposed as an acid dissociative group of a base resin for a chemically amplified resist composition.
Specifically, "acetal-type acid-dissociating group", "tertiary alkyl ester-type acid-dissociating group", and "" are proposed as acid-dissociating groups of the base resin for the chemically amplified resist composition. A tertiary alkyloxycarbonylic acid dissociative group ”can be mentioned.
The acetal-type acid dissociative group is an acetal-type acid dissociative group represented by -C (Ra ⁰⁰⁴ ) (Ra ⁰⁰⁵ ) -O- (Ra ⁰⁰⁶ ) in the formula (Pre-1b-2) described later. The same is true.
^{The tertiary alkyl ester type acid dissociative group is represented by −C (Ra 001} ) (Ra ⁰⁰² ) (Ra ⁰⁰³ ) in the above formula (Pre-1b-1) and has a tertiary alkyl ester type acid dissociative property. It is the same as the content explained in the base.

Tertiary alkyloxycarbonylic acid dissociative group:
Among the polar groups, the acid dissociable group that protects the hydroxyl group includes, for example, an acid dissociable group represented by the following general formula (a1-r-3) (hereinafter, for convenience, “tertiary alkyloxycarbonylic acid dissociable group”. ”).

［式中、Ｒａ’^７〜Ｒａ’^９はそれぞれアルキル基である。］

Wherein, Ra ^'7 ~Ra' ⁹ are each an alkyl group. ]

Wherein (a1-r-3), Ra '7 ~Ra' 9 is preferably an alkyl group having 1 to 5 carbon atoms, respectively, and more preferably an alkyl group having 1 to 3 carbon atoms.
The total carbon number of each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.

As the structural unit (a1), a structural unit derived from an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent, a structural unit derived from acrylamide, hydroxystyrene or hydroxy. A structural unit in which at least a part of hydrogen atoms in the hydroxyl group of a structural unit derived from a styrene derivative is protected by a substituent containing the acid-degradable group, a structural unit derived from vinyl benzoic acid or a vinyl benzoic acid derivative- Examples thereof include a structural unit in which at least a part of hydrogen atoms in C (= O) -OH is protected by a substituent containing the acid-degradable group.

As the structural unit (a1), a structural unit derived from an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent is preferable.
A preferable specific example of the structural unit (a1) is a structural unit represented by the following general formula (a1-1) or (a1-2).

［式中、Ｒは、水素原子、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である。Ｖａ^１は、エーテル結合を有していてもよい２価の炭化水素基である。ｎ_ａ１は、０〜２の整数である。Ｒａ^１は、上記の一般式（ａ１−ｒ−１）、（ａ１−ｒ２−１）、（ａ１−ｒ２−２）、（ａ１−ｒ２−３）、又は（ａ１−ｒ２−４）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の整数であり、Ｒａ^２は上記の一般式（ａ１−ｒ−１）又は（ａ１−ｒ−３）で表される酸解離性基である。］

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Va ¹ is a divalent hydrocarbon group that may have an ether bond. n _a1 is an integer of 0 to 2. Ra ¹ is represented by the above general formulas (a1-r-1), (a1-r2-1), (a1-r2-2), (a1-r2-3), or (a1-r2-4). It is an acid dissociative group. Wa ¹ is a n _a2 + 1 valent hydrocarbon group, n _a2 is an integer of 1 to 3, and Ra ² is represented by the above general formula (a1-r-1) or (a1-r-3). It is an acid dissociative group. ]

In the above formula (a1-1), the alkyl group having 1 to 5 carbon atoms of R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, a methyl group or an ethyl group. , Propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. The alkyl halide group having 1 to 5 carbon atoms is a group in which a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferable.
As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is most preferable from the viewpoint of industrial availability.

In the above formula (a1-1), the ^{divalent hydrocarbon group in Va 1} may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

The aliphatic hydrocarbon group as the divalent hydrocarbon group in Va ¹ may be saturated or unsaturated, and is usually preferably saturated.
More specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group having a ring in its structure, and the like.

The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. ..
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [−CH ₂ −], an ethylene group [− (CH ₂ ) ₂ −], and a trimethylene group [ − (CH ₂ ) ₃ −], tetramethylene group [− (CH ₂ ) ₄ −], pentamethylene group [− (CH ₂ ) ₅ −] and the like can be mentioned.
The branched-chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, further preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -C (CH ₃ ). Alkylene methylene groups such as _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _{2-, etc.;-} 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) Examples thereof include alkylalkylene groups such as alkyltetramethylene groups such as CH ₂ CH ₂ CH ₂ − and −CH ₂ CH (CH ₃ ) CH ₂ CH _{2 −.} As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

As the aliphatic hydrocarbon group containing a ring in the structure, an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from the aliphatic hydrocarbon ring) and an alicyclic hydrocarbon group are linear or branched. Examples thereof include a group bonded to the terminal of a chain-shaped aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like. Examples of the linear or branched aliphatic hydrocarbon group include the same as the linear aliphatic hydrocarbon group or the branched aliphatic hydrocarbon group.
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 a polycyclic type or a monocyclic type. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms, specifically adamantane. , Norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The aromatic hydrocarbon group as the divalent hydrocarbon group in Va ^{1 is a hydrocarbon group having an aromatic ring.}
The aromatic hydrocarbon 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 12 carbon atoms. .. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic ring contained in 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 hetero. Examples thereof include aromatic heterocycles substituted with atoms. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like.
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). ) Is an arylalkyl group in which one of the hydrogen atoms is substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.) A group in which one hydrogen atom is further removed from the aryl group in the group) and the like can be mentioned. 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 (a1-1), Ra ¹ is the above formula (a1-r-1), (a1-r2-1), (a1-r2-2), (a1-r2-3), or (a1). It is an acid dissociative group represented by −r2-4).

In the formula (a1-2), n _{a2 +1} monovalent hydrocarbon group for Wa ¹ may be an aliphatic hydrocarbon group may be an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromatic property, and 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 containing a ring in the structure, and a linear or branched aliphatic hydrocarbon group. Examples thereof include a group in combination with an aliphatic hydrocarbon group containing a ring in the structure.
The _na2 + 1 valence is preferably 2 to 4 valence, more preferably 2 or 3 valence.

In the formula (a1-2), Ra ² is an acid dissociative group represented by the above general formula (a1-r-1) or (a1-r-3).

Specific examples of the structural units represented by the above formula (a1-1) are shown below. In each of the following formulas, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

Specific examples of the structural units represented by the above formula (a1-2) are shown below.

The structural unit (a1) contained in the component (A1) may be one type or two or more types.
The ratio of the constituent unit (a1) in the component (A1) is preferably 5 to 80 mol%, preferably 10 to 75 mol%, based on the total (100 mol%) of all the constituent units constituting the component (A1). More preferably, 20 to 60 mol% is further preferable.
By setting the ratio of the structural unit (a1) to be equal to or higher than the lower limit of the above-mentioned preferable range, the lithography characteristics such as sensitivity, resolution, and roughness improvement are improved. On the other hand, when it is not more than the upper limit value of the above-mentioned preferable range, it is possible to balance with other constituent units and various lithography characteristics are improved.

≪Constructive unit (a2) ≫
The structural unit (a2), a lactone-containing cyclic group, -SO 2 _- is a structural unit containing an containing cyclic group or a carbonate-containing cyclic group (excluding those falling under the structural unit (a1)).
Lactone-containing cyclic group of the structural unit (a2), -SO 2 _- containing cyclic group or a carbonate-containing cyclic group, when used for forming a resist film (A1) component, the adhesion of the resist film and the substrate It is effective in enhancing sex. Further, by having the structural unit (a2), for example, the lithographic characteristics can be appropriately adjusted by adjusting the acid diffusion length, improving the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development. Etc. are good.

The “lactone-containing cyclic group” refers to a cyclic group containing a ring (lactone ring) containing −OC (= O) − in its cyclic skeleton. The lactone ring is counted as the first ring, and when it has only a lactone ring, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of its structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.
The lactone-containing cyclic group in the structural unit (a2) is not particularly limited, and any lactone-containing cyclic group can be used. Specifically, the groups represented by the following general formulas (a2-r-1) to (a2-r-7) can be mentioned.

［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、アルキル基、ラクトン含有環式基、カーボネート含有環式基、又は−ＳＯ_２−含有環式基であり；Ａ”は酸素原子（−Ｏ−）もしくは硫黄原子（−Ｓ−）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 represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, hydroxyl group, -COOR - in ", OC (= O) R ", a hydroxyalkyl group or a cyano group Yes; R "is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO ₂ -containing cyclic group; A" is an oxygen atom (-O-) or a sulfur atom (-O-). It is an alkylene group having 1 to 5 carbon atoms, an oxygen atom or a sulfur atom which may contain S-), n'is an integer of 0 to 2, and m'is 0 or 1. ]

In the general formula (a2-r-1) ~ (a2-r-7), 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 thereof 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, groups of the the Ra 'group and an oxygen atom mentioned as the alkyl group in ²¹ (-O-) are linked and the like.
As the halogen atom in ra ^'21, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom is preferable.
'Examples of the halogenated alkyl group for ^21, the Ra' Ra part or all of the hydrogen atoms of the alkyl group in ²¹ can be mentioned it has been substituted with the aforementioned halogen atoms. As the alkyl halide group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

Ra '-COOR in ^{21 ", - OC (= O} ) R" in, R "is also hydrogen either is an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO ₂ - containing cyclic group Is.
The alkyl group in "R" may be linear, branched or cyclic, and the number of carbon atoms is preferably 1 to 15.
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, a group obtained by removing one or more hydrogen atoms from a monocycloalkane that may or may not be substituted with an alkyl fluorinated group; a polycycloalkane such as a bicycloalkane, a tricycloalkane, or a tetracycloalkane. Examples thereof include a group obtained by removing one or more hydrogen atoms from the group. More specifically, a group obtained by removing one or more hydrogen atoms from a monocycloalkane such as cyclopentane or cyclohexane; Examples thereof include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as cyclodecane and tetracyclododecane.
Examples of the lactone-containing cyclic group in "R" include the same groups as those represented by the general formulas (a2-r-1) to (a2-r-7).
The carbonate-containing cyclic group in "R" is the same as the carbonate-containing cyclic group described later, and specifically, the groups represented by the general formulas (ax3-r-1) to (ax3-r-3), respectively. Can be mentioned.
The containing cyclic group, -SO ₂ below - - -SO ₂ in R "are the same as containing cyclic group, specifically the general formula (a5-r-1) ~ (a5-r-4) The groups represented by are listed.
Ra 'The hydroxyalkyl group in the ^21, preferably has 1 to 6 carbon atoms, specifically, the Ra' at least one of the hydrogen atoms of the alkyl group include groups substituted with a hydroxyl group in the ²¹ ..

In the general formulas (a2-r-2), (a2-r-3), and (a2-r-5), the alkylene group having 1 to 5 carbon atoms in A "has a linear or branched alkylene group. An alkylene group is preferable, 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 the terminal or carbon of the alkylene group. between atoms -O- or -S- can be mentioned a group intervening, for example, _{-O-CH 2 -, - CH} 2 -O-CH 2 -, - S-CH 2 -, - CH 2 -S-CH ₂ - such as .A "which include, an alkylene group or -O- is preferable of 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.

Specific examples of the groups represented by the 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} its ring skeleton, and specifically, the sulfur atom (S) in _{-SO 2-} A cyclic group that forms part of the cyclic skeleton of the cyclic group. _{A ring containing −SO 2} − in its ring skeleton is counted as the first ring, and if it is only the ring, it is a monocyclic group, and if it has another ring structure, it is a polycyclic group regardless of its structure. It is called. The −SO ₂ − containing cyclic group may be a monocyclic group or a polycyclic group.
-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 It is preferably a cyclic group containing a sultone ring to be formed.
-SO ₂ - containing cyclic group, and more specifically, include groups respectively represented by the following formula (a5-r-1) ~ (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、アルキル基、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 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, hydroxyl group, -COOR - in ", OC (= O) R ", a hydroxyalkyl group or a cyano group Yes; R "is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO ₂ -containing cyclic group; A" is a carbon that may contain an oxygen atom or a sulfur atom. It is an alkylene group of the number 1 to 5, an oxygen atom or a sulfur atom, and n'is an integer of 0 to 2. ]

In the general formulas (a5-r-1) to (a5-r-2), A "is a general formula (a2-r-2), (a2-r-3), (a2-r-5). It is the same as A "inside.
Alkyl group in ra ^'51, an alkoxy group, a halogen atom, a halogenated alkyl group, -COOR ", - OC (= O) R", The hydroxyalkyl group, each of the general formulas (a2-r-1) ~ ( a2-r-7) as in the same as those exemplified in the description of the Ra ^'21 of the like.
Specific examples of the groups represented by the general formulas (a5-r-1) to (a5-r-4) are given below. "Ac" in the formula indicates an acetyl group.

The "carbonate-containing cyclic group" refers to a cyclic group containing a ring (carbonate ring) containing -OC (= O) -O- in its cyclic skeleton. The carbonate ring is counted as the first ring, and when it has only a carbonate ring, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of its structure. The carbonate-containing cyclic group may be a monocyclic group or a polycyclic group.
As the carbonate ring-containing cyclic group, any one can be used without particular limitation. Specifically, the groups represented by the following general formulas (ax3-r-1) to (ax3-r-3) can be mentioned.

［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、アルキル基、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、ｐ’は０〜３の整数であり、ｑ’は０または１である。］

[In the formula, ^Ra'x31 is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, -COOR ", -OC (= O) R", a hydroxyalkyl group or a cyano group. Yes; R "is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO ₂ -containing cyclic group; A" is a carbon that may contain an oxygen atom or a sulfur atom. It is an alkylene group of the number 1 to 5, an oxygen atom or a sulfur atom, p'is an integer of 0 to 3, and q'is 0 or 1. ]

In the general formulas (ax3-r-2) to (ax3-r-3), A "is a general formula (a2-r-2), (a2-r-3), (a2-r-5). It is the same as A "inside.
Alkyl group in ra ^'31, an alkoxy group, a halogen atom, a halogenated alkyl group, -COOR ", - OC (= O) R", The hydroxyalkyl group, each of the general formulas (a2-r-1) ~ ( a2-r-7) as in the same as those exemplified in the description of the Ra ^'21 of the like.
Specific examples of the groups represented by the general formulas (ax3-r-1) to (ax3-r-3) are given below.

As the structural unit (a2), a structural unit derived from an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent is preferable.
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のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。Ｙａ^２１は単結合または２価の連結基である。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。］

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Ya ²¹ is a single bond or divalent linking group. La ²¹ is -O-, -COO-, -CON (R')-, -OCO-, -CONHCO- or -CONHCS-, where R'represents a hydrogen atom or a methyl group. However, when La ²¹ is −O−, Ya ²¹ is not −CO−. Ra ²¹ represents a lactone-containing cyclic group, a carbonate-containing cyclic group, or an -SO ₂ - containing cyclic group. ]

In the formula (a2-1), R is the same as described above. As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is particularly preferable from the viewpoint of industrial availability.

In the above formula (a2-1), the ^{divalent linking group of Ya 21} is not particularly limited, but is a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a heteroatom. Etc. are preferably mentioned. The description of the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom in Ya ²¹ is described in the above-mentioned substitution in ^{Ya x1 in the general formula (a10-1).} The same applies to the description of the divalent hydrocarbon group which may have a group and the divalent linking group containing a hetero atom, respectively.
The 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, -SO ₂ - is containing cyclic group or a carbonate-containing cyclic group.
Lactone-containing cyclic group for Ra ^21, -SO ₂ - containing cyclic group, respectively as the carbonate-containing cyclic group, represented respectively by the above general formula (a2-r-1) ~ (a2-r-7) Groups, groups represented by the general formulas (a5-r-1) to (a5-r-4), and groups represented by the general formulas (ax3-r-1) to (ax3-r-3), respectively. Is preferably mentioned.
Among them, a lactone-containing cyclic group or -SO ₂ - containing cyclic group are preferred, the formula (a2-r-1), (a2-r-2), (a2-r-6) or (a5-r The groups represented by -1) are more preferable. Specifically, the chemical formulas (r-lc-1-1) to (r-lc-1-7), (r-lc2-1) to (r-lc-2-18), (r- One of the groups represented by lc-6-1), (r-sl-1-1), and (r-sl-1-18) is more preferable.

The structural unit (a2) contained in the component (A1) may be one type or two or more types.
When the component (A1) has a constituent unit (a2), the ratio of the constituent unit (a2) is 20 to 70 mol% with respect to the total (100 mol%) of all the constituent units constituting the component (A1). It is preferably 40 to 60 mol%, and more preferably 40 to 60 mol%.
By setting the ratio of the constituent unit (a2) to a preferable lower limit value or more, the effect of containing the constituent unit (a2) can be sufficiently obtained, and when it is not more than the upper limit value, a balance with other constituent units is achieved. It is possible to improve various lithography characteristics.

≪Constructive unit (a3) ≫
The structural unit (a3) is a structural unit containing a polar group-containing aliphatic hydrocarbon group (however, excluding those corresponding to the structural unit (a1) and the structural unit (a2)). By having the component (A1) having the constituent unit (a3), for example, the acid diffusion length is appropriately adjusted, the adhesion of the resist film to the substrate is enhanced, the solubility during development is appropriately adjusted, and the etching resistance is improved. Due to the effect of improvement and the like, the lithography characteristics and the like are improved.

Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, a hydroxyalkyl group in which a part of hydrogen atoms of the alkyl group is replaced with a fluorine atom, and the like, and 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, and for example, in the resin for the resist composition for ArF excimer laser, it can be appropriately selected and used from a large number of proposed ones.

When the cyclic group is a monocyclic group, the number of carbon atoms is more preferably 3 to 10. Among them, a structural unit derived from an acrylic acid ester containing an aliphatic monocyclic 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. As the monocyclic group, a group obtained by removing two or more hydrogen atoms from a monocycloalkane can be exemplified. Specific examples thereof include groups obtained by removing two or more hydrogen atoms from monocycloalkanes such as cyclopentane, cyclohexane, and cyclooctane. Among these monocyclic groups, a group obtained by removing two or more hydrogen atoms from cyclopentane and a group obtained by removing two or more hydrogen atoms from cyclohexane are industrially preferable.

When the cyclic group is a polycyclic group, the polycyclic group preferably has 7 to 30 carbon atoms. Among them, a structural unit derived from 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 a group obtained by removing two or more hydrogen atoms from a bicycloalkane, a tricycloalkane, a tetracycloalkane, or the like. Specific examples thereof include groups obtained by removing two or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among these polycyclic groups, there are a group in which two or more hydrogen atoms are removed from adamantane, a group in which two or more hydrogen atoms are removed from norbornane, and a group in which two or more hydrogen atoms are 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 unit can be used.
The structural unit (a3) is a structural unit derived from an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent and includes a polar group-containing aliphatic hydrocarbon group. Constituent units are preferred.
As the structural unit (a3), 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, it is derived from the hydroxyethyl ester of acrylic acid. The structural unit to be formed is preferable.
Further, as the structural unit (a3), when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a polycyclic group, the structural unit represented by the following formula (a3-1), the formula (a3). The structural unit represented by -2) and the structural unit represented by the formula (a3-3) are preferable; in the case of a monocyclic group, the structural unit represented by the formula (a3-4) is used. It is mentioned as a preferable one.

［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０〜５の整数であり、ｓは１〜３の整数である。］

[In the formula, R is the same as above, j is an integer of 1-3, k is an integer of 1-3, t'is an integer of 1-3, and l is an integer of 0-5. And s is an integer of 1-3. ]

In the 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 3- and 5-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 preferable 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 attached to the 5- or 6-position of the norbornyl group.

In formula (a3-3), t'is preferably 1. l is preferably 1. s is preferably 1. These preferably have a 2-norbornyl group or a 3-norbornyl group bonded to the end of the carboxy group of acrylic acid. The fluorinated alkyl alcohol is preferably bonded to the 5 or 6 position of the norbornyl group.

In formula (a3-4), t'is preferably 1 or 2. l is preferably 0 or 1. s is preferably 1. The fluorinated alkyl alcohol is preferably bonded to the 3 or 5 position of the cyclohexyl group.

The structural unit (a3) contained in the component (A1) may be one type or two or more types.
When the component (A1) has a constituent unit (a3), the ratio of the constituent unit (a3) is 1 to 30 mol% with respect to the total (100 mol%) of all the constituent units constituting the component (A1). It is preferably 2 to 25 mol%, more preferably 5 to 20 mol%.
By setting the ratio of the constituent unit (a3) to be equal to or higher than the preferable lower limit value, the effect of containing the constituent unit (a3) can be sufficiently obtained by the above-mentioned effect, and if it is equal to or lower than the preferable upper limit value, other configurations are obtained. It can be balanced with the unit and various lithography characteristics are improved.

≪Other structural units≫
The component (A1) may have other structural units other than the above-mentioned structural unit (a1), structural unit (a2), and structural unit (a3).
Other structural units include, for example, a structural unit (a10) containing a hydroxystyrene skeleton, which will be described later, a structural unit (a9) represented by the general formula (a9-1), and a structural unit derived from styrene (however, a structural unit). (Excluding those corresponding to (a10)), a structural unit (a4) containing an acid non-dissociable aliphatic cyclic group, and the like.

<< Structural unit containing hydroxystyrene skeleton (a10) >>
The structural unit (a10) is a structural unit represented by the following general formula (a10-1).

［式中、Ｒは、水素原子、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である。Ｙａ^ｘ１は、単結合又は２価の連結基である。Ｗａ^ｘ１は、置換基を有してもよい芳香族炭化水素基である。ｎ_ａｘ１は、１以上の整数である。］

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Ya ^x1 is a single bond or divalent linking group. Wa ^x1 is an aromatic hydrocarbon group which may have a substituent. n _ax1 is an integer of 1 or more. ]

In the formula (a10-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms.
The alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, or n-. Examples thereof include a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
The alkyl halide group having 1 to 5 carbon atoms in R is a group in which a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. As the halogen atom, a fluorine atom is particularly preferable.
As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom, a methyl group or a trifluoromethyl group is more preferable because of industrial availability. Preferably, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.

In the formula (a10-1), Ya ^x1 is a single bond or a divalent linking group.
In the above chemical formula, the ^{divalent linking group in Ya x1} is not particularly limited, but a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, or the like is preferable. Is listed as.

A divalent hydrocarbon group that may have a substituent:
When Ya ^x1 is a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

· · ^{Aliphatic hydrocarbon group in Ya x1} Aliphatic hydrocarbon group means a hydrocarbon group having no aromatic property. 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, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

... Linear or branched aliphatic hydrocarbon group The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Numbers 1 to 4 are more preferable, and carbon numbers 1 to 3 are most preferable.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [−CH ₂ −], an ethylene group [− (CH ₂ ) ₂ −], and a trimethylene group [ − (CH ₂ ) ₃ −], tetramethylene group [− (CH ₂ ) ₄ −], pentamethylene group [− (CH ₂ ) ₅ −] and the like can be mentioned.
The branched-chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, further preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -C (CH ₃ ). Alkylene methylene groups such as _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _{2-, etc.;-} 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) Examples thereof include alkylalkylene groups such as alkyltetramethylene groups such as CH ₂ CH ₂ CH ₂ − and −CH ₂ CH (CH ₃ ) CH ₂ CH _{2 −.} As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

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, a carbonyl group and the like.

... An aliphatic hydrocarbon group containing a ring in the structure As the aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group may contain a substituent containing a hetero atom in the ring structure. (A group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), a group in which the cyclic aliphatic hydrocarbon group is bonded to the terminal of a linear or branched aliphatic hydrocarbon group, the cyclic fat Examples thereof include a group in which a group hydrocarbon group is present in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same groups as described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms, specifically. Examples thereof include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

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, an alkyl halide group, a hydroxyl group, a carbonyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are more preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group are more preferable. A methoxy group and an ethoxy group are more preferable.
As the halogen atom as the substituent, a fluorine atom is preferable.
Examples of the alkyl halide group as the substituent include a group in which a part or all of the hydrogen atom of the alkyl group is substituted with the halogen atom.
The cyclic aliphatic hydrocarbon group may be substituted with a substituent containing a hetero atom as a part of the carbon atom constituting the ring structure. The substituent containing a hetero atom, -O -, - C (= O) -O -, - S -, - S (= O) 2 -, - S (= O) 2 -O- are preferred.

Aromatic hydrocarbon group in Ya ^x1 The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be a monocyclic type or a polycyclic type. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 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, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); an aromatic compound containing two or more aromatic rings. A group obtained by removing two hydrogen atoms from (for example, biphenyl, fluorene, etc.); one of the hydrogen atoms of the group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring. Hydrogen from an aryl group in an arylalkyl group such as a group substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group). A group obtained by removing one more atom) and the like. The alkylene group bonded to the aryl group or the heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon number.

In the aromatic hydrocarbon group, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the 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, an alkyl halide group, a hydroxyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are more preferable.
Examples of the alkoxy group, halogen atom and alkyl halide 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 heteroatom:
When Ya ^x1 is a divalent linking group containing a heteroatom, preferred linking groups are -O-, -C (= O) -O-, -OC (= O)-,-. C (= O)-, -OC (= O) -O-, -C (= O) -NH-, -NH-, -NH-C (= NH)-(H is an alkyl group or an acyl group) may be substituted with substituent _{such), -. S -, -} S (= O) 2 -, - S (= O) 2 -O-, the formula ^-Y 21 ^{-O-Y 22} -, ^{-Y 21 -O -, - Y 21} -C (= O) -O -, - C (= O) -O-Y 21 -, - [Y 21 -C (= O) -O] m "-Y ^{22 -, - Y 21 -O-} C (= O) -Y 22 - or _{^{-Y 21 -S (= O) 2}} -O-Y 22 - group represented by ^{wherein, Y 21} and ^{Y 22} Each is a divalent hydrocarbon group which may have a substituent independently, O is an oxygen atom, and m "is an integer of 0 to 3. ] Etc. can be mentioned.
The divalent linking group containing the hetero atom is -C (= O) -NH-, -C (= O) -NH-C (= O)-, -NH-, -NH-C (= NH). In the case of −, the H may be substituted with a substituent such as an alkyl group or an acyl. 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 -, - C (= O) -O-Y 21 -, - [Y 21 - _{^{C (= O) -O] m}} "-Y 22 -, - Y 21 -O-C (= O) -Y 22 - or _{^{-Y 21 -S (= O) 2}} -O-Y 22 - in, Y ²¹ and Y ²² are divalent hydrocarbon groups which may independently have a substituent. The divalent hydrocarbon group will be described as a divalent linking group in ^{Ya x1.} The same as those mentioned in (divalent hydrocarbon group which may have a substituent) can be mentioned.
As Y ²¹ , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or an ethylene group is particularly preferable. preferable.
As Y ²² , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group or an alkyl methylene group is more preferable. 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.
Formula _{^{- [Y 21 -C (= O}} ) -O] m "-Y 22 - In the group represented by, m" is an integer of 0 to 3, preferably an integer of 0 to 2, 0 Or 1 is more preferable, and 1 is particularly preferable. In other words, the formula ^- Examples of the group represented by the formula ^{-Y 21 -C (= O) -O} -Y 22 - - [Y 21 -C (= O) -O] m "-Y 22 represented by A group is particularly preferable. Among _{them, a group represented by the formula − (CH 2} ) _{a ′} −C (= O) −O− (CH ₂ ) _{b ′} − is preferable. In the formula, a ′ is 1 to 1. It is an integer of 10, preferably an integer of 1-8, more preferably an integer of 1-5, even more preferably 1 or 2, and most preferably 1. b'is an integer of 1-10, 1-8. Is preferable, an integer of 1 to 5 is more preferable, 1 or 2 is more preferable, and 1 is most preferable.

Among the above, ^{as Ya x1} , single bond, ester bond [-C (= O) -O-, -OC (= O)-], ether bond (-O-), linear or branched chain It is preferably a alkylene group having a shape, or a combination thereof, and more preferably a single bond or an ester bond [-C (= O) -O-, -O-C (= O)-].

In the formula (a10-1), Wa ^x1 is an aromatic hydrocarbon group which may have a substituent.
Examples of the aromatic hydrocarbon group in Wa ^x1 _{include a group obtained by removing} (n ax1 + 1) hydrogen atoms from an aromatic ring which may have a substituent. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be a monocyclic type or a polycyclic type. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specifically, the aromatic ring is an aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, or phenanthrene; an aromatic heterocycle in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom or the like. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Further, ^{as the aromatic hydrocarbon group in Wa x1} _{, (nax1} + 1) hydrogen atoms are excluded from aromatic compounds (for example, biphenyl, fluorene, etc.) containing an aromatic ring which may have two or more substituents. There is also a group.
Among the above, ^{as Wa x1} _{, a group obtained by removing (n ax1} + 1) hydrogen atoms from benzene, naphthalene, anthracene or biphenyl is preferable, and a group obtained by removing (n _ax1 + 1) hydrogen atoms from benzene or naphthalene. Is more preferable, and a group obtained by removing _{(n ax1 + 1) hydrogen atoms from benzene is even more preferable.}

The aromatic hydrocarbon group in Wa ^x1 may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group and the like. Examples of the alkyl group, alkoxy group, halogen atom, and alkyl halide group as the substituent include those similar to those mentioned as the substituent of the cyclic aliphatic hydrocarbon group in ^{Ya x1.} The substituent is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, and an ethyl group or a methyl group. Further preferred, a methyl group is particularly preferred. The aromatic hydrocarbon group in Wa ^x1 preferably does not have a substituent.

In the above formula (a10-1), n _ax1 is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably 1, 2 or 3, and 1 or 2. Especially preferable.

A specific example of the structural unit (a10) represented by the above formula (a10-1) is shown below.
In each of the following formulas, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

The structural unit (a10) contained in the component (A1) may be one type or two or more types.
When the component (A1) has a constituent unit (a10), the ratio of the constituent unit (a10) in the component (A1) is relative to the total (100 mol%) of all the constituent units constituting the component (A1). 5 to 80 mol% is preferable, 10 to 75 mol% is more preferable, 30 to 70 mol% is further preferable, and 40 to 60 mol% is particularly preferable.
By setting the ratio of the structural unit (a10) within the above-mentioned preferable range, the efficiency of supplying protons in the resist film can be improved, and the solubility of the developing solution can be appropriately ensured, so that the effect of the present invention can be further obtained. It will be easier.

Structural unit (a4):
The structural unit (a4) is a structural unit containing an acid non-dissociative cyclic group. Since the component (A1) has the structural unit (a4), the dry etching resistance of the photosensitive resin pattern to be formed is improved. In addition, the hydrophobicity of the component (A1) is increased.
The "acid non-dissociative cyclic group" in the structural unit (a4) is contained in the structural unit as it is without dissociation even if the acid acts when an acid is generated from the component (B) described later by exposure. It is a cyclic group that remains in.

As the structural unit (a4), for example, a structural unit derived from an acrylic acid ester containing an acid non-dissociative aliphatic cyclic group is preferable. As the cyclic group, for example, the same ones as those exemplified in the case of the above-mentioned structural unit (a1) can be exemplified, such as for ArF excimer laser, for KrF excimer laser (preferably for ArF excimer laser), and the like. A large number of conventionally known ones used for the resin component of the resist composition of the above can be used. 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 that it is easily available industrially. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

As the structural unit (a4), specifically, those having the structures of the following general formulas (a4-1) to (a4-7) can be exemplified.

［式中、Ｒ^αは、水素原子、メチル基またはトリフルオロメチル基を示す。］

[In the formula, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group. ]

The structural unit (a4) contained in the component (A1) may be one kind or two or more kinds.
When the constituent unit (a4) is contained in the component (A1), the ratio of the constituent unit (a4) is preferably 1 to 30 mol% with respect to the total of all the constituent units constituting the component (A1). More preferably, it is 10 to 20 mol%.

In the component (A1), a monomer inducing each structural unit is dissolved in a polymerization solvent, and radical polymerization of, for example, azobisisobutyronitrile (AIBN), dimethyl azobisisobutyrate (for example, V-601, etc.) is started. It can be produced by adding an agent and polymerizing. Alternatively, the component (A1) includes a monomer for inducing a structural unit (a1) and, if necessary, a precursor monomer (a monomer having a protected functional group) for inducing a structural unit other than the structural unit (a1). Is dissolved in a polymerization solvent, a radical polymerization initiator as described above is added thereto for polymerization, and then a deprotection reaction is carried out to produce the product. At the time of polymerization, for _example, by using a combination of chain transfer agent such as _{HS-CH 2 -CH 2 -CH 2} -C (CF 3) 2 -OH, -C terminated _(CF 3) _2- OH groups may be introduced. In this way, the copolymer in which the hydroxyalkyl group in which a part of the hydrogen atom of the alkyl group is replaced with the fluorine atom is introduced can reduce development defects and LER (line edge roughness: non-uniform unevenness of the line side wall). It is effective in reducing.

The weight average molecular weight (Mw) of the component (A1) (polystyrene conversion standard by gel permeation chromatography (GPC)) is not particularly limited, and is preferably 1000 to 50000, more preferably 2000 to 30000, and 3000 to 3000. 20000 is even more preferred.
When the Mw of the component (A1) is not more than a preferable upper limit value in this range, there is sufficient solubility in a resist solvent to be used as a resist, and when it is not more than a preferable lower limit value in this range, dry etching resistance and dry etching resistance are increased. The resist pattern has a good cross-sectional shape.
The dispersity (Mw / Mn) of the component (A1) is not particularly limited, and is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.1 to 2.0. .. Mn indicates a number average molecular weight.

≪ (B) component ≫
The component (B) is an acid generator component that generates an acid upon exposure.
The component (B) is not particularly limited, and those previously proposed as an acid generator for a chemically amplified resist composition can be used.
Examples of such an acid generator include onium salt-based acid generators such as iodonium salt and sulfonium salt, and oxime sulfonate-based acid generators; diazomethanes such as bisalkyl or bisarylsulfonyldiazomethanes and poly (bissulfonyl) diazomethanes. Acid generators: Various types such as nitrobenzyl sulfonate-based acid generators, imino sulfonate-based acid generators, and disulfon-based acid generators can be mentioned.

Examples of the onium salt-based acid generator include a compound represented by the following general formula (b-1) (hereinafter, also referred to as “component (b-1)”) and a general formula (b-2). Examples thereof include a compound (hereinafter, also referred to as “(b-2) component”) or a compound represented by the general formula (b-3) (hereinafter, also referred to as “(b-3) component”).

［式中、Ｒ^１０１及びＲ^１０４〜Ｒ^１０８は、それぞれ独立に、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、又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。Ｒ^１０４とＲ^１０５とは相互に結合して環構造を形成していてもよい。Ｒ^１０２は、炭素数１〜５のフッ素化アルキル基又はフッ素原子である。Ｙ^１０１は、酸素原子を含む２価の連結基又は単結合である。Ｖ^１０１〜Ｖ^１０３は、それぞれ独立に、単結合、アルキレン基又はフッ素化アルキレン基である。Ｌ^１０１〜Ｌ^１０２は、それぞれ独立に、単結合又は酸素原子である。Ｌ^１０３〜Ｌ^１０５は、それぞれ独立に、単結合、−ＣＯ−又は−ＳＯ_２−である。ｍは１以上の整数であって、Ｍ’^ｍ＋はｍ価のオニウムカチオンである。］

[In the formula, R ¹⁰¹ and R ^{104 to} R ¹⁰⁸ each independently have a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. It is a chain alkenyl group that may have. R ¹⁰⁴ and R ¹⁰⁵ may be coupled to each other to form a ring structure. R ¹⁰² is a fluorinated alkyl group or a fluorine atom having 1 to 5 carbon atoms. Y ¹⁰¹ is a divalent linking group or a single bond containing an oxygen atom. V ^{101 to} V ¹⁰³ are each independently a single bond, an alkylene group or a fluorinated alkylene group. L ^{101 to} L ¹⁰² are each independently a single bond or an oxygen atom. L ^{103 to} L ¹⁰⁵ are each independently single-bonded, -CO- or -SO _2- . m is an integer of 1 or more, ^{and M'm +} is an m-valent onium cation. ]

{Anion part}
-In the anion formula (b-1) in the component (b-1), R ¹⁰¹ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or It is a chain alkenyl group which may have a substituent.

Cyclic group which may have a substituent:
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. Aliphatic hydrocarbon groups mean hydrocarbon groups that do not have aromatic properties. Further, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

The aromatic hydrocarbon group in R ¹⁰¹ is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon 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 number of carbon atoms does not include the number of carbon atoms in the substituent.
^{Specifically, as the aromatic ring contained} in the aromatic hydrocarbon group in R 101, benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or a part of carbon atoms constituting these aromatic rings was substituted with a hetero atom. Examples include aromatic heterocycles. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like.
Specifically, as the aromatic hydrocarbon group in R ^101, a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.) and one of the hydrogen atoms of the aromatic ring are alkylene. Examples thereof include groups substituted with a group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.). 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.

Examples of the cyclic aliphatic hydrocarbon group in R ¹⁰¹ include an aliphatic hydrocarbon group containing a ring in the structure.
As the aliphatic hydrocarbon group containing a ring in this structure, an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from the aliphatic hydrocarbon ring) and an alicyclic hydrocarbon group are linear or branched. Examples thereof include a group bonded to the terminal of a chain-shaped aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like.
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 a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among them, the polycycloalkane includes a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; a fused ring system such as a cyclic group having a steroid skeleton. Polycycloalkanes having a polycyclic skeleton of are more preferred.

Among them, as ^{the cyclic aliphatic hydrocarbon group in R 101} , a group obtained by removing one or more hydrogen atoms from monocycloalkane or polycycloalkane is preferable, and a group obtained by removing one hydrogen atom from polycycloalkane is more preferable. Preferably, an adamantyl group and a norbornyl group are particularly preferable, and an adamantyl group is most preferable.

The linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms. 1-3 are most preferable. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [−CH ₂ −], an ethylene group [− (CH ₂ ) ₂ −], and a trimethylene group [ − (CH ₂ ) ₃ −], tetramethylene group [− (CH ₂ ) ₄ −], pentamethylene group [− (CH ₂ ) ₅ −] and the like can be mentioned.
The branched-chain aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, and further preferably 3 or 4 carbon atoms. 3 is the most preferable. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -C (CH ₃ ). Alkylene methylene groups such as _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _{2-, etc.;-} 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) Examples thereof include alkylalkylene groups such as alkyltetramethylene groups such as CH ₂ CH ₂ CH ₂ − and −CH ₂ CH (CH ₃ ) CH ₂ CH _{2 −.} As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

Further, ^{the cyclic hydrocarbon group in R 101} may contain a hetero atom such as a heterocycle. Specifically, the lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), respectively, and the general formulas (a5-r-1) to (a5-r-). _{Examples thereof include a -SO 2} -containing cyclic group represented by 4) and a heterocyclic group represented by the following chemical formulas (r-hr-1) to (r-hr-16). * In the formula represents a bond that binds to ^{Y 101} in the formula (b-1).

Examples of the substituent in the cyclic group of R ¹⁰¹ include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group, a nitro group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferable, and methoxy. Groups and ethoxy groups are most preferable.
As the halogen atom as the substituent, a fluorine atom is preferable.
As the alkyl halide group as a substituent, a part or all of hydrogen atoms such as an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group are described above. Examples include groups substituted with halogen atoms.
The carbonyl group as a substituent is a group that substitutes the _{methylene group (−CH 2−) constituting the cyclic hydrocarbon group.}

The cyclic hydrocarbon group in R ¹⁰¹ may be a fused cyclic group containing a condensed ring in which an aliphatic hydrocarbon ring and an aromatic ring are condensed. Examples of the fused ring include those obtained by condensing one or more aromatic rings with a polycycloalkane having a polycyclic skeleton of a crosslinked ring system. Specific examples of the crosslinked ring-based polycycloalkane include bicycloalkanes such as bicyclo [2.2.1] heptane (norbornane) and bicyclo [2.2.2] octane. As the condensed ring type, a group containing a condensed ring in which two or three aromatic rings are condensed with bicycloalkane is preferable, and two or three aromatic rings are condensed with bicyclo [2.2.2] octane. Groups containing fused rings are more preferred. Specific examples of the fused cyclic group in R ¹⁰¹ include those represented by the following formulas (r-br-1) to (r-br-2). * In the formula represents a bond that binds to ^{Y 101} in the formula (b-1).

Examples of the substituent that the fused cyclic group in R ¹⁰¹ may have include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group, a nitro group, an aromatic hydrocarbon group, and a fat. Examples include a cyclic hydrocarbon group.
Examples of the alkyl group, alkoxy group, halogen atom, and alkyl halide group as the substituent of the fused cyclic group include the same as those mentioned as the substituent of the cyclic group in ^{R 101.}
Examples of the aromatic hydrocarbon group as a substituent of the fused cyclic group include a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), and a hydrogen atom of the aromatic ring. A group in which one is substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.), the above. Examples thereof include heterocyclic groups represented by the formulas (r-hr-1) to (r-hr-6), respectively.
The alicyclic hydrocarbon group as a substituent of the fused cyclic group is a group obtained by removing one hydrogen atom from monocycloalkane such as cyclopentane and cyclohexane; adamantan, norbornan, isobornane, tricyclodecane and tetra. A group obtained by removing one hydrogen atom from a polycycloalkane such as cyclododecane; a lactone-containing cyclic group represented by the general formulas (a2-r-1) to (a2-r-7), respectively; the general formula. _{-SO 2} -containing cyclic group represented by (a5-r-1) to (a5-r-4); represented by the above formulas (r-hr-7) to (r-hr-16), respectively. Examples thereof include a heterocyclic group.

Chain-like alkyl group which may have a substituent:
The chain alkyl group of R ¹⁰¹ may be either linear or branched.
The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specifically, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decanyl group, an undecyl group, a dodecyl group, a tridecyl group, an isotridecyl group and a tetradecyl group. Examples thereof include a group, a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group, an icosyl group, a henicosyl group, a docosyl group and the like.
The branched-chain 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 thereof include 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group and 4-methylpentyl group.

Chain alkenyl group which may have a substituent:
The chain alkenyl group of R ¹⁰¹ may be either linear or branched, preferably having 2 to 10 carbon atoms, more preferably 2 to 5, further preferably 2 to 4, and 3 Is particularly preferable. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), a butynyl group and the like. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, a 2-methylpropenyl group and the like.
Among the above, as the chain alkenyl group, a linear alkenyl group is preferable, a vinyl group and a propenyl group are more preferable, and a vinyl group is particularly preferable.

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

Among the above, R ¹⁰¹ is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane; represented by the general formulas (a2-r-1) to (a2-r-7), respectively. _{Lactone-containing cyclic group; -SO 2} -containing cyclic group represented by the general formulas (a5-r-1) to (a5-r-4), respectively, is preferable.

In formula (b-1), Y ¹⁰¹ is a divalent linking group containing a single bond or an oxygen atom.
When Y ¹⁰¹ is a divalent linking group ^{containing an oxygen atom, the Y 101} may contain an atom other than the oxygen atom. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, nitrogen atoms and the like.
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 oxycarbonyl group (−OC (= O−). )-), Amid bond (-C (= O) -NH-), carbonyl group (-C (= O)-), carbonate bond (-OC (= O) -O-) and other non-hydrocarbons Oxygen atom-containing linking group of the system; Examples thereof include a combination of the oxygen atom-containing linking group of the non-hydrocarbon system and an alkylene group. A sulfonyl group (-SO _2- ) may be further linked to this combination. Examples of the divalent linking group containing such an oxygen atom include linking groups represented by the following general formulas (y-al-1) to (y-al-7), respectively.

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

Divalent saturated hydrocarbon group in V ^'102 is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, alkylene group having 1 to 5 carbon atoms Is more preferable.

The alkylene group for V ^'101 and V' ^102, may be linear well branched alkylene group with an alkylene group, a linear alkylene group is preferable.
As the alkylene group for V ^'101 and V' ^102, specifically, a methylene group _{[-CH 2 -]; - CH} (CH 3) -, - CH (CH 2 CH 3) -, - C (CH 3) Alkylene methylene groups such as _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _{2-, etc.; 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 CH) ₃ ) _{Alkylethylene groups such as 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 ) Alkyl methylene groups such as CH _{2- ; tetramethylene groups [-CH 2} CH ₂ CH ₂ CH _2- ]; -CH (CH ₃ ) CH ₂ CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ Alkyltetramethylene groups such as CH _2- ; pentamethylene groups [-CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ] and the like can be mentioned.
A part of the methylene groups in the alkylene group for V ^'101 or V' ¹⁰² may be substituted by a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group, the formula (a1-r-1) aliphatic Ra 'of ³ circular in the hydrocarbon group (monocyclic aliphatic hydrocarbon group, a polycyclic aliphatic hydrocarbon group ), A divalent group obtained by further removing one hydrogen atom is preferable, and a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group is more preferable.

As Y ¹⁰¹ , a divalent linking group containing an ester bond or a divalent linking group containing an ether bond is preferable, and they are represented by the above formulas (y-al-1) to (y-al-5), respectively. Linking groups are more preferred.

In formula (b-1), V ¹⁰¹ is a single bond, an alkylene group or a fluorinated alkylene group. The alkylene group and the fluorinated alkylene group in V ^{101 preferably have 1 to 4 carbon atoms. Examples} of the fluorinated alkylene group in V ¹⁰¹ include a group in which a part or all of hydrogen atoms of the alkylene group in V 101 are substituted with a fluorine atom. Among them, 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 a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. R ¹⁰² is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.

Specific examples of the anion portion represented by the above formula (b-1) include fluorinated alkyl sulfonate anions such as trifluoromethanesulfonate anion and perfluorobutane sulfonate anion when ^{Y 101 has a single bond.} 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、置換基を有してもよい脂肪族環式基、上記の化学式（ｒ−ｈｒ−１）〜（ｒ−ｈｒ−６）でそれぞれ表される１価の複素環式基、前記式（ｒ−ｂｒ−１）又（ｒ−ｂｒ−２）で表される縮合環式基、又は置換基を有してもよい鎖状のアルキル基である。Ｒ”^１０２は、置換基を有してもよい脂肪族環式基、前記式（ｒ−ｂｒ−１）又（ｒ−ｂｒ−２）で表される縮合環式基、前記一般式（ａ２−ｒ−１）、（ａ２−ｒ−３）〜（ａ２−ｒ−７）でそれぞれ表されるラクトン含有環式基、又は前記一般式（ａ５−ｒ−１）〜（ａ５−ｒ−４）でそれぞれ表される−ＳＯ_２−含有環式基である。Ｒ”^１０３は、置換基を有してもよい芳香族環式基、置換基を有してもよい脂肪族環式基、又は置換基を有してもよい鎖状のアルケニル基である。Ｖ”^１０１は、単結合、炭素数１〜４のアルキレン基、又は炭素数１〜４のフッ素化アルキレン基である。Ｒ^１０２は、フッ素原子又は炭素数１〜５のフッ素化アルキル基である。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０〜２０の整数であり、ｎ”は０または１である。］

[In the formula, R " ¹⁰¹ is an aliphatic cyclic group that may have a substituent, and a monovalent complex represented by the above chemical formulas (r-hr-1) to (r-hr-6), respectively. It is a cyclic group, a fused cyclic group represented by the above formula (r-br-1) or (r-br-2), or a chain alkyl group which may have a substituent. R " ^102. Is an aliphatic cyclic group which may have a substituent, a fused cyclic group represented by the above formula (r-br-1) or (r-br-2), and the above general formula (a2-r-). 1), lactone-containing cyclic groups represented by (a2-r-3) to (a2-r-7), respectively, or the general formulas (a5-r-1) to (a5-r-4), respectively. It is a -SO ₂ -containing cyclic group represented. 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 " ¹⁰¹ is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms. R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. v "is an integer of 0 to 3 independently, q" is an integer of 0 to 20 independently, and n "is an integer of 0 or 1."

The aliphatic cyclic group which may have a substituent of R " ¹⁰¹ , R" ¹⁰² and R " ¹⁰³ is a group exemplified as a cyclic aliphatic hydrocarbon group in ^{R 101 in the above formula (b-1).} As the substituent, the same group as the substituent which may replace the cyclic aliphatic hydrocarbon group in ^{R 101 in the above formula (b-1) can be mentioned.}

The aromatic cyclic group which may have a substituent in R " ¹⁰³ may be the group exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in ^{R 101 in the above formula (b-1).} Preferred. Examples of the substituent include the same substituents in which the aromatic hydrocarbon group in ^{R 101} in the formula (b-1) may be substituted.

The chain-like alkyl group that may have a substituent at R " ¹⁰¹ is preferably the group exemplified as the chain-like alkyl group ^{at R 101 in the above formula (b-1).}
The chain alkenyl group which may have a substituent in R " ¹⁰³ is preferably the group exemplified as the chain alkenyl group in ^{R 101 in the above formula (b-1).}

-In the anion formula (b-2) in the component (b-2), R ¹⁰⁴ and R ¹⁰⁵ may independently have a cyclic group and a substituent, respectively. A chain-like alkyl group or a chain-like alkenyl group which may have a substituent, each of which is similar to ^{R 101 in the formula (b-1).} However, R ¹⁰⁴ and R ¹⁰⁵ may be coupled to each other to form a ring.
R ¹⁰⁴ and R ¹⁰⁵ are preferably a chain-like alkyl group which may have a substituent, and are a linear or branched alkyl group, or a linear or branched fluorinated alkyl group. Is more preferable.
The chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and further preferably 1 to 3 carbon atoms. The carbon number of the chain alkyl group of R ¹⁰⁴ and R ¹⁰⁵ is preferably as small as possible because the solubility in the resist solvent is also good within the above carbon number range. Further, in ^{the chain alkyl groups of R 104} and R ^105, the larger the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, and the stronger the acid strength, and the higher the acid strength with respect to high-energy light or electron beam of 250 nm or less. This is preferable because it improves transparency. The ratio of fluorine atoms in the chain alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all hydrogen atoms are substituted with fluorine atoms. It is a perfluoroalkyl group.
In formula (b-2), V ¹⁰² and V ¹⁰³ are independently single-bonded, alkylene groups, or fluorinated alkylene groups, respectively, which are similar to ^{V 101 in formula (b-1).} Can be mentioned.
In formula (b-2), L ¹⁰¹ and L ¹⁰² are independently single bonds or oxygen atoms, respectively.

-In the anion formula (b-3) in the component (b-3), R ^{106 to} R ¹⁰⁸ may independently have a cyclic group and a substituent, respectively. A chain-like alkyl group or a chain-like alkenyl group which may have a substituent, and the same as ^{R 101 in the formula (b-1) can be mentioned.}
Formula (b-3) ^in, L 103 ^{~L 105} are each independently a single bond, -CO- or -SO ₂ - is.

Among the above, as the anion portion of the component (B), the anion in the component (b-1) is preferable. Among these, the anion represented by any of the above general formulas (an-1) to (an-3) is more preferable, and it is represented by either the general formula (an-1) or (an-2). Anions are more preferred, and anions represented by the general formula (an-2) are particularly preferred.

{Cation part}
In the above formulas (b-1), (b-2), and (b-3) ^{, M'm +} represents an m-valent onium cation. Of these, sulfonium cations and iodonium cations are preferable.
m is an integer of 1 or more.

Preferred cation portions (( ^{M'm +} ) _{1 / m} ) include organic cations represented by the following general formulas (ca-1) to (ca-5), respectively.

［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もよいアリール基、アルキル基またはアルケニル基を表す。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い。Ｒ^２０８〜Ｒ^２０９は、それぞれ独立に水素原子または炭素数１〜５のアルキル基を表す。Ｒ^２１０は、置換基を有してもよいアリール基、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、又は置換基を有してもよいＳＯ_２−含有環式基である。Ｌ^２０１は、−Ｃ（＝Ｏ）−または−Ｃ（＝Ｏ）−Ｏ−を表す。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を表す。ｘは１または２である。Ｗ^２０１は（ｘ＋１）価の連結基を表す。］

[In the formula, R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² each represent an aryl group, an alkyl group or an alkenyl group which may independently have a substituent. 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 independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ²¹⁰ contains an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or SO _{2- which may have a substituent.} It is a cyclic group. L ²⁰¹ represents −C (= O) − or −C (= O) −O−. Y ²⁰¹ independently represents an arylene group, an alkylene group or an alkaneylene group. x is 1 or 2. W ²⁰¹ represents a linking group of (x + 1) valence. ]

In the above general formulas (ca-1) to (ca-5), ^{examples of the aryl group in R 201 to} R ²⁰⁷ and R ^{211 to} R ²¹² include an unsubstituted aryl group having 6 to 20 carbon atoms. A phenyl group and a naphthyl group are preferable.
The alkyl groups in R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² are preferably chain or cyclic alkyl groups having 1 to 30 carbon atoms.
The alkenyl group in R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² preferably has 2 to 10 carbon atoms.
Substituents that R ^{201 to} R ²⁰⁷ and R ^{210 to} R ²¹² may have include, for example, an alkyl group, a halogen atom, an alkyl halide group, a carbonyl group, a cyano group, an amino group, an aryl group, and the following. Examples thereof include groups represented by the general formulas (ca-r-1) to (ca-r-7) of.

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

[In the formula, ^R'201 may independently have a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. It is a good chain alkenyl group. ]

Cyclic group which may have a substituent:
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. Aliphatic hydrocarbon groups mean hydrocarbon groups that do not have aromatic properties. Further, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

Aromatic hydrocarbon group for R ^'201 is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon 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 6 to 6 carbon atoms. 10 is the most preferable. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic ring with an aromatic hydrocarbon group in R ^'201, benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or a portion of these carbon atoms constituting the aromatic ring is replaced with a heteroatom Examples include aromatic heterocycles. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like.
Specific examples of the aromatic hydrocarbon group for R ^'201, wherein one hydrogen atom from an aromatic ring group formed by removing (aryl group: for example, a phenyl group, a naphthyl group), one of the hydrogen atoms of the aromatic ring but alkylene Examples thereof include groups substituted with a group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.). 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 number.

R 'cyclic in ²⁰¹ aliphatic hydrocarbon group include aliphatic hydrocarbon group containing a ring in the structure.
As the aliphatic hydrocarbon group containing a ring in this structure, an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from the aliphatic hydrocarbon ring) and an alicyclic hydrocarbon group are linear or branched. Examples thereof include a group bonded to the terminal of a chain-shaped aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like.
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 a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among them, the polycycloalkane includes a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; a fused ring system such as a cyclic group having a steroid skeleton. Polycycloalkanes having a polycyclic skeleton of are more preferred.

Among them, the aliphatic cyclic hydrocarbon group in R ^'201, one or more exception groups is preferably a hydrogen atom from a monocycloalkane or a polycycloalkane, a group in which one hydrogen atom is eliminated from a polycycloalkane More preferably, an adamantyl group and a norbornyl group are particularly preferable, and an adamantyl group is most preferable.

The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and carbon. Numbers 1 to 4 are more preferable, and carbon numbers 1 to 3 are particularly preferable.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [−CH ₂ −], an ethylene group [− (CH ₂ ) ₂ −], and 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 preferable, and specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -C (CH ₃ ). Alkylene methylene groups such as _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _{2-, etc.;-} 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) Examples thereof include alkylalkylene groups such as alkyltetramethylene groups such as CH ₂ CH ₂ CH ₂ − and −CH ₂ CH (CH ₃ ) CH ₂ CH _{2 −.} As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

Moreover, cyclic hydrocarbon group in R ^'201 may contain a hetero atom as such a heterocyclic ring. Specifically, the lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), respectively, and the general formulas (a5-r-1) to (a5-r-). _{Examples thereof include the -SO 2} -containing cyclic group represented by 4) and the heterocyclic group represented by the above chemical formulas (r-hr-1) to (r-hr-16), respectively.

Examples of the substituent in the cyclic group of R ^'201, for example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferable, and methoxy. Groups and ethoxy groups are most preferable.
As the halogen atom as the substituent, a fluorine atom is preferable.
As the alkyl halide group as a substituent, a part or all of hydrogen atoms such as an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group are described above. Examples include groups substituted with halogen atoms.
The carbonyl group as a substituent is a group that substitutes the _{methylene group (−CH 2−) constituting the cyclic hydrocarbon group.}

Chain-like alkyl group which may have a substituent:
The chain alkyl group R ^'201, may be either linear or branched.
The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms.
The branched-chain 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 thereof include 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group and 4-methylpentyl group.

Chain alkenyl group which may have a substituent:
The chain alkenyl group R ^'201, may be either linear or branched, preferably has a carbon number of 2 to 10, 2 to 5 carbon atoms, more preferably, a carbon number from 2 to 4 Is more preferable, and 3 carbon atoms is particularly preferable. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), a butynyl group and the like. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, a 2-methylpropenyl group and the like.
Among the above, as the chain alkenyl group, a linear alkenyl group is preferable, a vinyl group and a propenyl group are more preferable, and a vinyl group is particularly preferable.

'The substituent in chain alkyl group or alkenyl group of ^201, for example, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, the R' R cyclic group for ²⁰¹ And so on.

R ^'201 of an optionally substituted cyclic group, an optionally substituted chain alkyl group, or a substituent good chain alkenyl group which may have a, although the above-described other , A cyclic group which may have a substituent or a chain alkyl group which may have a substituent, which is the same as the acid dissociable group represented by the above formula (a1-r-2). Can also be mentioned.

Among them, ^R'201 is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, for example, a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane; represented by the general formulas (a2-r-1) to (a2-r-7), respectively. lactone-containing cyclic group are; -SO ₂ respectively represented by the general formula (a5-r-1) ~ (a5-r-4) - such as containing cyclic group.

In the above general formulas (ca-1) to (ca-5), R ^{201 to} R ²⁰³ , R ^{206 to} R ²⁰⁷ , and R ^{211 to} R ²¹² are bonded to each other to form a ring together with the sulfur atom in the formula. If you, sulfur atom, oxygen atom, or a hetero atom such as nitrogen atom, a carbonyl _{group, -SO -, - SO 2 -} , - SO 3 -, - COO -, - CONH- , or -N _(R N) - ₍ the R _N may be bonded via a functional group such as an alkyl group having 1 to 5 carbon atoms.). As the ring to be formed, one ring containing a sulfur atom in its ring skeleton, including the sulfur atom, is preferably a 3 to 10-membered ring, and particularly preferably a 5- to 7-membered ring. preferable. Specific examples of the ring to be formed include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxatiin ring, and a tetrahydro. Examples thereof include a thiophenium ring and a tetrahydrothiopyranium ring.

R ^{208 to} R ²⁰⁹ independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and when they are alkyl groups, they are bonded to each other. A ring may be formed.

R ²¹⁰ contains an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or SO _{2- which may have a substituent.} It is a cyclic group.
^Examples of the aryl group in R 210 include an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable.
The alkyl group in R ²¹⁰ is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group in R ²¹⁰ preferably has 2 to 10 carbon atoms.
As the _{SO 2} -containing cyclic group which may have a substituent in ^{R 210} _{, "-SO 2} -containing polycyclic group" is preferable, and it is represented by the above general formula (a5-r-1). Groups are more preferred.

Y ²⁰¹ independently represents an arylene group, an alkylene group or an alkaneylene group.
Examples of the arylene group in Y ²⁰¹ include a group obtained by removing one hydrogen atom from the aryl group exemplified as the aromatic hydrocarbon group in ^{R 101} in the above formula (b-1).
Examples of the alkylene group and the alkaneylene group in Y ^{201 include a chain alkyl group in R 101} in the above formula (b-1) and a group obtained by removing one hydrogen atom from the group exemplified as the chain alkenyl group. ..

In the formula (ca-4), x is 1 or 2.
W ²⁰¹ is a (x + 1) valence, i.e., a divalent or trivalent linking group.
As the ^{divalent linking group in W 201, a} divalent hydrocarbon group which may have a substituent is preferable, and it has a substituent similar to ^{Ya 21 in the above general formula (a2-1).} A divalent hydrocarbon group may be exemplified. 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 obtained by removing one hydrogen atom from the divalent linking group in W 201} , a group in which the divalent linking group is further bonded to the divalent linking group, and the like. Can be mentioned. As the ^{trivalent linking group in W 201} , a group in which two carbonyl groups are bonded to an arylene group is preferable.

Specific examples of suitable cations represented by the formula (ca-1) include cations represented by the following chemical formulas (ca-1-1) to (ca-1-70).

［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。］

[In the formula, g1, g2, and g3 indicate 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、該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。］

[In the formula, R " ²⁰¹ is a hydrogen atom or a substituent, and the substituents are the same as those listed as the substituents that ^{R 201 to} R ²⁰⁷ and R ^{210 to} R ^{212 may have.} Is.]

Specific examples of the suitable cation represented by the formula (ca-2) include a diphenyl iodonium cation and a bis (4-tert-butylphenyl) iodonium cation.

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

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

Specific examples of suitable cations represented by the formula (ca-5) include cations represented by the following general formulas (ca-5-1) to (ca-5-3).

Among the above, the cation portion (( ^{M'm +} ) _{1 / m} ) is preferably a cation represented by the general formula (ca-1).

In the resist composition of the present embodiment, the component (B) may be used alone or in combination of two or more.
When the resist composition contains the component (B), the content of the component (B) in the resist composition is preferably less than 50 parts by mass, preferably 1 to 40 parts by mass with respect to 100 parts by mass of the component (A). Is more preferable, and 5 to 25 parts by mass is further preferable.
By setting the content of the component (B) to the above-mentioned preferable range, pattern formation is sufficiently performed. Further, when each component of the resist composition is dissolved in an organic solvent, a uniform solution can be easily obtained, and the storage stability of the resist composition becomes good, which is preferable.

<< Organic solvent component (S) >>
The resist composition in the present embodiment can be produced by dissolving a resist material in an organic solvent component (hereinafter referred to as "(S) component").
The component (S) may be any component as long as it can dissolve each component to be used to form a uniform solution, and any conventionally known solvent for the chemically amplified resist composition may be appropriately used. It can be selected and used.
Examples of the component (S) include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone and 2-heptanone; ethylene glycol, diethylene glycol and propylene glycol. , Polyhydric alcohols such as dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, said polyhydric alcohols or having said ester bond. Derivatives of polyhydric alcohols such as monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether and monobutyl ether of compounds or compounds having an ether bond such as monophenyl ether [among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred]; cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate. , Esters such as methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenitol, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, Examples thereof include aromatic organic solvents such as xylene, simene and mesityrene, dimethyl sulfoxide (DMSO) and the like.
In the resist composition of the present embodiment, the component (S) may be used alone or as a mixed solvent of two or more kinds. Of these, PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone are preferable.

Further, as the component (S), a mixed solvent in which PGMEA and a polar solvent are mixed is also preferable. The blending ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, but is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. It is preferably 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. .. When PGME is blended as the polar solvent, the mass ratio of PGMEA: PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, and even more preferably 3: 7 to 7 :. It is 3. Further, a mixed solvent of PGMEA, PGME and cyclohexanone is also preferable.
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 mass ratio of the former and the latter is preferably 70:30 to 95: 5 as the mixing ratio.
The amount of the component (S) used is not particularly limited, and is a concentration that can be applied to a substrate or the like, and is appropriately set according to the coating film thickness. Generally, the component (S) is used so that the solid content concentration of the resist composition is in the range of 0.1 to 20% by mass, preferably 0.2 to 15% by mass.

The resist composition in the present embodiment may further contain components other than the above-mentioned component (A), component (B), and component (S). Examples of such a component include the following components (D), (E), and (F).

≪ (D) component ≫
The resist composition in the present embodiment further contains a base component (hereinafter referred to as "(D) component") in addition to the component (A) or in addition to the components (A) and (B). You may. The component (D) acts as a quencher (acid diffusion control agent) that traps the acid generated by exposure in the resist composition.
The component (D) may be a photodisintegrating base (D1) (hereinafter referred to as “component (D1)”) that is decomposed by exposure and loses acid diffusion controllability, and includes a component (D1) that does not correspond to the component (D1). It may be a nitrogen organic compound (D2) (hereinafter referred to as “(D2) component”).
By using a resist composition containing the component (D), the contrast between the exposed portion and the unexposed portion of the resist film can be further improved when the resist pattern is formed.

-Regarding the component (D1) By using a resist composition containing the component (D1), the contrast between the exposed portion and the unexposed portion of the resist film can be further improved when forming the resist pattern.
The component (D1) is not particularly limited as long as it decomposes by exposure and loses acid diffusion controllability, and is a compound represented by the following general formula (d1-1) (hereinafter, “component (d1-1)”). The compound represented by the following general formula (d1-2) (hereinafter referred to as "(d1-2) component") and the compound represented by the following general formula (d1-3) (hereinafter referred to as "(d1-d1-) component"). 3) One or more compounds selected from the group consisting of "components") are preferable.
The components (d1-1) to (d1-3) do not act as a quencher because they decompose in the exposed part of the resist film and lose the acid diffusion controllability (basicity), and the quenching occurs in the unexposed part of the resist film. Acts as a char.

［式中、Ｒｄ^１〜Ｒｄ^４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、又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。但し、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は単結合又は２価の連結基である。ｍは１以上の整数であって、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, Rd ^{1 to Rd 4} have 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. It is an alkenyl group of. However, it is assumed that the fluorine atom is not bonded to the carbon atom adjacent to the S atom in ^{Rd 2} in the formula (d1-2). Yd ¹ is a single bond or divalent linking group. m is an integer of 1 or more, and M ^{m +} is an independently m-valent organic cation. ]

{(D1-1) component}
-In the anion part formula (d1-1), Rd ¹ has a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. is also a good chain alkenyl groups include respective the same as the R ^'201.
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 alkyl group is preferred. Substituents that these groups may have include hydroxyl groups, oxo groups, alkyl groups, aryl groups, fluorine atoms, alkyl fluorinated groups, and the above general formulas (a2-r-1) to (a2-r-). Examples thereof include a lactone-containing cyclic group represented by 7), an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is contained as a substituent, an alkylene group may be used as a substituent, and the substituent in this case is represented by the above formulas (y-al-1) to (y-al-5), respectively. Linking groups are preferred.
Preferable examples of the aromatic hydrocarbon group include a polycyclic structure containing a phenyl group, a naphthyl group, and a bicyclooctane skeleton (a polycyclic structure composed of a bicyclooctane skeleton and a ring structure other than the bicyclooctane skeleton).
The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane.
The chain alkyl group preferably has 1 to 10 carbon atoms, and specifically, 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 the like. Linear alkyl groups such as nonyl group and decyl group; 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl Examples thereof include branched alkyl groups such as a group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

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

A preferable specific example of the anion portion of the component (d1-1) is shown below.

-In the cation part formula (d1-1), M ^{m +} is an m-valent organic cation.
As ^{the organic cation of M m +,} the same cations as those represented by the general formulas (ca-1) to (ca-4) are preferably mentioned, and are represented by the general formula (ca-1). Cations are more preferable, and cations represented by the formulas (ca-1-1) to (ca-1-78) and (ca-1-101) to (ca-1-149) are even more 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}
-In the anion part formula (d1-2), Rd ² has a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. is also a good chain alkenyl group include the same as the R ^'201.
However, it is assumed that the carbon atom adjacent to the S atom in ^{Rd 2 does not have a fluorine atom bonded (fluorine-substituted).} As a result, the anion of the component (d1-2) becomes an appropriate weak acid anion, and the citric acid ability as the component (D) is improved.
Rd ² is preferably a chain alkyl group which may have a substituent or an aliphatic cyclic group which may have a substituent. The chain alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. As the aliphatic cyclic group, a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (may have a substituent); one from camphor, etc. It is more preferable that the group is a group excluding the above hydrogen atom.
The hydrocarbon group of Rd ² may have a substituent, and the substituent may be a hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group ^{) in Rd 1 of the above formula (d1-1).} , The same as the substituent which the chain alkyl group) may have.

A preferable specific example of the anion portion of the component (d1-2) is shown below.

-In the cation part formula (d1-2), M ^{m +} is an m-valent organic cation, which is the same as M ^{m +} in the above 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}
-In the anion part formula (d1-3), Rd ³ has a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. is also a good chain alkenyl group, wherein R ^'201 like can be mentioned a cyclic group containing a fluorine atom, chain alkyl group, or is preferably a chain alkenyl group. Of these, an alkyl fluorinated group is preferable, and the same group as the alkyl fluorinated group of ^{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. a chain alkenyl group include the same as the R ^'201.
Of 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, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, or an isobutyl group. , Tert-Butyl group, pentyl group, isopentyl group, neopentyl group and the like. A part of the hydrogen atom 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, and specifically, the alkoxy group having 1 to 5 carbon atoms is a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, or n-. Examples thereof include a butoxy group and a tert-butoxy group. Of these, a methoxy group and an ethoxy group are preferable.

Alkenyl group for Rd ^4, the R ^'201 the same as the alkenyl group and the like in a vinyl group, a propenyl group (allyl group), 1-methyl propenyl group, 2-methyl-propenyl group. These groups may further have an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms as a substituent.

The cyclic group for Rd ^4, the R ^'201 the same as the cyclic groups are exemplified in, cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, 1 or more from a cycloalkane such as tetracyclododecane An alicyclic group excluding the hydrogen atom of the above, or an aromatic group such as a phenyl group or a naphthyl group is preferable. When Rd ⁴ is an alicyclic group, the resist composition is well dissolved in an organic solvent, so that the lithography characteristics are improved. Further, when Rd ⁴ is an aromatic group, the resist composition has excellent light absorption efficiency and good sensitivity and lithography characteristics in lithography using EUV or the like as an exposure light source.

In formula (d1-3), Yd ¹ is a single bond or divalent linking group.
The ^{divalent linking group in Yd 1} is not particularly limited, but includes a divalent hydrocarbon group (aliphatic hydrocarbon group, aromatic hydrocarbon group) which may have a substituent and a hetero atom 2 Examples include valuation linking groups. Each of these includes a divalent hydrocarbon group and a heteroatom which may have a substituent, which are mentioned in the description of the divalent linking group in ^{Ya 21} in the above formula (a2-1). Examples include those similar to divalent linking groups.
Yd ¹ is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof. The alkylene group is more preferably a linear or branched alkylene group, and even more preferably a methylene group or an ethylene group.

A preferable specific example of the anion portion of the component (d1-3) is shown below.

-In the cation part formula (d1-3), M ^{m +} is an m-valent organic cation, which is the same as M ^{m +} in the above 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 of them may be used in combination.
When the resist composition contains the component (D1), the content of the component (D1) in the resist composition is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the component (A), and 1 to 1 15 parts by mass is more preferable, and 5 to 10 parts by mass is further preferable.
When the content of the component (D1) is at least a preferable lower limit value, particularly good lithography characteristics and a resist pattern shape can be easily 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) Ingredient manufacturing method:
The method for producing the component (d1-1) and the component (d1-2) is not particularly limited, and the component (d1-1) and the component (d1-2) can be produced by a known method.
The method for producing the component (d1-3) is not particularly limited, and for example, the component (d1-3) is produced in the same manner as described in US2012-01499116.

-Regarding the component (D2) As the acid diffusion control agent component, a nitrogen-containing organic compound component (hereinafter referred to as "(D2) component") that does not correspond to the above component (D1) may be contained.
The component (D2) is not particularly limited as long as it acts 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 are preferable, and among them, secondary aliphatic amines and tertiary aliphatic amines are more preferable.
The aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group preferably has 1 to 12 carbon atoms.
Examples of the aliphatic amine include _{an amine (alkylamine or alkylalcoholamine) in which at least one hydrogen atom of ammonia NH 3} is replaced with an alkyl group or a hydroxyalkyl group having 12 or less carbon atoms, or a cyclic amine.
Specific examples of alkylamines and alkylalcohol 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 , Tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine and other trialkylamines; diethanolamine, triethanolamine, diisopropanolamine, tri Alkyl alcohol amines such as isopropanolamine, di-n-octanolamine and tri-n-octanolamine can be mentioned. Among these, trialkylamines having 5 to 10 carbon atoms are more preferable, and tri-n-pentylamine or tri-n-octylamine is particularly preferable.

Examples of the cyclic amine include a heterocyclic compound containing a nitrogen atom as a hetero atom. The heterocyclic compound may be a monocyclic compound (aliphatic monocyclic amine) or a polycyclic compound (aliphatic polycyclic amine).
Specific examples of the aliphatic monocyclic amine include piperidine and piperazine.
The aliphatic polycyclic amine preferably has 6 to 10 carbon atoms, and specifically, 1,5-diazabicyclo [4.3.0] -5-nonen and 1,8-diazabicyclo [5. 4.0] -7-undecene, hexamethylenetetramine, 1,4-diazabicyclo [2.2.2] octane and the like can be mentioned.

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

Further, as the component (D2), an aromatic amine may be used.
Examples of the aromatic amine include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or a derivative thereof, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine and the like.

As the component (D2), one type may be used alone, or two or more types may be used in combination.
When the resist composition contains the component (D2), the content of the component (D2) in the resist composition is usually in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the component (A). Used. Within the above range, the shape of the resist pattern, stability over time, and the like are improved.

<< At least one compound (E) selected from the group consisting of organic carboxylic acids and phosphorus oxo acids and derivatives thereof >>
The resist composition of the present embodiment contains organic carboxylic acid, phosphorus oxo acid and its derivatives as optional components for the purpose of preventing sensitivity deterioration, improving the resist pattern shape, stability over time, and the like. At least one compound (E) selected from the above 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 the oxo acid of phosphorus include phosphoric acid, phosphonic acid, phosphinic acid and the like, and among these, phosphonic acid is particularly preferable.
Examples of the derivative of the oxo acid of phosphorus include an ester in which the hydrogen atom of the oxo acid is replaced with a hydrocarbon group, and the hydrocarbon group includes an alkyl group having 1 to 5 carbon atoms and 6 to 6 carbon atoms. Examples include 15 aryl groups.
Examples of the phosphoric acid derivative include phosphoric acid esters such as phosphoric acid di-n-butyl ester and phosphoric acid diphenyl ester.
Examples of the phosphonic acid derivative 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 the derivative of phosphinic acid include phosphinic acid ester and phenylphosphinic acid.
In the resist composition of the present embodiment, the component (E) may be used alone or in combination of two or more.
When the resist composition contains the component (E), the content of the component (E) is usually used in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the component (A).

≪Fluorine additive component (F) ≫
The resist composition in the present embodiment may contain a fluorine additive component (hereinafter referred to as "component (F)") in order to impart water repellency to the resist film or to improve the lithography characteristics.
Examples of the component (F) are described in JP-A-2010-002870, JP-A-2010-032994, JP-A-2010-277043, JP-A-2011-13569, and JP-A-2011-128226. Fluorine-containing polymer compounds can be used.
More specifically, as the component (F), a polymer having a structural unit (f1) represented by the following general formula (f1-1) can be mentioned. The polymer is a polymer consisting of only the structural unit (f1) represented by the following formula (f1-1); a copolymer of the structural unit (f1) and the structural unit (a1). A copolymer of the structural unit (f1), a structural unit derived from acrylic acid or methacrylic acid, and the structural unit (a1) is preferable. Here, the structural unit (a1) copolymerized with the structural unit (f1) is a structural unit derived from 1-ethyl-1-cyclooctyl (meth) acrylate, 1-methyl-1-adamantyl (1-methyl-1-adamantyl). Constituent units derived from meta) acrylates are 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０〜５の整数であり、Ｒｆ^１０１はフッ素原子を含む有機基である。］

[In the formula, R is the same as described above, and Rf ¹⁰² and Rf ¹⁰³ independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms, respectively. Rf ¹⁰² and Rf ¹⁰³ may be the same or different. nf ¹ is an integer from 0 to 5, and Rf ¹⁰¹ is an organic group containing a fluorine atom. ]

In the formula (f1-1), R bonded to the carbon atom at the α-position is the same as described above. As R, a hydrogen atom or a methyl group is preferable.
In the formula (f1-1), ^{as the halogen atom of Rf 102} and Rf ^103, 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 alkyl group as the above-mentioned alkyl group having 1 to 5 carbon atoms of R, and a methyl group or an ethyl group is preferable. Specific examples of the alkyl halide groups having 1 to 5 carbon atoms of Rf ¹⁰² and Rf ¹⁰³ include groups in which some or all of the hydrogen atoms of the alkyl groups having 1 to 5 carbon atoms are substituted with halogen atoms. Be done. As the halogen atom, a fluorine atom is particularly preferable. Among them, as Rf ¹⁰² and Rf ¹⁰³ , a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group is preferable.
In the formula (f1-1), nf ¹ is an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably 1 or 2.

In the 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, and more preferably 1 to 15 carbon atoms. , 1 to 10 carbon atoms are particularly preferable.
Further, as for the hydrocarbon group containing a fluorine atom, it is preferable that 25% or more of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferably 50% or more is fluorinated, and 60% or more is fluorinated. It is particularly preferable that it is fluorinated because the hydrophobicity of the resist film during immersion exposure is increased.
Among ^these, as ^{Rf 101,} more preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, trifluoromethyl _{group, -CH 2 -CF 3, -CH 2} -CF 2 -CF 3, -CH (CF 3 ) ₂ , -CH _2- CH _2- CF ₃ , -CH _2- CH _2- CF _2- CF _2- CF _2- CF ₃ are particularly preferable.

The weight average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography) of the component (F) is preferably 1000 to 50000, more preferably 5000 to 40,000, and most preferably 1000 to 30000. When it is not more than the upper limit value of this range, it has sufficient solubility in a solvent for resist to be used as a resist, and when it is more than the lower limit value of this range, the water repellency of the resist film is 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 1.0 to 2.5.

In the resist composition of the present embodiment, the component (F) may be used alone or in combination of two or more.
When the resist composition contains the component (F), the content of the component (F) is usually used in a ratio of 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A).

The resist composition according to the present embodiment includes additives that are more miscible as desired, such as additional resins for improving the performance of resist films, dissolution inhibitors, plasticizers, stabilizers, colorants, and antihalation agents. , Dyes and the like can be appropriately added and contained.

In the resist composition of the present embodiment, after the resist material is dissolved in the component (S), impurities and the like may be removed by using a polyimide porous membrane, a polyamide-imide porous membrane, or the like. For example, the resist composition may be filtered using a filter made of a polyimide porous membrane, a filter made of a polyamide-imide porous membrane, a filter made of a polyimide porous membrane, a polyamide-imide porous membrane, or the like. Examples of the polyimide porous film and the polyamide-imide porous film include those described in JP-A-2016-155121.

<Process (via)>
The step (via) is a step of forming a resist film on the support using the resist composition described above.
In the above step, a specific resist composition described later is applied onto the support with a spinner or the like, and a bake (post-apply bake (PAB)) treatment is performed, for example, at 80 to 150 ° C., preferably 100 to 150 ° C. ( More preferably, it is applied for 40 to 120 seconds, preferably 60 to 120 seconds under a temperature condition of more than 100 ° C. and 150 ° C. or lower) to form a resist film.

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

<Process (via)>
The step (via) is a step of exposing the resist film and a step of developing the resist film after the exposure to form a resist pattern.
In the above step, the resist film is selectively exposed by exposure through a mask (mask pattern) on which a predetermined pattern is formed, for example, using an exposure apparatus or the like.

Wavelength used for the exposure is not particularly limited, ArF excimer laser, KrF excimer laser, _{F 2} excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays It can be done using radiation.

The exposure method of the resist film may be a normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or an immersion exposure (Liquid Imaging 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 the refractive index of air, and exposure (immersion exposure) is performed in that state. This 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 fluorine-based compounds 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 main components.} Examples thereof include liquids, those having a boiling point of 70 to 180 ° C., and more preferably those having a boiling point of 80 to 160 ° C. It is preferable that the fluorine-based inert liquid has a boiling point in the above range because the medium used for immersion can be removed by a simple method after the end of exposure.
As the fluorine-based inert liquid, a perflooloalkyl 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.
Further, specifically, the perfluoroalkyl ether compound may include perfluoro (2-butyl-tetrahydrofuran) (boiling point 102 ° C.), and the perfluoroalkylamine compound may include perfluorotributylamine (perfluorotributylamine). Boiling point 174 ° C.).
As the immersion medium, water is preferably used from the viewpoints of cost, safety, environmental problems, versatility and the like.

Then, the baking (post-exposure baking (PEB)) treatment is performed for 40 to 120 seconds, preferably 60 to 100 seconds under temperature conditions of, for example, 80 to 150 ° C., preferably 90 to 130 ° C.
Next, the exposed resist film is developed with an alkaline developer containing a nonionic surfactant to form a resist pattern.

An alkaline developer containing a nonionic surfactant is used as the developer. For example, the developer includes a 0.1 to 10 mass% tetramethylammonium hydroxide (TMAH) aqueous solution containing a nonionic surfactant.
Further, as the nonionic surfactant contained in the alkaline developer, a known nonionic surfactant can be blended. Specifically, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether. Polyoxyethylene alkyl allyl ethers such as sorbitan monolaurates, sorbitan monopalmitates, sorbitan monostearate, sorbitan monooleates, sorbitan trioleates, sorbitan fatty acid esters such as sorbitan tristearate; and polyoxyethylene sorbitans. Polyoxyethylene sorbitan fatty acid esters such as monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate; Examples thereof include acetylenes such as oxyethylene adducts.

The blending amount of the nonionic surfactant is usually preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, and further preferably 0.01 to 0.5% by mass with respect to the total amount of the developing solution. preferable.

The developing process can be carried out by a known developing method. For example, a method of immersing the support in a developing solution for a certain period of time (dip method), a method of raising the developing solution on the surface of the support by surface tension and allowing it to stand still for a certain period of time. (Paddle method), spraying the developer on the surface of the support (spray method), applying the developer on the support rotating at a constant speed while scanning the developer dispensing nozzle. Examples include a method of continuing (dynamic dispense method).

After the development treatment, a rinsing treatment is preferably performed. The rinsing treatment is preferably a water rinse using pure water.
Drying is performed after the development treatment or the rinsing treatment. In some cases, a baking process (post-baking) may be performed after the development process.
In this way, the resist pattern can also be formed.

The rinsing treatment (cleaning treatment) using the rinsing liquid can be carried out by a known rinsing method. Examples of the rinsing treatment method include a method of continuously spraying the rinsing liquid on a support rotating at a constant speed (rotary coating method), a method of immersing the support in the rinsing liquid for a certain period of time (dip method), and the like. Examples thereof include a method of spraying a rinse liquid on the surface of the support (spray method).

(Second aspect)
In the second aspect of the present invention, (ib) a compound represented by the following general formula (m0-1) and a compound represented by the following general formula (m0-2) are copolymerized by living radical polymerization. The step of obtaining the alternate copolymer represented by the following general formula (p0) (hereinafter, also referred to as step (ib)) and (iib) hydrolysis of the alternate copolymer are carried out by the following general formula (Pre). The step of obtaining the first copolymer compound precursor represented by -2a) (hereinafter, also referred to as step (iib)), (iiib) the first copolymer compound precursor, and the following general formula (Add-). The step of reacting the compound represented by 1) with the compound represented by the following general formula (p1) to obtain the polymer compound (A01) represented by the following general formula (p1) (hereinafter, also referred to as step (iiib)) and (ivb) said high. A step of preparing a resist composition by mixing a molecular compound (A01) and an organic solvent (hereinafter, also referred to as step (ivb)) and a resist film using the resist composition on the (vb) support. (Hereinafter referred to as step (vb)), (vib) a step of exposing the resist film, and a step of developing the exposed resist film to form a resist pattern (hereinafter, step (vib)). ), A resist pattern forming method including.

［式中、Ｒｐ^０１は、水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒｐ^０２及びＲｐ^０３は、それぞれ独立に置換基を有してもよい炭化水素基である。Ｒｐ^０２及びＲｐ^０３は、相互に結合して環を形成していてもよい。Ｒｐ^０４は、水素原子、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である。Ｒｐ^０５は、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、シアノ基又は水酸基である。Ｒｐ^０６は、直鎖状又は分岐鎖状の脂肪族炭化水素基である。ｎ_１は０〜４の整数である。］

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰² and Rp ⁰³ are hydrocarbon groups that may have independent substituents, respectively. Rp ⁰² and Rp ⁰³ may be coupled to each other to form a ring. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. ]

［式中、Ｒｐ^０１は、水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒｐ^０４は、水素原子、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である。Ｒｐ^０５は、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、シアノ基又は水酸基である。ｎ_１は０〜４の整数である。Ｒａ^００１、Ｒａ^００２及びＲａ^００３は、それぞれ独立に置換基を有してもよい炭化水素基である。Ｒａ^００２及びＲａ^００３は、相互に結合して環を形成していてもよい。］

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. n ₁ is an integer from 0 to 4. Ra ⁰⁰¹ , Ra ⁰⁰² and Ra ⁰⁰³ are hydrocarbon groups that may each have an independent substituent. Ra ⁰⁰² and Ra ⁰⁰³ may be coupled to each other to form a ring. ]

<Process (ib)>
The step (ib) is the same as the step (ia) described above.

<Step (iib)>
The step (ib) is a step of hydrolyzing the alternating copolymer represented by the general formula (p0) to obtain a first polymer compound precursor represented by the general formula (Pre-2a). be.

The method for hydrolyzing the alternating copolymer can be carried out by adding the alternating copolymer and the acid component to a solvent and mixing them. Examples of the solvent include the same solvents as those used for atom transfer radical polymerization described above.

≪Acid component≫
The acid component is not particularly limited, and may be an inorganic acid or an organic acid.
Examples of such acid components include organic acids such as acetic acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and malonic acid; and inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and hydrobromic acid. Can be mentioned.
In the production method of the present embodiment, one type of acid component may be used alone, or two or more types may be used in combination.

The temperature conditions during the reaction between the alternating copolymer and the acid component are not particularly limited, and are, for example, about 0 to 120 ° C.
The reaction time between the alternating copolymer and the acid component is not particularly limited, and is, for example, about 1 to 72 hours.

<Process (iii)>
In the step (iii), the first polymer compound precursor represented by the general formula (Pre-2a) is reacted with the compound represented by the general formula (Add-1), and the general formula is described. This is a step of obtaining the polymer compound represented by (p1).

As a method for reacting the first polymer compound precursor with the compound represented by the general formula (Add-1), the first polymer compound precursor and the general formula (Add-1) are used. ) And the above-mentioned acid component as a catalyst are added to the solvent and mixed. Examples of the solvent include the same solvents as those used for atom transfer radical polymerization described above.

The temperature conditions for reacting the first polymer compound precursor with the compound represented by the general formula (Add-1) are not particularly limited, and are, for example, about 0 to 120 ° C.
The reaction time for reacting the first polymer compound precursor with the compound represented by the general formula (Add-1) is not particularly limited, and is, for example, about 1 to 72 hours.

The temperature conditions during the reaction between the alternating copolymer and the acid component are not particularly limited, and are, for example, about 0 to 120 ° C.
The reaction time between the alternating copolymer and the acid component is not particularly limited, and is, for example, about 1 to 72 hours.

The compound represented by the general formula (Add-1) and the polymer compound represented by the general formula (p1) are the same as those described in the first aspect.

The steps (ivb) to (viv) are the same as the steps (va) to (via).

(Third aspect)
In the third aspect of the present invention, (ic) the compound represented by the general formula (m0-1) and the compound represented by the general formula (m0-2) are copolymerized by living radical polymerization. The step of obtaining the alternate copolymer represented by the general formula (p0) (hereinafter, also referred to as step (ic)) and (ic) the alternate copolymer are hydrolyzed to form the general formula (Pre). The step of obtaining the first polymer compound precursor represented by -1a) (hereinafter, also referred to as step (iic)), (iii) the first polymer compound precursor, and the above general formula (Add-). The step of reacting the compound represented by 2) with the compound represented by the above general formula (Pre-1b-2) to obtain a second polymer compound precursor (hereinafter, also referred to as step (iii)). , (Ivc) a step of hydrolyzing the second polymer compound precursor to obtain the polymer compound (A02) represented by the general formula (p2) (hereinafter, also referred to as step (ivc)). (Vc) A step of preparing a resist composition by mixing the polymer compound (A02) with an organic solvent (hereinafter, also referred to as step (vc)), and a step of preparing the resist composition on a (vic) support. (Hereinafter referred to as a step (vic)), a step of exposing the resist film, and a step of developing the exposed resist film to form a resist pattern (viic). Hereinafter, it is also referred to as a step (viic)), and is a method for forming a resist pattern.

The above-mentioned step (ic) is the same as the above-mentioned step (ia), and the above-mentioned step (ic) is the same as the above-mentioned step (ia).

<Process (iii)>
In the step (iii), the first polymer compound precursor represented by the following general formula (Pre-1a) is reacted with the compound represented by the following general formula (Add-2), and the following general is carried out. This is a step of obtaining a second polymer compound precursor represented by the formula (Pre-1b-2).

［式中、Ｒｐ^０１は、水素原子、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である。Ｖｐ^０１は、単結合又は２価の連結基である。Ｒｐ^０４は、水素原子、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である。Ｒｐ^０５は、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、シアノ基又は水酸基である。Ｒｐ^０６は、直鎖状又は分岐鎖状の脂肪族炭化水素基である。ｎ_１は０〜４の整数である。Ｒａ^００４、Ｒａ^００５は水素原子又はアルキル基である。Ｒａ^００６は炭化水素基であって、Ｒａ^００６は、Ｒａ^００４、Ｒａ^００５のいずれかと結合して環を形成してもよい。Ｘは、ハロゲン原子である。］

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. Ra ⁰⁰⁴ and Ra ⁰⁰⁵ are hydrogen atoms or alkyl groups. Ra ⁰⁰⁶ is a hydrocarbon group, and Ra ⁰⁰⁶ may be bonded to either Ra ⁰⁰⁴ or Ra ^{005 to form a ring.} X is a halogen atom. ]

The first polymer compound precursor represented by the above general formula (Pre-1a) is the same as that described in the above-mentioned step (ia).

In the above general formula (Add-2), Ra ⁰⁰⁴ and Ra ⁰⁰⁵ are hydrogen atoms or alkyl groups.
Of Ra ⁰⁰⁴ and Ra ⁰⁰⁵ , at least one is preferably a hydrogen atom, and more preferably both are hydrogen atoms.

When Ra ⁰⁰⁴ or Ra ⁰⁰⁵ is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms. Specifically, a linear or branched alkyl group is preferable. More 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 can be mentioned, and the methyl group or the ethyl group can be mentioned. More preferably, a methyl group is even more preferable.

In the above general formula (Add-2), ^{examples of the hydrocarbon group of Ra 006} include a linear or branched alkyl group or a cyclic hydrocarbon group.
The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and the like. 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-chain alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, a 2,2-dimethylbutyl group and the like, and an isopropyl group is preferable.

When Ra ⁰⁰⁶ is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
As the aliphatic hydrocarbon group which is a polycyclic group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferable, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically. Examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

When ^{the cyclic hydrocarbon group of Ra 006} is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be a monocyclic type or a polycyclic type. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group in Ra ⁰⁰⁶ is a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); and includes two or more aromatic rings. A group obtained by removing one hydrogen atom from an aromatic compound (for example, biphenyl, fluorene, etc.); a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (for example, a benzyl group, etc.). Examples thereof include an phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, an arylalkyl group such as a 2-naphthylethyl group) and the like. The alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom. preferable.

The cyclic hydrocarbon group in Ra ^{006 may have a substituent.} Examples of this substituent include -R ^P1 , -R ^P2, -O-R ^P1 , -R ^P2, -CO-R ^P1 , -R ^P2, -CO-OR ^P1 , -R ^P2, -O-CO-R ^P1 , and so on. Examples thereof include -R ^P2- OH, -R ^P2- CN or -R ^P2- COOH (hereinafter, these substituents are collectively referred to as "Ra ⁰⁵ ") and the like.
Here, ^RP1 is a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic group having 6 to 30 carbon atoms. It is a group hydrocarbon group. In addition, ^RP2 is a single bond, a divalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent hydrocarbon having 6 to 30 carbon atoms. It is an aromatic hydrocarbon group of. However, a chain saturated hydrocarbon group R ^P1 and R ^P2, some or all of the hydrogen atoms included in the aliphatic cyclic saturated hydrocarbon group and aromatic hydrocarbon group may be substituted with a fluorine atom. The aliphatic cyclic hydrocarbon group may have one or more of the above-mentioned substituents alone, or may have one or more of the above-mentioned substituents.
Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms include 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 decyl group. ..
Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group and a cyclododecyl group. Monocyclic aliphatic saturated hydrocarbon group; bicyclo [2.2.2] octanyl group, tricyclo [5.2.1.02,6] decanyl group, tricyclo [3.3.1.13,7] decanyl group , Tetracyclo [6.2.1.13, 6.02,7] Polycyclic aliphatic saturated hydrocarbon groups such as dodecanyl group and adamantyl group can be mentioned.
Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include a group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene.

Ra ⁰⁰⁶ is, Ra if ^'1, Ra' ² of bonded either to form a ring, a cyclic group, 4- to 7-membered ring is preferred, 4 to 6-membered ring is more preferable. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.

In the above general formula (Add-2), examples of the halogen atom in X include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a chlorine atom is preferable from the viewpoint of ease of handling. ..

As a method for reacting the first polymer compound precursor with the compound represented by the general formula (Add-2), a method known as esterification can be used. For example, it can be carried out by adding the first polymer compound precursor, the compound represented by the general formula (Add-2), and a base component (DBU (registered trademark), etc.) to a solvent and mixing them. ..
Examples of the solvent include the same solvents as those used for atom transfer radical polymerization described above.

The temperature conditions for reacting the first polymer compound precursor with the compound represented by the general formula (Add-2) are not particularly limited, and are, for example, about 0 to 120 ° C.
The reaction time for reacting the first polymer compound precursor with the compound represented by the general formula (Add-2) is not particularly limited, and is, for example, about 1 to 72 hours.

^{Rp 01} , Vp ⁰¹ , Rp ⁰⁴ , Rp ⁰⁵ , Rp ⁰⁶ , and n ₁ in the above formula (Pre-1b-2) are the contents described in the above formula (m0-1) and the above formula (m0-2). The same is true.

^{Ra 004, Ra 005, Ra 006} in the above formula (Pre-1b-2) are respectively identical to ^{Ra 004, Ra 005, Ra 006} of the above formula (Add-2).
In the above formula (Pre-1b-2), -C (Ra ⁰⁰⁴ ) (Ra ⁰⁰⁵ ) -O- (Ra ⁰⁰⁶ ) is an acid dissociative group (acetal type acid dissociative group). Due to the action of the acid, -C (Ra ⁰⁰⁴ ) (Ra ⁰⁰⁵ ) -O- (Ra ⁰⁰⁶ ) is dissociated, and a highly polar polar group (carboxy group) is generated to increase the polarity.

<Process (ivc)>
The step (ivc) is a step of hydrolyzing a second polymer compound precursor represented by the above formula (Pre-1b-2) to obtain a polymer compound represented by the above general formula (p2). Is.

The method for hydrolyzing the second polymer compound precursor can be carried out by adding the second polymer compound precursor and the base component to a solvent and mixing them. Examples of the solvent include the same solvents as those used for atom transfer radical polymerization described above.
The base component, the amount of the base component used, the reaction time, and the like are the same as those described in the above-mentioned <Step (iva)>.

^{Rp 01} , Vp ⁰¹ , Rp ⁰⁴ , Rp ⁰⁵ , and n ₁ in the general formula (p2) are the same as those described in the above formula (m0-1) and the above formula (m0-2).
^{Ra 004, Ra 005, Ra 006} in the general formula (p2) are respectively identical to ^{Ra 004, Ra 005, Ra 006} of the above formula (Add-2).

The steps (vc) to (viic) are the same as those described in the above steps (va) to (via) except that the component (A) of the resist composition contains the polymer compound (A02).

(Fourth aspect)
In the fourth aspect of the present invention, (id) the compound represented by the general formula (m0-1) and the compound represented by the general formula (m0-2) are copolymerized by living radical polymerization. The step of obtaining the alternating copolymer represented by the general formula (p0) (hereinafter, also referred to as step (id)) and (id) hydrolyzing the alternating copolymer to obtain the above general formula (Pre). The step of obtaining the first copolymer compound precursor represented by -2a) (hereinafter, also referred to as step (iid)), (iiid) the first copolymer compound precursor, and the above general formula (Add-). A step (hereinafter, also referred to as step (iii)) of reacting the compound represented by 2) with the compound represented by the above general formula (p2) to obtain the polymer compound (A02), and (ivd) the above-mentioned high. A step of preparing a resist composition by mixing a molecular compound (A02) and an organic solvent (hereinafter, also referred to as step (ivd)) and a resist film using the resist composition on the (vd) support. (Hereinafter, also referred to as step (vd)), (vid) a step of exposing the resist film, and a step of developing the exposed resist film to form a resist pattern (hereinafter, step (vid). ), A resist pattern forming method including.

The above-mentioned step (id) is the same as the above-mentioned step (ib), and the above-mentioned step (iid) is the same as the above-mentioned step (iib).

<Process (iiid)>
In the step (iii), the first polymer compound precursor represented by the general formula (Pre-2a) is reacted with the compound represented by the general formula (Add-2), and the general formula is described. This is a step of obtaining a polymer compound represented by the formula (p2).

Examples of the method for reacting the first polymer compound precursor with the compound represented by the general formula (Add-2) include the above-mentioned known esterification reaction.

The temperature conditions for reacting the first polymer compound precursor with the compound represented by the general formula (Add-2) are not particularly limited, and are, for example, about 0 to 120 ° C.
The reaction time for reacting the first polymer compound precursor with the compound represented by the general formula (Add-2) is not particularly limited, and is, for example, about 1 to 72 hours.

The compound represented by the general formula (Add-2) and the polymer compound represented by the general formula (p2) are the same as those described in the third aspect.

The steps (ivd) to (vid) are the same as those described in the above steps (via) to (viia) except that the component (A) of the resist composition contains the polymer compound (A02).

In the resist pattern forming method of the present embodiment described above, a compound (monomer) (m0-1) in which the hydroxystyrene skeleton is protected by a group capable of deprotection with an acid component and a compound (monomer) having a specific imide structure are used. By copolymerizing with (m0-2), the polymerization is controlled by the electronic and chemical properties, so that the variation of each structural unit of the obtained alternating copolymer is suppressed. Therefore, it is presumed that the lithography characteristics can be improved by forming a resist pattern using a resist composition containing a polymer compound obtained from the alternating copolymer.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these examples.

<Production Example 1 of Alternating Copolymer>
In a 50 mL reactor, 6.4 ^{mg (0.0080 mol) of RuCp *} catalyst and 0.615 mL (4.0 mmol) of p-acetoxystyrene (PACS) were dissolved in 1.0 mL of cyclohexanone. Further, in the 50 mL reactor, 0.02 mL (0.080 mmol) of tributylamine, 0.988 g (4.0 mmol) of the monomer (M0-1-1), 0.014 mL of ethyl 2-chloro-2-phenylacetate ( 0.080 mmol) was added, and the polymerization reaction was carried out at 80 ° C. for 24 hours. After completion of the polymerization reaction, the reaction solution was rapidly cooled to −78 ° C. in an ice bath of methanol-dry ice to obtain an alternating copolymer (p0-1) (0.564 g).

For the obtained alternating copolymer (p0-1), the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 13700, and the molecular weight dispersion (Mw / Mn) was 1.25.
The carbon 13 nuclear magnetic resonance spectra (150MHz_ ¹³ C-NMR) and proton 1 nuclear magnetic resonance spectrum (600 MHz - ¹ H-NMR) as a result of an analysis by (the ratio of the respective structural units within the structural formula (molar ratio )) Was l / m = 50/50.

The alternate copolymerizability of the above alternating copolymer (p0-1) was evaluated using MALDI-TOF-MS. As a result, the peaks of each structural unit were confirmed alternately, and it was confirmed that the variation of each structural unit in the alternating copolymer was small.

<Production Example 1 of Polymer Compound>
The above alternating copolymer (p0-1) (0.15 mol (30.71 g)) and hydrazine monohydrate (0.19 mol) were dissolved in THF (200 mL) and stirred at 65 ° C. for 4 hours.
After allowing the reaction solution to cool to room temperature, the reaction solution was further cooled to 0 ° C., hydrochloric acid (100 mL) was added dropwise, and the obtained powder was recovered. The powder was dried under reduced pressure to obtain a first polymer compound precursor (Pre-1a-1) (0.13 mol (16.14 g)).

The first polymer compound precursor (Pre-1a-1) (0.13 mol (16.14 g)) was dissolved in 3 times the amount of dichloromethane in a 500 mL three-necked flask, replaced with nitrogen, and cooled to 5 ° C. or lower. Was done. A solution of 4-dimethylaminopyridine (DMAP) (0.03 mol) in dichloromethane was added dropwise thereto over 5 minutes so as not to exceed 10 ° C. Further, tert-butyl alcohol (0.45 mol) was added dropwise over 15 minutes, and aging was carried out for 10 minutes.
Then, a dichloromethane solution of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC / HCl) (0.38 mol) was added dropwise at 10 ° C. or lower over 90 minutes at 10 ° C. or lower for 18 hours. Stirring was performed.
Then, it was washed with 1% hydrochloric acid and the organic layer was recovered. Then, washing with water was repeated three times.
Then, the organic layer was concentrated, and tert-butyl methyl ether (TBME) was added dropwise to the concentrated solution over 1 hour.
The solid content was recovered and dried under reduced pressure to obtain a second polymer compound precursor (Pre-1b-11) (0.10 mol (16.52 g)).

The second polymer compound precursor (Pre-1b-11) (0.1 mol (16.52 g)) was dissolved in methyl ethyl ketone (MEK), and an equimolar 1% K ₂ CO ₃ aqueous solution was used at room temperature. Stirring was performed for 1 hour.
Then, it was added dropwise to a mixed solvent of heptane / isopropyl alcohol over 30 minutes and precipitated to obtain a powder.
The obtained powder was dispersed and washed a plurality of times using a mixed solvent of heptane / isopropyl alcohol.
The solid content was recovered and dried under reduced pressure to obtain a polymer compound (p1-1-1) (0.06 mol (7.8 g)).

For the obtained polymer compound (p1-1-1), the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 9000.
The carbon 13 nuclear magnetic resonance spectra (150MHz_ ¹³ C-NMR) and proton 1 nuclear magnetic resonance spectrum (600 MHz - ¹ H-NMR) as a result of an analysis by (the ratio of the respective structural units within the structural formula (molar ratio )) Was l / m = 50/50.

<Production example 2 of polymer compound>
The above alternating copolymer (p0-1) (0.15 mol (29.50 g)) was dissolved in methyl ethyl ketone (MEK) (100 mL), and the mixture was stirred at room temperature for 1 hour using methanesulfonic acid (50 mL).
Then, it was added dropwise to a mixed solvent of heptane / isopropyl alcohol over 30 minutes and precipitated to obtain a powder. The obtained powder was dispersed and washed a plurality of times using a mixed solvent of heptane / isopropyl alcohol.
The solid content was recovered and dried under reduced pressure to obtain a polymer compound precursor (Pre-2a-1) (0.11 mol (21.63 g)).

The polymer compound precursor (Pre-2a-1) was dissolved in a mixed solvent of dimethylformamide (DMF) / tert-butyl alcohol in a 500 mL three-necked flask, concentrated sulfuric acid was added, and the mixture was heated under reflux for 12 hours.
After completion of the reaction, the temperature was returned to room temperature, water was added to precipitate a solid, and dispersion washing with water was repeated 3 times to return the pH to neutral.
The solid content was recovered and dried under reduced pressure to obtain a polymer compound (p1-2-1) (0.02 mol (2.62 g)).

For the obtained polymer compound (p1-2-1), the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 9000.
The carbon 13 nuclear magnetic resonance spectra (150MHz_ ¹³ C-NMR) and proton 1 nuclear magnetic resonance spectrum (600 MHz - ¹ H-NMR) as a result of an analysis by (the ratio of the respective structural units within the structural formula (molar ratio )) Was l / m = 50/50.

The following polymer compounds (p1-1-2) to polymer compounds (p1-1-8) were produced by the same method as in Production Example 1 of the above polymer compound.
With respect to the obtained polymer compound, the copolymer composition ratio (ratio of each structural unit in the polymer compound (molecular ratio)) of the polymer compound determined by ^{13 C-NMR, and the standard polystyrene conversion determined by GPC measurement.} The weight average molecular weight (Mw) and the molecular weight dispersion (Mw / Mn) of the above are also shown in Table 1.

<Production example 2 of polymer compound>
An alternating copolymer (p0-1) was obtained by the same method as in the above-mentioned production example of the alternating copolymer. The alternating copolymer (p0-1) (0.15 mol (29.50 g)) was dissolved in methyl ethyl ketone (MEK) (100 mL), and the mixture was stirred at room temperature for 1 hour using methanesulfonic acid (50 mL).
Then, it was added dropwise to a mixed solvent of heptane / isopropyl alcohol over 30 minutes and precipitated to obtain a powder. The obtained powder was dispersed and washed a plurality of times using a mixed solvent of heptane / isopropyl alcohol.
The solid content was recovered and dried under reduced pressure to obtain a polymer compound precursor (Pre-2a-1) (0.11 mol (21.63 g)).

The precursor (Pre-2a-1) of the first polymer compound was dissolved in DBU (registered trademark) (0.08 mol) and 100 ml of DMF in a 500 mL three-necked flask, compound 1 (0.15 mol) was added, and the mixture was heated for 4 hours. Reflux was performed. After allowing to cool, water was added to obtain a solid content, and then dispersed washing was performed twice with water.
The solid content was recovered and dried under reduced pressure to obtain a polymer compound (p2-1-1) (0.02 mol: 3.70 g).

Regarding the obtained polymer compound (p2-1-1), the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 12300, and the molecular weight dispersion (Mw / Mn) was 1.32.
The carbon 13 nuclear magnetic resonance spectra (150MHz_ ¹³ C-NMR) and proton 1 nuclear magnetic resonance spectrum (600 MHz - ¹ H-NMR) as a result of an analysis by (the ratio of the respective structural units within the structural formula (molar ratio )) Was l / m = 50/50.

<Production example 3 of polymer compound>
10.0 g of monomer (a10-1pre), 9.5 g of monomer (a1-1-1), 1.4 g of azobis (isobutyric acid) dimethyl (V-601) as a polymerization initiator, and 50.0 g of MEK (methylethylketone) It was dissolved, heated to 85 ° C. under a nitrogen atmosphere, and stirred for 5 hours. Then, 9.4 g of acetic acid and 160 g of methanol were added to the reaction solution, and a deprotection reaction was carried out at 30 ° C. for 8 hours. After completion of the reaction, the obtained reaction solution was precipitated in 2500 g of heptane and washed. The obtained white solid was filtered and dried under reduced pressure overnight to obtain 10.1 g of the target polymer compound (A-10).

The following polymer compounds (A-11) to polymer compounds (A-19) were produced in the same manner as the above polymer compound (A-10).
With respect to the obtained polymer compound, the copolymer composition ratio (ratio of each structural unit in the polymer compound (molecular ratio)) of the polymer compound determined by ^{13 C-NMR, and the standard polystyrene conversion determined by GPC measurement.} The weight average molecular weight (Mw) and the molecular weight dispersion (Mw / Mn) of the above are also shown in Table 2.

<Preparation of resist composition>
(Examples 1 to 9, Comparative Examples 1 to 9)
Each component shown in Tables 3 and 4 was mixed and dissolved to prepare a resist composition of each example.

In Tables 3 and 4, each abbreviation has the following meaning. The value in [] is the blending amount (part by mass).
(A) -1: The above-mentioned polymer compound (p1-1-1).
(A) -2: The above-mentioned polymer compound (p1-1-2).
(A) -3: The above polymer compound (p1-1-3).
(A) -4: The above polymer compound (p1-1-4).
(A) -5: The above polymer compound (p1-1-5).
(A) -6: The above-mentioned polymer compound (p2-1-1).
(A) -7: The above polymer compound (p1-1-6).
(A) -8: The above-mentioned polymer compound (p1-1-7).
(A) -9: The above polymer compound (p1-1-8).

(A) -10 to (A) -18: The above-mentioned polymer compounds (A-10) to (A-18).
(B) -1: An acid generator composed of a compound represented by the following chemical formula (B-1).

(S) -1: Mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 80/20 (mass ratio).

<Formation of resist pattern>
Each of the resist compositions of each example was applied on a hexamethyldisilazane (HMDS) -treated 8-inch silicon substrate using a spinner, and prebaked (PAB) on a hot plate at a temperature of 110 ° C. for 60 seconds. The treatment was carried out and dried to form a resist film having a film thickness of 50 nm.
Next, for the resist film, an electron beam drawing apparatus JEOL-JBX-9300FS (manufactured by JEOL Ltd.) was used, and the target size was set to a 1: 1 line-and-space pattern with a line width of 50 nm at an acceleration voltage of 100 kV (hereinafter,). After drawing (exposure) as "LS pattern"), post-exposure heating (PEB) treatment was performed at 90 ° C. for 60 seconds.
Then, at 23 ° C., alkaline development was carried out for 60 seconds using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.). , Water rinse was performed for 15 seconds using pure water. As a result, a 1: 1 LS pattern with a line width of 50 nm was formed.

[Evaluation of Optimal Exposure (Eop)]
^{The optimum exposure amount Eop (μC / cm 2} ) at which the target size LS pattern is formed was determined by the above <resist pattern formation>. This is shown in Tables 5 and 6 as "Eop (μC / cm ^2)".

[Evaluation of LWR (Linewise Roughness)]
For the LS pattern formed in the above <Formation of resist pattern>, 3σ, which is a scale indicating LWR, was determined. This is shown in Tables 5 and 6 as "LWR (nm)".
"3σ" is a standard deviation obtained by measuring 400 line positions in the longitudinal direction of the line with a scanning electron microscope (acceleration voltage 800V, trade name: S-9380, manufactured by Hitachi High-Technologies Corporation). It shows a triple value (3σ) (unit: nm) of (σ).
The smaller the value of 3σ, the smaller the roughness of the side wall of the line, which means that an LS pattern having a more uniform width was obtained.

From the results shown in Tables 5 and 6, it can be confirmed that the resist pattern forming method of the example is excellent in reducing roughness as compared with the resist pattern forming method of the comparative example.

Claims (4)

The compound represented by the following general formula (m0-1) and the compound represented by the following general formula (m0-2) are copolymerized by living radical polymerization and represented by the following general formula (p0). The process of obtaining an alternating copolymer and
A step of hydrolyzing the alternating copolymer to obtain a first polymer compound precursor represented by the following general formula (Pre-1a).
The first polymer compound precursor is reacted with a compound represented by the following general formula (Add-1), and the second polymer represented by the following general formula (Pre-1b-1) is reacted. The process of obtaining the compound precursor and
A step of hydrolyzing the second polymer compound precursor to obtain a polymer compound (A01) represented by the following general formula (p1).
A step of mixing the polymer compound (A01) with an organic solvent to prepare a resist composition, and
A step of forming a resist film on the support using the resist composition, and
The step of exposing the resist film and
The step of developing the resist film after exposure to form a resist pattern, and
A method for forming a resist pattern, including.

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰² and Rp ⁰³ are hydrocarbon groups that may have independent substituents, respectively. Rp ⁰² and Rp ⁰³ may be coupled to each other to form a ring. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. ]

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. Ra ⁰⁰¹ , Ra ⁰⁰² and Ra ⁰⁰³ are hydrocarbon groups that may each have an independent substituent. Ra ⁰⁰² and Ra ⁰⁰³ may be coupled to each other to form a ring. ]

[In the formula, Rp ⁰¹ and Rp ⁰⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Ra ⁰⁰¹ , Ra ⁰⁰² and Ra ⁰⁰³ are hydrocarbon groups that may each have an independent substituent. Ra ⁰⁰² and Ra ⁰⁰³ may be coupled to each other to form a ring. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. n ₁ is an integer from 0 to 4. ] The compound represented by the following general formula (m0-1) and the compound represented by the following general formula (m0-2) are copolymerized by living radical polymerization and represented by the following general formula (p0). The process of obtaining an alternating copolymer and
A step of hydrolyzing the alternating copolymer to obtain a first polymer compound precursor represented by the following general formula (Pre-2a).
A step of reacting the first polymer compound precursor with a compound represented by the following general formula (Add-1) to obtain a polymer compound (A01) represented by the following general formula (p1). When,
A step of mixing the polymer compound (A01) with an organic solvent to prepare a resist composition, and
A step of forming a resist film on the support using the resist composition, and
The step of exposing the resist film and
The step of developing the resist film after exposure to form a resist pattern, and
A method for forming a resist pattern, including.

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰² and Rp ⁰³ are hydrocarbon groups that may have independent substituents, respectively. Rp ⁰² and Rp ⁰³ may be coupled to each other to form a ring. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. ]

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. n ₁ is an integer from 0 to 4. Ra ⁰⁰¹ , Ra ⁰⁰² and Ra ⁰⁰³ are hydrocarbon groups that may each have an independent substituent. Ra ⁰⁰² and Ra ⁰⁰³ may be coupled to each other to form a ring. ] The compound represented by the following general formula (m0-1) and the compound represented by the following general formula (m0-2) are copolymerized by living radical polymerization and represented by the following general formula (p0). The process of obtaining an alternating copolymer and
A step of hydrolyzing the alternating copolymer to obtain a first polymer compound precursor represented by the following general formula (Pre-1a).
The first polymer compound precursor is reacted with a compound represented by the following general formula (Add-2), and the second polymer represented by the following general formula (Pre-1b-2) is reacted. The process of obtaining the compound precursor and
A step of hydrolyzing the second polymer compound precursor to obtain a polymer compound (A02) represented by the following general formula (p2).
A step of mixing the polymer compound (A02) with an organic solvent to prepare a resist composition, and
A step of forming a resist film on the support using the resist composition, and
The step of exposing the resist film and
The step of developing the resist film after exposure to form a resist pattern, and
A method for forming a resist pattern, including.

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰² and Rp ⁰³ are hydrocarbon groups that may have independent substituents, respectively. Rp ⁰² and Rp ⁰³ may be coupled to each other to form a ring. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. ]

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. Ra ⁰⁰⁴ and Ra ⁰⁰⁵ are hydrogen atoms or alkyl groups. Ra ⁰⁰⁶ is a hydrocarbon group, and Ra ⁰⁰⁶ may be bonded to either Ra ⁰⁰⁴ or Ra ^{005 to form a ring.} X is a halogen atom. ]

[In the formula, Rp ⁰¹ and Rp ⁰⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Ra ⁰⁰⁴ and Ra ⁰⁰⁵ are hydrogen atoms or alkyl groups. Ra ⁰⁰⁶ is a hydrocarbon group, and Ra ⁰⁰⁶ may be bonded to either Ra ⁰⁰⁴ or Ra ^{005 to form a ring.} Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. n ₁ is an integer from 0 to 4. ] The compound represented by the following general formula (m0-1) and the compound represented by the following general formula (m0-2) are copolymerized by living radical polymerization and represented by the following general formula (p0). The process of obtaining an alternating copolymer and
A step of hydrolyzing the alternating copolymer to obtain a first polymer compound precursor represented by the following general formula (Pre-2a).
A step of reacting the first polymer compound precursor with a compound represented by the following general formula (Add-2) to obtain a polymer compound (A02) represented by the following general formula (p2). When,
A step of mixing the polymer compound (A02) with an organic solvent to prepare a resist composition, and
A step of forming a resist film on the support using the resist composition, and
The step of exposing the resist film and
The step of developing the resist film after exposure to form a resist pattern, and
A method for forming a resist pattern, including.

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰² and Rp ⁰³ are hydrocarbon groups that may have independent substituents, respectively. Rp ⁰² and Rp ⁰³ may be coupled to each other to form a ring. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. Rp ⁰⁶ is a linear or branched aliphatic hydrocarbon group. n ₁ is an integer from 0 to 4. ]

[In the formula, Rp ⁰¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Vp ⁰¹ is a single bond or divalent linking group. Rp ⁰⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Rp ⁰⁵ is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a cyano group or a hydroxyl group. n ₁ is an integer from 0 to 4. Ra ⁰⁰⁴ and Ra ⁰⁰⁵ are hydrogen atoms or alkyl groups. Ra ⁰⁰⁶ is a hydrocarbon group, and Ra ⁰⁰⁶ may be bonded to either Ra ⁰⁰⁴ or Ra ^{005 to form a ring.} X is a halogen atom. ]