JP7094146B2 - Resist composition and resist pattern forming method - Google Patents

Description

The present invention relates to a resist composition and a resist pattern forming method.

In the lithography technique, 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 devices and liquid crystal display devices, 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. Further, studies have been conducted on EUV (extreme ultraviolet rays), EB (electron beam), X-rays, etc., which have shorter wavelengths (higher energy) than these excimer lasers.

The resist material is required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing fine dimensional patterns.
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 (alkaline developing process), the positive chemically amplified resist composition includes a resin component (base resin) whose solubility in an 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 developing solution. 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 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 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.

Further, 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 having a great influence on the lithography characteristics.
As the acid generator used in the chemically amplified resist composition, a wide variety of acid generators 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. For 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. ..
Further, in order to improve the lithography characteristics in the formation of the resist pattern, an onium salt-based acid generator having an anion having a specific structure including an aromatic ring has been proposed as an anion portion of the onium salt-based acid generator. (See, for example, Patent Document 1).

Japanese Patent No. 5149236

As the lithography technology further advances and the resist pattern becomes finer, for example, in lithography using an electron beam or EUV, the goal is to form a fine pattern of several tens of nm. As the resist pattern size becomes smaller as described above, the resist composition is required to have good lithography characteristics such as high sensitivity, high resolution, defect suppression and roughness reduction with respect to the exposure light source.
However, in the conventional resist composition containing an onium salt-based acid generator as described above, if an attempt is made to increase the sensitivity to an exposure light source such as EUV, it becomes difficult to obtain a desired resist pattern shape or the like. There was a problem and it was difficult to satisfy all of these characteristics.

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

In order to solve the above problems, the present invention has adopted the following configuration.
That is, the first aspect of the present invention is a resist composition 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. It is a resist composition containing a base material component (A) and a compound (BD1) composed of an anionic portion and a cation moiety represented by the following general formula (bd1).

［式中、Ｒｘ^１～Ｒｘ^４はそれぞれ独立に、置換基を有してもよい炭化水素基もしくは水素原子を表すか、又は２個以上が相互に結合して環構造を形成していてもよい。Ｒｙ^１～Ｒｙ^２はそれぞれ独立に、置換基を有してもよい炭化水素基もしくは水素原子を表すか、又は相互に結合して環構造を形成していてもよい。

は二重結合又は単結合である。Ｒｚ^１～Ｒｚ^４は、それぞれ独立に、原子価が許容する場合、置換基を有してもよい炭化水素基もしくは水素原子を表すか、又は２個以上が相互に結合して環構造を形成していてもよい。ただし、Ｒｘ^１～Ｒｘ^４、Ｒｙ^１～Ｒｙ^２、Ｒｚ^１～Ｒｚ^４のうち、少なくとも１個はアニオン基を有し、アニオン部全体でｎ価のアニオンとなる。ｎは１以上の整数である。ｍは１以上の整数であって、Ｍ^ｍ＋は、下記一般式（ｃａ－０）で表されるカチオンを表す。］

[In the formula, Rx ¹ to Rx ⁴ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, or even if two or more of them are bonded to each other to form a ring structure. good. Ry ¹ and Ry ² may independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, or may be bonded to each other to form a ring structure.

Is a double bond or a single bond. Rz ¹ to Rz ⁴ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, if the valence allows, or two or more of them are bonded to each other to form a ring structure. You may be doing it. However, at least one of Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ has an anion group, and the entire anion portion becomes an n-valent anion. n is an integer of 1 or more. m is an integer of 1 or more, and M ^{m +} represents a cation represented by the following general formula (ca-0). ]

［式中、Ｒ^ｂ１は、置換基を有してもよいアリール基である。Ｒ^ｂ２～Ｒ^ｂ３は、それぞれ独立に置換基を有してもよいアリール基又は置換基を有してもよいアルキル基である。Ｒ^ｂ２～Ｒ^ｂ３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。ただし、Ｒ^ｂ１～Ｒ^ｂ３の少なくとも１つは、スルホニル基を含む置換基を有する。］

[In the formula, R ^b1 is an aryl group which may have a substituent. R ^b2 to R ^b3 are aryl groups which may independently have a substituent or alkyl groups which may have a substituent. R ^b2 to R ^b3 may be bonded to each other to form a ring together with the sulfur atom in the formula. However, at least one of R ^b1 to R ^b3 has a substituent containing a sulfonyl group. ]

A second aspect of the present invention is a step of forming a resist film on a support using the resist composition according to the first aspect, a step of exposing the resist film, and a step of exposing the resist film after exposure. It is a resist pattern forming method including a step of developing and forming a resist pattern.

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

As used herein and in the claims, "aliphatic" is defined as a relative concept to aromatics, meaning groups, compounds, etc. that do not have aromaticity.
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" includes linear, branched and cyclic divalent saturated hydrocarbon groups.
The "alkyl halide group" is a group in which a part or all of the hydrogen atom of the alkyl group is substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The "fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which a part or all of the hydrogen atom of the alkyl group or the alkylene group is substituted with a fluorine atom.
The "constituent unit" means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
When it is described that "may have a substituent" or "may have a substituent", the case where the hydrogen atom (-H) is substituted with a monovalent group and the case where the methylene group (-CH ₂ ) is substituted. Includes both cases where-) is replaced with a divalent group.
"Exposure" is a concept that includes general irradiation of radiation.

The “constituent unit derived from the acrylic acid ester” means a structural unit formed by cleaving the ethylenic double bond of the acrylic acid ester.
The "acrylic acid ester" is a compound in which the hydrogen atom at the terminal of the carboxy group of acrylic acid (CH ₂ = CH-COOH) is replaced with an organic group.
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 ^α0 ) that replaces the hydrogen atom bonded to the carbon atom at the α-position is an atom or group other than the hydrogen atom, for example, an alkyl group having 1 to 5 carbon atoms and a halogenation having 1 to 5 carbon atoms. Examples thereof include an alkyl group. In addition, an itaconic acid diester in which the substituent (R ^α0 ) is substituted with a substituent containing an ester bond, and an α-hydroxyacrylic ester in which the substituent (R ^α0 ) is substituted with a hydroxyalkyl group or a group modified with a hydroxyl group thereof are also available. It shall include. 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, unless otherwise specified.
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. Further, the acrylic acid ester and the α-substituted acrylic acid ester may be collectively referred to as “(α-substituted) acrylic acid ester”.

"Constituent unit derived from acrylamide" means a structural unit composed by cleavage of the ethylenic double bond of acrylamide.
In acrylamide, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, or one or both of the hydrogen atoms of the amino group of acrylamide may be substituted with a substituent. The carbon atom at the α-position of acrylamide is a carbon atom to which the carbonyl group of acrylamide is bonded, unless otherwise specified.
As the substituent for substituting the hydrogen atom bonded to the carbon atom at the α-position of acrylamide, the same group as that mentioned as the substituent at the α-position in the α-substituted acrylic acid ester (substituent (R ^α0 )) is used. Can be mentioned.

The “constituent unit derived from hydroxystyrene” means a structural unit composed by cleavage of the ethylenic double bond of hydroxystyrene. The “constituent unit derived from the hydroxystyrene derivative” means a structural unit formed by cleaving the ethylenic double bond of the hydroxystyrene derivative.
The "hydroxystyrene derivative" is a concept including a hydrogen atom at the α-position of hydroxystyrene 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 hydroxystyrene is substituted with an organic group; even if the hydrogen atom at the α-position is substituted with a substituent. Examples thereof include those in which a substituent other than a hydroxyl group is bonded to a good hydroxystyrene benzene ring. The α-position (carbon atom at the α-position) refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.
Examples of the substituent substituting the hydrogen atom at the α-position of hydroxystyrene include the same as those mentioned as the substituent at the α-position in the α-substituted acrylic acid ester.

The "constituent unit derived from vinyl benzoic acid or a vinyl benzoic acid derivative" means a structural unit formed by cleavage of an ethylenic double bond of vinyl benzoic acid or a vinyl benzoic acid derivative.
The "vinyl benzoic acid derivative" is a concept including a hydrogen atom at the α-position of vinyl benzoic acid 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 carboxy group of vinyl benzoic acid is substituted with an organic group; the hydrogen atom at the α-position is substituted with a substituent. Examples thereof include those in which a substituent other than a hydroxyl group and a carboxy group is bonded to the benzene ring of vinyl benzoic acid. The α-position (carbon atom at the α-position) refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.

The term "styrene derivative" is a concept including a hydrogen atom at the α-position of styrene substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. Examples of these derivatives include those in which a substituent is bonded to a benzene ring of hydroxystyrene in which a hydrogen atom at the α-position may be substituted with a substituent. The α-position (carbon atom at the α-position) refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.
“Constituent unit derived from styrene” and “constituent unit derived from a styrene derivative” mean a structural unit formed by cleavage of an ethylenic double bond of styrene or a styrene derivative.

The alkyl group as the substituent at the α-position is preferably a linear or branched alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group). , N-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.
Further, the alkyl halide group as the substituent at the α-position is specifically a group in which a part or all of the hydrogen atom of the above-mentioned "alkyl group as the substituent at the α-position" is substituted with a halogen atom. Be done. 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.
Further, as the hydroxyalkyl group as the substituent at the α-position, specifically, a group in which a part or all of the hydrogen atom of the above-mentioned "alkyl group as the substituent at the α-position" is substituted with a hydroxyl group can be mentioned. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, most preferably 1.

In the present specification and claims, depending on the structure represented by the chemical formula, an asymmetric carbon may be present, and an enantiomer or a diastereomer may be present. In that case, those isomers are represented by one chemical formula. These isomers may be used alone or as a mixture.

(Resist composition)
The resist composition according to the first aspect of the present invention generates an acid by exposure and changes its solubility in a developing solution by the action of the acid, and the solubility in the developing solution is changed by the action of the acid. It contains a changing base material component (A) (hereinafter, also referred to as “(A) component”) and a compound (BD1) represented by the general formula (bd1) (hereinafter, also referred to as “(BD1) component”). ..
As one embodiment of such a resist composition, a resist composition containing the component (A) and an acid generator component (B) (hereinafter, also referred to as “component (B)”) that generates an acid by exposure. Can be mentioned. Preferably, in addition to the component (A) and the component (B), a base component (hereinafter, also referred to as “component (D)” that traps (that is, controls the diffusion of the acid) the acid generated from the component (B) by exposure). ) Is further contained.
In the resist composition of the present embodiment, the component (BD1) can be used as the component (B) or the component (D) by selecting an anion group in the molecule.

When a resist film is formed using the resist composition of the present embodiment and selective exposure is performed on the resist film, acid is generated from the component (B) in the exposed portion of the resist film, and the action of the acid is generated. As a result, the solubility of the component (A) in the developing solution changes, while the solubility of the component (A) in the developing solution does not change in the unexposed portion of the resist film. There is a difference in solubility in the developing 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 melted and removed to form a negative resist pattern.

In the present specification, a resist composition in which a resist film exposed portion is melted and removed to form a positive resist pattern is referred to as a positive resist composition, and a resist film unexposed portion is melted and removed to form a negative resist pattern. The resist composition to be used is called a negative resist composition. The resist composition of the present embodiment may be a positive resist composition or a negative resist composition. Further, the resist composition of 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.

The resist composition of the present embodiment has an acid-generating ability to generate an acid by exposure, and the component (A) may generate an acid by exposure in addition to the component (B).
When the component (A) generates an acid by exposure, the component (A) becomes "a base material component that generates an acid by exposure and whose solubility in a developing solution is changed by the action of the acid".
When the component (A) is a base material component that generates an acid by exposure and whose solubility in a developing solution changes due to the action of the acid, the component (A1) described later generates an acid by exposure and the solubility in the developer changes. It is preferably a polymer compound whose solubility in a developing solution changes due to the action of an acid. Examples of such a polymer compound include a resin having a structural unit that generates an acid upon exposure. Known monomers can be used as the monomer for inducing the structural unit that generates an acid by exposure.

<Ingredient (A)>
In the resist composition of the present embodiment, the component (A) is a base material component whose solubility in a developing solution is changed by the action of an acid.
In the present invention, the "base material component" is an organic compound having a film-forming ability, and an organic compound having a molecular weight of 500 or more is preferably used. When the molecular weight of the organic compound is 500 or more, the film forming ability is improved, and in addition, it becomes easy to form a nano-level resist pattern.
Organic compounds used as base material components are roughly classified into non-polymers and polymers.
As the non-polymer, one having a molecular weight of 500 or more and less than 4000 is usually used. Hereinafter, the term "small molecule compound" means 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 term "resin", "polymer compound" or "polymer" means a polymer having a molecular weight of 1000 or more.
As the molecular weight of the polymer, the mass average molecular weight in terms of polystyrene by GPC (gel permeation chromatography) shall be used.

When the resist composition of the present embodiment is a "negative resist composition for an alkali developing process" that forms a negative resist pattern in an alkali developing process, or a "solvent" that forms a positive resist pattern in a solvent developing process. In the case of "a positive resist composition for a developing process", the component (A) is preferably a substrate component (A-2) soluble in an alkaline developer (hereinafter referred to as "component (A-2)"). It is used, and further, a cross-linking agent component is blended. In such a resist composition, for example, when an acid is generated from the component (B) by exposure, the acid acts to cause cross-linking between the component (A-2) and the cross-linking agent component, resulting in alkaline development. Solubility in liquid decreases (solubility in organic developer increases). Therefore, in forming a resist pattern, when the resist film obtained by applying the resist composition on a support is selectively exposed, the resist film exposed portion is sparingly soluble in an alkaline developing solution (in an organic developing solution). On the other hand, the unexposed part of the resist film remains soluble in the alkaline developing solution (slightly soluble in the organic developing solution) and does not change. A pattern is formed. Further, at this time, a positive resist pattern is formed by developing with an organic developer.
As the preferred component (A-2), a resin soluble in an alkaline developer (hereinafter referred to as "alkali-soluble resin") is used.
Examples of the alkali-soluble resin include α- (hydroxyalkyl) acrylic acid or an alkyl ester of α- (hydroxyalkyl) acrylic acid (preferably having 1 to 5 carbon atoms) disclosed in Japanese Patent Application Laid-Open No. 2000-2066694. A resin having a structural unit derived from at least one selected from (alkyl esters); a hydrogen atom bonded to an α-position carbon atom having a sulfonamide group, which is disclosed in US Pat. No. 6,49,325, is substituted with a substituent. Acrylic resin or polycycloolefin resin which may be used; A fluorinated alcohol-containing, α-position disclosed in US Pat. No. 6,49,325, JP-A-2005-336452, JP-A-2006-317803. Acrylic resin in which a hydrogen atom bonded to a carbon atom may be substituted with a substituent; a polycycloolefin resin having a fluorinated alcohol disclosed in JP-A-2006-259582 is good with little swelling. It is preferable because a resist pattern can be formed.
In the α- (hydroxyalkyl) acrylic acid, hydrogen atom at the α-position to which the carboxy group is bonded is hydrogen among the acrylic acids in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. Indicates one or both of the acrylic acid to which an atom is bonded and the α-hydroxyalkylacrylic acid to which a hydroxyalkyl group (preferably a hydroxyalkyl group having 1 to 5 carbon atoms) is bonded to the carbon atom at the α-position. ..
As the cross-linking agent component, for example, it is preferable to use an amino-based cross-linking agent such as glycoluryl having a methylol group or an alkoxymethyl group, or a melamine-based cross-linking agent because a good resist pattern with less swelling is easily formed. .. The blending amount of the cross-linking agent component is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.

When the resist composition of the present embodiment is a "positive resist composition for an alkaline developing process" that forms a positive resist pattern in an alkaline developing process, or a "solvent" that forms a negative resist pattern in a solvent developing process. In the case of "negative resist composition for developing process", the component (A) is preferably a substrate component (A-1) whose polarity is increased by the action of an acid (hereinafter referred to as "component (A-1)"). ) Is used. By using the component (A-1), the polarity of the base material component changes before and after exposure, so that good development contrast can be obtained not only in the alkaline development process but also in the solvent development process.
When the alkaline developing process is applied, the component (A-1) is sparingly soluble in an alkaline developer before exposure. For example, when an acid is generated from the component (B) by exposure, the action of the acid causes the component (B). The polarity increases and the solubility in alkaline developers increases. 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 sparingly soluble to alkaline developing solution to soluble. On the other hand, since the unexposed portion of the resist film remains sparingly soluble in alkali, a positive resist pattern is formed by alkaline development.
On the other hand, when a solvent developing process is applied, the component (A-1) is highly soluble in an organic developer before exposure, and when an acid is generated from the component (B) by exposure, the action of the acid The polarity becomes higher and the solubility in an organic developer decreases. Therefore, in forming a resist pattern, when the resist composition is selectively exposed to a resist film obtained by applying the resist composition on a 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.
In the resist composition of the present embodiment, the component (A) is preferably the component (A-1). That is, the resist composition of the present embodiment is a "positive resist composition for an alkali developing process" that forms a positive resist pattern in an alkali developing process, or a "solvent developing" that forms a negative resist pattern in a solvent developing process. It is preferably a negative resist composition for processing. As the component (A), at least one of a high molecular weight compound and a low molecular weight compound can be used.
When the component (A) is the component (A-1), the component (A-1) preferably contains a resin component (A1) (hereinafter, also referred to as “component (A1)”).

-Regarding the component (A1) The component (A1) is a resin component, and preferably contains a polymer compound having a structural unit (a1) containing an acid-degradable group whose polarity is increased by the action of an acid.
As the component (A1), those having a structural unit (a10) containing a hydroxystyrene skeleton in addition to the structural unit (a1) are preferable.
Further, as the component (A1), in addition to the structural unit (a1), a structural unit (a2) containing a lactone-containing cyclic group, a _—SO2 -containing cyclic group or a carbonate-containing cyclic group is further included. Is also preferable.
Further, as the component (A1), in addition to the constituent unit (a1), the constituent unit (a3) containing a polar group-containing aliphatic hydrocarbon group (provided that the constituent unit (a1) or the constituent unit (a2) is used. Those having (excluding applicable ones) are also preferable.
Further, the component (A1) may have a constituent unit other than the constituent unit (a1), the constituent unit (a2), the constituent unit (a3), and the constituent unit (a10).

<< 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 form a polar group.
Examples of the polar group include a carboxy group, a hydroxyl group, an amino group, a sulfo group (-SO _3H ) 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 specifically, the acid-degradable group includes 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 (i) a group having an acid dissociative property 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, (ii) after a part of the bond is cleaved by the action of the acid, a further decarbonation reaction occurs, 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 be obtained.
The acid dissociative 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 dissociative group, whereby the acid dissociative group is affected by the action of the acid. When the acid dissociates, 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 proposed as an acid dissociable group of a base resin for a chemically amplified resist composition.
Specifically, as the acid dissociative group of the base resin for the chemically amplified resist composition, the "acetal type acid dissociative group" and the "tertiary alkyl ester type acid dissociative group" described below are described below. Examples include "group" and "tertiary alkyloxycarbonyl acid dissociable group".

Acetal-type acid dissociative group:
Among the polar groups, the acid dissociable group that protects the carboxy group or the hydroxyl group is, for example, an acid dissociable group represented by the following general formula (a1-r-1) (hereinafter referred to as “acetal type acid dissociative group”). There are times.).

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

[In the formula, ^Ra'1 and ^Ra'2 are hydrogen atoms or alkyl groups. ^Ra'3 is a hydrocarbon group, and ^Ra'3 may be bonded to either ^Ra'1 or ^Ra'2 to form a ring. ]

In the formula (a1-r-1), it is preferable that at ^{least one} of Ra'1 and Ra'2 is a hydrogen atom, and it is more preferable that both are hydrogen atoms.
When ^Ra'1 or ^Ra'2 is an alkyl group, the alkyl group includes the alkyl group mentioned as a substituent that may be bonded to the carbon atom at the α-position in the above description of the α-substituted acrylic acid ester. The same can be mentioned, and an alkyl group having 1 to 5 carbon atoms is preferable. Specifically, a linear or branched alkyl group is preferable. More specifically, 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 the like can be mentioned, and a methyl group or an ethyl group can be used. More preferably, a methyl group is particularly preferable.

In the formula (a1-r-1), examples of the hydrocarbon group of ^Ra'3 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'3 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.
The aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms. Examples include adamantan, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

When the cyclic hydrocarbon group of ^Ra'3 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 substituted 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'3 , a group obtained by removing one hydrogen atom from the 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 (for example, biphenyl, fluorene, etc.); a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or the aromatic heterocycle is substituted with an alkylene group (for example, a benzyl group). , Penetyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group and other arylalkyl groups) 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 carbon number. preferable.

The cyclic hydrocarbon group in ^Ra'3 may have a substituent. Examples of this substituent include -R ^P1 , -R ^P2 , -OR ^{P1, -R P2, -CO-R P1 , -R P2 , -CO} -OR ^P1 , -R ^P2 , -O-CO-R ^P1 , and so on. -R ^P2 -OH, -R ^P2 -CN or -R ^P2 -COOH (hereinafter, these substituents are collectively referred to as "Ra ⁰⁵ ") and the like can be mentioned.
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 product having 6 to 30 carbon atoms. It is an aromatic hydrocarbon group of. However, some or all of the hydrogen atoms of the chain saturated hydrocarbon group, the aliphatic cyclic saturated hydrocarbon group and the aromatic hydrocarbon group of ^RP1 and ^RP2 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 [5.2.2.102,6] 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.

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

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

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

[In the formula, ^Ra'4 to ^Ra'6 are hydrocarbon groups, respectively, and ^Ra'5 and ^Ra'6 may be bonded to each other to form a ring. ]

Examples of the hydrocarbon group of ^Ra'4 include a linear or branched alkyl group, a chain or cyclic alkenyl group, or a cyclic hydrocarbon group.
Linear or branched alkyl group in ^Ra'4 , cyclic hydrocarbon group (monocyclic group, aliphatic hydrocarbon group, polycyclic group, aliphatic hydrocarbon group, aromatic hydrocarbon group) ) Is the same as that of ^Ra'3 .
The chain or cyclic alkenyl group in ^Ra'4 is preferably an alkenyl group having 2 to 10 carbon atoms.
Examples of the hydrocarbon group of ^Ra'5 and ^Ra'6 include the same as those of ^Ra'3 .

When ^Ra'5 and ^Ra'6 are bonded to each other to form a ring, a group represented by the following general formula (a1-r2-1) and a group represented by the following general formula (a1-r2-2). , The group represented by the following general formula (a1-r2-3) is preferably mentioned.
On the other hand, when ^Ra'4 to ^Ra'6 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）。］

[In the formula (a1-r2-1), Ra'10 represents an alkyl group having 1 to ¹⁰ carbon atoms or a group represented by the following general formula (a1-r2-r1). ^Ra'11 indicates a group forming an aliphatic cyclic group together with a carbon atom to which Ra ^'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 the hydrogen atom 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 the formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group that forms an aliphatic cyclic group together with Yaa. Ra ⁰⁴ is an aromatic hydrocarbon group which may have a substituent. In the formula (a1-r2-4), ^Ra'12 and ^Ra'13 are independently monovalent chain saturated hydrocarbon groups or hydrogen atoms having 1 to 10 carbon atoms. A part or all of the hydrogen atom 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 a substituent. 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 used as the linear or branched alkyl group of ^Ra'3 in the formula (a1-r-1). The listed groups are preferred. ^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, or 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.
The aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms. Examples include adamantan, 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 substituted 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 the 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 the aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

When the above-mentioned hydrocarbon group represented by Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ is substituted, the substituent may be, for example, a hydroxy group, a carboxy group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.). ), 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. Linear alkyl groups are 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 a group in which the methylene group ( _-CH2- ) constituting the hydrocarbon group is replaced with a polar group, or at least one hydrogen atom constituting the hydrocarbon group is used. Any of those substituted with a polar group are included.
As the "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 above 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 alkanediyl group; propane-1,2-diyl group, 1-methylbutane-1,3-diyl group, 2-methylpropane-1,3-diyl group, pentane-1,4-diyl group, 2 -Branch chain alkanediyl 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 cyclic divalent alicyclic hydrocarbon group.
Among the above, an alkanediyl group is preferable, and a linear alkanediyl group is more preferable.

In the above 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 -,- S (= O) ₂ -O- and the like can be mentioned.
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 above 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, still more preferably 1 to 3 carbon atoms, and more preferably carbon number 1 to 3 from the viewpoint of solubility in a developing solution. 1 or 2 is particularly preferable, and 1 is the 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an 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 or 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. Examples thereof include cycloalkyl groups such as cyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cycloheptyl group and cyclodecyl group. 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 xylyl 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 bond to a quaternary carbon atom (Ya ⁰ ).

In the above formula (a1-r2-r1), among Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ , the number of hydrocarbon groups having at least one polar group is one or more, but the developer 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.

In the formula (a1-r2-1), ^Ra'11 (an aliphatic cyclic group formed together with the carbon atom bonded to ^Ra'10 ) is a monocyclic group of ^Ra'3 in the formula (a1-r-1). Alternatively, the group mentioned as the aliphatic hydrocarbon group which is a polycyclic group is preferable.

In the formula (a1-r2-2), the cyclic hydrocarbon group formed by Xa together with Ya is the cyclic monovalent hydrocarbon group (lipid group) in ^Ra'3 in the formula (a1-r-1). A group obtained by further removing one or more hydrogen atoms from a hydrocarbon 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'3 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 [5.2.2.102,6] decanyl group, tricyclo [3.3.1] .13,7] decanyl group, tetracyclo [6.2.1.13,6.02,7] dodecanyl group, polycyclic aliphatic saturated hydrocarbon group such as adamantyl group and the like can be mentioned.
Among Ra ⁰¹ to Ra ⁰³ , a hydrogen atom and a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms are preferable from the viewpoint of easiness of synthesizing the monomer compound that induces the structural unit (a1). Among them, a hydrogen atom, a methyl group and an ethyl group are more preferable, and a hydrogen atom is particularly preferable.

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 groups as Ra ⁰⁵ described above.

Examples of the group containing a carbon-carbon double bond generated 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 cyclopentylideneethenyl group, a cyclohexylideneethenyl group and the like. Among these, a cyclopentenyl group, a cyclohexenyl group, and a cyclopentylideneethenyl group are preferable from the viewpoint of easiness of synthesizing the monomer compound that induces the structural unit (a1).

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 of ^Ra'3 in the formula (a1-r-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 and the like can be mentioned.

In the formula (a1-r2-4), ^Ra'12 and ^Ra'13 are independently monovalent chain saturated hydrocarbon groups or hydrogen atoms having 1 to 10 carbon atoms. As the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in ^Ra'12 and ^Ra'13 , the monovalent chain saturated hydrocarbon having 1 to 10 carbon atoms in Ra ⁰¹ to Ra ⁰³ described above is used. The same as the group can be mentioned. A part or all of the hydrogen atom contained in this chain saturated hydrocarbon group may be substituted.
Among ^Ra'12 and ^Ra'13 , a hydrogen atom and an alkyl group having 1 to 5 carbon atoms are preferable, an alkyl group having 1 to 5 carbon atoms is more preferable, a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable. preferable.
When the chain saturated hydrocarbon group represented by ^Ra'12 and ^Ra'13 is substituted, examples of the substituent include the same groups as ^Ra'05 described above.

In the formula (a1-r2-4), ^Ra'14 is a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group in ^Ra'14 include a linear or branched alkyl group or a cyclic hydrocarbon group.

The linear alkyl group in ^Ra'14 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'14 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'14 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.
The aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms. Examples include adamantan, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

Examples of the aromatic hydrocarbon group in Ra ^'14 include the same as the aromatic hydrocarbon group in Ra ⁰⁴ . Among them, ^Ra'14 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. Preferably, a group having one or more hydrogen atoms removed from benzene, naphthalene or anthracene is more preferable, a group having one or more hydrogen atoms removed from naphthalene or anthracene is particularly preferable, and a group having one or more hydrogen atoms removed from naphthalene is particularly preferable. Most preferred.
Examples of the substituent that Ra ^'14 may have include the same substituents that Ra ⁰⁴ may have.

When Ra'14 in the formula (a1- ^r2-4 ) is a naphthyl group, the position of bonding with the tertiary carbon atom in the formula (a1-r2-4) is at the 1-position or the 2-position of the naphthyl group. It may be either.
When Ra'14 in the formula (a1- ^r2-4 ) is an anthryl group, the position at which the tertiary carbon atom is bonded in the formula (a1-r2-4) is the 1-position, 2-position or the anthryl group. It may be any of the 9th place.

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

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

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

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

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

［式中、Ｒａ’^７～Ｒａ’^９はそれぞれアルキル基である。］

[In the formula, ^Ra'7 to ^Ra'9 are alkyl groups, respectively. ]

In the formula (a1-r-3), ^Ra'7 to ^Ra'9 are preferably alkyl groups having 1 to 5 carbon atoms, and more preferably alkyl groups having 1 to 3 carbon atoms, respectively.
The total number of carbon atoms of each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4 carbon atoms.

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 the hydrogen atom in the hydroxyl group of the structural unit derived from the styrene derivative is protected by the substituent containing the acid-degradable group, vinyl benzoic acid or a structural unit derived from the vinyl benzoic acid derivative- Examples thereof include a structural unit in which at least a part of a hydrogen atom in C (= O) -OH is protected by a substituent containing the acid-degradable group.

Among the above, the structural unit (a1) is preferably 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.
Preferred specific examples of such a structural unit (a1) include 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）又は（ａ１－ｒ－２）で表される酸解離性基である。Ｗａ^１はｎ_ａ２＋１価の炭化水素基であり、ｎ_ａ２は１～３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 an acid dissociative group represented by the above general formula (a1-r-1) or (a1-r-2). Wa ¹ is a n _a2 + 1 valent hydrocarbon group, na ₂ 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 halogenated alkyl group having 1 to 5 carbon atoms is a group in which a part or all of hydrogen atoms of the alkyl group having 1 to 5 carbon atoms is 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- ], a trimethylene group [ -(CH ₂ ) _3- ], tetramethylene group [-(CH ₂ ) _4- ], pentamethylene group [-(CH ₂ ) _5- ] and the like can be mentioned.
The branched 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 ). _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) ₂ -etc. Alkyl methylene groups;- 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 -etc. Alkylethylene groups; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ -etc. Alkyltrimethylene groups; -CH (CH ₃ ) Examples thereof include alkylalkylene groups such as alkyltetramethylene groups such as CH ₂ CH ₂ CH _2- , −CH ₂ CH (CH ₃ ) CH ₂ CH _2- and the like. 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 an alicyclic hydrocarbon ring) and an alicyclic hydrocarbon group are linear or branched. Examples thereof include a group bonded to the end of a chain-shaped aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include 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 adamantan. , Norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The aromatic hydrocarbon group as a 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, still more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. .. 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 heterogeneous. 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 a 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 and the like. A group in which one hydrogen atom is further removed from the aryl group in the group) and the like can be mentioned. The carbon number of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

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

In the above formula (a1-2), the _na2 + 1-valent hydrocarbon group in Wa ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity, 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 valences, more preferably 2 or 3 valences.

In the above 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 kind or two or more kinds.
As the structural unit (a1), the structural unit represented by the above formula (a1-1) is more preferable because it is easy to improve the characteristics (sensitivity, shape, etc.) in lithography by electron beam or EUV.
Among these, as the structural unit (a1), a unit including a structural unit represented by the following general formula (a1-1-1) is particularly preferable.

［式中、Ｒａ^１”は、一般式（ａ１－ｒ２－１）、（ａ１－ｒ２－３）又は（ａ１－ｒ２－４）で表される酸解離性基である。］

[In the formula, Ra ¹ "is an acid dissociative group represented by the general formula (a1-r2-1), (a1-r2-3) or (a1-r2-4)].

In the formula ( _a1-1-1 ), R, Va ¹ and na 1 are the same as R, Va ¹ and _na 1 in the formula (a 1-1).
The description of the acid dissociative group represented by the general formula (a1-r2-1), (a1-r2-3) or (a1-r2-4) is as described above.

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, 30 to 70 mol% is further preferable.
By setting the ratio of the structural unit (a1) to the lower limit value or more, the lithography characteristics such as sensitivity, resolution, and roughness improvement are improved. Further, when it is not more than the upper limit value, it is possible to balance with other constituent units and various lithography characteristics are improved.

<< Structural unit containing hydroxystyrene skeleton (a10) >>
The component (A1) preferably has a structural unit (a10) containing a hydroxystyrene skeleton in addition to the structural unit (a1).
As the structural unit (a10), for example, the structural unit represented by the following general formula (a10-1) is preferably mentioned.

［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、（ｎ_ａｘ１＋１）価の芳香族炭化水素基である。ｎ_ａｘ１は、１～３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 having a (n _ax1 + 1) valence. n _ax1 is an integer of 1 to 3. ]

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 of 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 halogenated alkyl group having 1 to 5 carbon atoms of R is a group in which a part or all of hydrogen atoms of the alkyl group having 1 to 5 carbon atoms is 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 formula (a10-1), Ya ^x1 is a single bond or a divalent linking group.
As the divalent linking group in Ya ^x1 , for example, a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a heteroatom are preferable.

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.

An aliphatic hydrocarbon group in Ya ^x1 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, and carbon. The number 1 to 4 is more preferable, and the number of carbons 1 to 3 is 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- ], a trimethylene group [ -(CH ₂ ) _3- ], tetramethylene group [-(CH ₂ ) _4- ], pentamethylene group [-(CH ₂ ) _5- ] and the like can be mentioned.
The branched 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 ). _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) ₂ -etc. Alkyl methylene groups;- 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 -etc. Alkylethylene groups; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ -etc. Alkyltrimethylene groups; -CH (CH ₃ ) Examples thereof include alkylalkylene groups such as alkyltetramethylene groups such as CH ₂ CH ₂ CH _2- , −CH ₂ CH (CH ₃ ) CH ₂ CH _2- and the like. 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 end of a linear or branched aliphatic hydrocarbon group, the cyclic fat. Examples thereof include a group in which a group hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include 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 one having 7 to 12 carbon atoms, specifically. Examples thereof include adamantan, 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 halogenated alkyl 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. As the substituent containing the heteroatom, —O—, —C (= O) —O—, —S—, —S (= O) _2- , —S (= O) ₂ -O— are preferable.

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 substituted 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 from which one atom is further removed) and the like can be mentioned. 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 atom.

In the aromatic hydrocarbon group, the hydrogen atom of 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, the halogen atom and the alkyl halide group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.

-A divalent linking group containing a heteroatom:
When Ya ^x1 is a divalent linking group containing a hetero atom, 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-, general formula-Y ²¹ -O-Y ^22- , -Y ²¹ -O-, -Y ^21- C (= O) -O-, -C (= O) -OY ²¹ -,-[Y ²¹ -C (= O) -O] _{m "} -Y ^22- , -Y ²¹ -OC ( = O) -Y ^22- or -Y ²¹ -S (= O) ₂ -O-Y ^22- [In the formula, Y ²¹ and Y ²² each have an independent substituent. It is also a good divalent hydrocarbon group, where O is an oxygen atom and m "is an integer of 0-3. ] And so on.
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. 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.
General 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 - ^OC (= O) -Y ^{22- or -Y 21 -} S (= O) ₂ -O-Y ²² -Medium, 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. The same as (divalent hydrocarbon group which may have a substituent) can be mentioned.
As ^Y21 , 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.
In the group represented by the formula- [Y ²¹ -C (= O) -O] _{m "} -Y ^22- , m" is an integer of 0 to 3, preferably an integer of 0 to 2, and 0. Or 1 is more preferable, and 1 is particularly preferable. That is, the group represented by the formula- [Y ²¹ -C (= O) -O] _{m "} -Y ^22- is represented by the formula-Y ²¹ -C ⁽ = O) -OY 22-. 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 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 1 to 8. An integer is preferred, an integer of 1 to 5 is more preferred, 1 or 2 is even more preferred, and 1 is most preferred.

As Ya ^x1 , 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 particularly preferable.

In the formula (a10-1), Wa ^x1 is an aromatic hydrocarbon group having a (n _ax1 + 1) valence.
Examples of the aromatic hydrocarbon group in Wa ^x1 include a group obtained by removing (n _ax1 + 1) hydrogen atoms from the aromatic ring. 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. 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 substituted 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.

In the formula (a10-1), n _ax1 is an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

Hereinafter, specific examples of the structural units represented by the general formula (a10-1) will be shown.
In the formula below, 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 kind or two or more kinds.
The proportion of the constituent unit (a10) in the component (A1) is, for example, 0 to 80 mol% with respect to the total (100 mol%) of all the constituent units constituting the component (A1), and is 10 to 80. Mol% is preferred, 20-70 mol% is more preferred, and 30-60 mol% is particularly preferred.
By setting the ratio of the structural unit (a10) 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. Further, when it is not more than the upper limit value, it is possible to balance with other constituent units and various lithography characteristics are improved.

<< Structural unit (a2) >>
The component (A1) is a structural unit (a2) containing a lactone-containing cyclic group, a _—SO2 -containing cyclic group or a carbonate-containing cyclic group in addition to the structural unit (a1) (provided that the structural unit (however, the structural unit (a1)). Those having (excluding those corresponding to a1)) are preferable.
The lactone-containing cyclic group, _-SO2 -containing cyclic group, or carbonate-containing cyclic group of the structural unit (a2) adheres to the substrate of the resist film when the component (A1) is used for forming the resist film. It is effective in enhancing sex. Further, by having the structural unit (a2), 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, the etching resistance is improved, and the like. Due to the effect of the above, the lithography characteristics and the like are improved.

The “lactone-containing cyclic group” refers to a cyclic group containing a ring (lactone ring) containing —O—C (= O) —in its ring 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.
As the lactone-containing cyclic group in the structural unit (a2), any one can be used without particular limitation. 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。］

[In the formula, ^Ra'21 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 -SO ₂ -containing cyclic group; A" is an oxygen atom (-O-) or a sulfur atom (-). 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 formulas (a2-r-1) to (a2-r-7), the alkyl group in ^Ra'21 is 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.
As the alkoxy group in ^Ra'21 , an alkoxy group having 1 to 6 carbon atoms is preferable. The alkoxy group is preferably linear or branched. Specifically, the group in which the alkyl group mentioned as the alkyl group in ^Ra'21 and the oxygen atom (—O—) are linked can be mentioned.
Examples of the halogen atom in ^Ra'21 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 in ^Ra'21 include a group in which a part or all of the hydrogen atom of the alkyl group in ^Ra'21 is replaced with the halogen atom. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

In -COOR "and -OC (= O) R" in Ra ^'21 , R "is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or _-SO2 -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 a fluorinated alkyl 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 and 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 —SO ₂ -containing cyclic group in R ”is the same as the —SO ₂ -containing cyclic group described later, and specifically, the general formulas (a5-r-1) to (a5-r-4). The groups represented by are listed below.
The hydroxyalkyl group in ^Ra'21 is preferably one having 1 to 6 carbon atoms, and specific examples thereof include a group in which at least one hydrogen atom of the alkyl group in ^Ra'21 is substituted with a hydroxyl group. ..

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 "is 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. Examples include groups with -O- or -S- intervening between atoms, such as -O-CH _2- , -CH ₂ -O-CH _2- , -S-CH _2- , -CH ₂ -SCH. ₂ − And the like. As A ”, an alkylene group having 1 to 5 carbon atoms or —O— is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group is most preferable.

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. -SO ₂ -The contained cyclic group may be a monocyclic group or a polycyclic group.
-SO ₂ -containing cyclic groups are particularly cyclic groups containing -O-SO ₂ -in their cyclic skeleton, that is, -OS- in -O-SO _2- contains a part of the cyclic skeleton. It is preferably a cyclic group containing a sultone ring to be formed.
More specifically, examples of the _-SO2 -containing cyclic group include groups represented by the following general formulas (a5-r-1) to (a5-r-4).

［式中、Ｒａ’^５１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、－ＣＯＯＲ”、－ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり；Ｒ”は水素原子、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。］

[In the formula, ^Ra'51 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 containing 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.
The alkyl group, alkoxy group, halogen atom, alkyl halide group, -COOR ", -OC (= O) R", and hydroxyalkyl group in Ra ^'51 are the above-mentioned general formulas (a2-r-1) to (1), respectively. The same as those mentioned in the description of ^Ra'21 in a2-r-7) can be mentioned.
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 —O—C (= 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 containing an oxygen atom or a sulfur atom. The number 1 to 5 is an alkylene group, 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.
The alkyl group, alkoxy group, halogen atom, alkyl halide group, -COOR ", -OC (= O) R", and hydroxyalkyl group in ^Ra'31 are the above general formulas (a2-r-1) to (1), respectively. The same as those mentioned in the description of ^Ra'21 in a2-r-7) can be mentioned.
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 is a lactone-containing cyclic group, a carbonate-containing cyclic group, or a _-SO2 -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 the substitution in Ya ^x1 in the above 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.
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, a _—SO2 -containing cyclic group, or a carbonate-containing cyclic group.
The lactone-containing cyclic group, _-SO2 -containing cyclic group, and carbonate-containing cyclic group in Ra ²¹ are represented by the above-mentioned general formulas (a2-r-1) to (a2-r-7), respectively. 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.
Of these, a lactone-containing cyclic group or a _-SO2 -containing cyclic group is preferable, and the general formulas (a2-r-1), (a2-r-2), (a2-r-6) or (a5-r) are preferable. The groups represented by -1) are more preferable. Specifically, the chemical formulas (r-lc-1-1) to (r-lc-1-7), (r-lc-2-1) 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 kind or two or more kinds.
When the component (A1) has a constituent unit (a2), the ratio of the constituent unit (a2) is 1 to 50 mol% with respect to the total (100 mol%) of all the constituent units constituting the component (A1). It is preferably 5 to 45 mol%, more preferably 10 to 40 mol%, and particularly preferably 10 to 30 mol%.
By setting the ratio of the constituent unit (a2) to be equal to or higher than the preferable lower limit value, the effect of containing the constituent unit (a2) can be sufficiently obtained, while by setting the ratio to be equal to or lower than the preferable upper limit value, the effect can be obtained with other constituent units. Can be balanced, and various lithography characteristics and pattern shapes are improved.

<< Structural unit (a3) >>
The component (A1) corresponds to the structural unit (a3) (however, the structural unit (a1) and the structural unit (a2)) containing the polar group-containing aliphatic hydrocarbon group in addition to the structural unit (a1). It is preferable to have (excluding). Since the component (A1) has the constituent unit (a3), the hydrophilicity of the component (A) is increased, which contributes to the improvement of the resolution.

Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, a hydroxyalkyl group in which a part of the hydrogen atom 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 from a large number of proposed ones and used. The cyclic group is preferably a polycyclic group, and more preferably 7 to 30 carbon atoms.
Among them, a structural unit derived from an acrylic acid ester containing an aliphatic polycyclic group containing a hydroxyalkyl group in which a part of the hydrogen atom 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 adamantan, a group in which two or more hydrogen atoms are removed from norbornan, 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.

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

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

In 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-position and the 5-position 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.
It is preferable that j is 1, and it is particularly preferable that the hydroxyl group is bonded to the 3-position of the adamantyl group.

In the formula (a3-2), k is preferably 1. The cyano group is preferably attached to the 5- or 6-position of the norbornyl group.

In the 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 terminal of the carboxy group of acrylic acid. The fluorinated alkyl alcohol is preferably bonded to the 5 or 6 position of the norbornyl group.

The structural unit (a3) contained in the component (A1) may be one type or two or more types.
When the component (A1) has a constituent unit (a3), it is preferably 1 to 40 mol%, more preferably 2 to 30 mol%, based on the total of all the constituent units constituting the component (A1). 5 to 25 mol% is more preferable, and 5 to 20 mol% is particularly preferable.
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, while by setting the ratio to be equal to or lower than the preferable upper limit value, the effect can be obtained with other constituent units. It becomes easy to balance and various lithography characteristics become good.

≪Other structural units≫
The component (A1) may have other structural units other than the above-mentioned structural unit (a1), structural unit (a10), structural unit (a2), and structural unit (a3).
Other structural units include, for example, a structural unit derived from styrene, a structural unit derived from a styrene derivative (excluding those corresponding to the structural unit (a10)), and an acid non-dissociative aliphatic cyclic group. Examples include structural units including.

As the component (A1) contained in the resist composition, one kind may be used alone, or two or more kinds may be used in combination.
The component (A1) preferably contains a polymer compound (A1-1) having a structural unit (a1) (hereinafter, also referred to as “component (A1-1)”).
Preferred (A1-1) components include, for example, a polymer compound having a repeating structure of a structural unit (a1) and a structural unit (a2), and a repeating structure of a structural unit (a1) and a structural unit (a10). Examples include polymer compounds.
In addition to the combination of each of the above two structural units, the structural units described above may be combined as a third or three or more structural units as appropriate according to a desired effect. The third structural unit is preferably a structural unit (a3).

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). Can be produced by dissolving the above in a polymerization solvent, adding a radical polymerization initiator as described above to polymerize, and then carrying out a deprotection reaction. At the time of polymerization, for example, by using a chain transfer agent such as HS-CH ₂ -CH ₂ -CH ₂ -C (CF ₃ ) ₂ -OH in combination, -C (CF ₃ ) is used at the end. 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 amount of hydrogen.

The mass average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography (GPC)) of the component (A1) 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, it has sufficient solubility in a resist solvent to be used as a resist, and when it is more than a preferable lower limit value in this range, it has dry etching resistance and dry etching resistance. 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.

-Regarding the component (A2) In the resist composition of the present embodiment, as the component (A), a substrate component whose solubility in a developing solution changes due to the action of an acid, which does not correspond to the component (A1) (hereinafter, "(A2)". ) Ingredients ”) may be used in combination.
The component (A2) is not particularly limited, and may be arbitrarily selected and used from a large number of conventionally known base material components for chemically amplified resist compositions.
As the component (A2), one kind of a high molecular weight compound or a low molecular weight compound may be used alone, or two or more kinds may be used in combination.

The ratio of the component (A1) to the component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, further preferably 75% by mass or more, and 100% by mass with respect to the total mass of the component (A). May be. When the ratio is 25% by mass or more, a resist pattern excellent in various lithography characteristics such as high sensitivity, resolution, and roughness improvement is likely to be formed. Such an effect is particularly remarkable in lithography using an electron beam or EUV.

The content of the component (A) in the resist composition of the present embodiment may be adjusted according to the resist film thickness to be formed and the like.

<Compound (BD1)>
In the resist composition of the present embodiment, the component (BD1) is a compound represented by the following general formula (bd1), which is composed of an anion portion and a cation portion.

［式中、Ｒｘ^１～Ｒｘ^４は、それぞれ独立に、置換基を有してもよい炭化水素基もしくは水素原子を表すか、又は２個以上が相互に結合して環構造を形成していてもよい。Ｒｙ^１～Ｒｙ^２は、それぞれ独立に、置換基を有してもよい炭化水素基もしくは水素原子を表すか、又は相互に結合して環構造を形成していてもよい。

は二重結合又は単結合である。Ｒｚ^１～Ｒｚ^４は、それぞれ独立に、原子価が許容する場合、置換基を有してもよい炭化水素基もしくは水素原子を表すか、又は２個以上が相互に結合して環構造を形成していてもよい。但し、Ｒｘ^１～Ｒｘ^４、Ｒｙ^１～Ｒｙ^２及びＲｚ^１～Ｒｚ^４のうち少なくとも１個はアニオン基を有し、アニオン部全体でｎ価のアニオンとなる。ｎは１以上の整数である。ｍは１以上の整数であって、Ｍ^ｍ＋は、下記一般式（ｃａ－０）で表されるカチオンを表す。］

[In the formula, Rx ¹ to Rx ⁴ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, or two or more of them are bonded to each other to form a ring structure. May be good. Ry ¹ and Ry ² may independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, or may be bonded to each other to form a ring structure.

Is a double bond or a single bond. Rz ¹ to Rz ⁴ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, if the valence allows, or two or more of them are bonded to each other to form a ring structure. You may be doing it. However, at least one of Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² and Rz ¹ to Rz ⁴ has an anion group, and the entire anion portion becomes an n-valent anion. n is an integer of 1 or more. m is an integer of 1 or more, and M ^{m +} represents a cation represented by the following general formula (ca-0). ]

［式中、Ｒ^ｂ１は、置換基を有してもよいアリール基である。Ｒ^ｂ２～Ｒ^ｂ３は、それぞれ独立に置換基を有してもよいアリール基又は置換基を有してもよいアルキル基である。Ｒ^ｂ２～Ｒ^ｂ３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。ただし、Ｒ^ｂ１～Ｒ^ｂ３の少なくとも１つは、スルホニル基を含む置換基を有する。］

[In the formula, R ^b1 is an aryl group which may have a substituent. R ^b2 to R ^b3 are aryl groups which may independently have a substituent or alkyl groups which may have a substituent. R ^b2 to R ^b3 may be bonded to each other to form a ring together with the sulfur atom in the formula. However, at least one of R ^b1 to R ^b3 has a substituent containing a sulfonyl group. ]

-Regarding the anion portion In the above formula (bd1), Rx ¹ to Rx ⁴ independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, or two or more of them are bonded to each other. It may form a ring structure.
Ry ¹ and Ry ² may independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, or may be bonded to each other to form a ring structure.
Rz ¹ to Rz ⁴ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, if the valence allows, or two or more of them are bonded to each other to form a ring structure. You may be doing it.

The hydrocarbon groups in Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a cyclic hydrocarbon group, respectively. It may be a hydrocarbon group in the form.
For example, in Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ , the hydrocarbon group which may have a substituent includes a cyclic group and a substituent which may have a substituent. Examples thereof include a chain-like alkyl group which may have a substituent and a chain-like 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. An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. Further, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. Further, the cyclic hydrocarbon group in Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ may contain a hetero atom such as a hetero ring.

The aromatic hydrocarbon groups in Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ are hydrocarbon groups 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, and particularly preferably 6 to 15 carbon atoms. Most preferably, it has 6 to 10 carbon atoms. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic rings of the aromatic hydrocarbon groups in Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic rings thereof. Examples thereof include aromatic heterocycles in which a part of the carbon atoms constituting the above is replaced with a hetero atom. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. The aromatic ring of the aromatic hydrocarbon group in Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ preferably does not contain a hetero atom from the viewpoint of compatibility with the component (A). Aromatic rings such as benzene, fluorene, naphthalene, anthracene, phenanthrene, and biphenyl are more preferable.
Specifically, as the aromatic hydrocarbon group in Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ , a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, a phenyl group, A naphthyl group, etc.), a group in which one of the hydrogen atoms of the aromatic ring 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, 2- Arylalkyl groups such as naphthylethyl groups) and the like. 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 Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ 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 an alicyclic hydrocarbon ring) and an alicyclic hydrocarbon group are linear or branched. Examples thereof include a group bonded to the end of a chain-shaped aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group.
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 is a polycycloalkane having a polycyclic skeleton of a crosslinked ring system such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecan; 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 Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ , a group obtained by removing one or more hydrogen atoms from a monocycloalkane or a polycycloalkane is preferable. , A group obtained by removing one hydrogen atom from a monocycloalkane is more preferable, and a group obtained by removing one hydrogen atom from cyclopentane or cyclohexane is particularly 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, and more preferably 1 to 4 carbon atoms. Is more preferable, and 1 to 3 carbon atoms 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- ], a trimethylene group [ -(CH ₂ ) _3- ], tetramethylene group [-(CH ₂ ) _4- ], pentamethylene group [-(CH ₂ ) _5- ] and the like can be mentioned.
The branched 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 has 3 or 4 carbon atoms. Is more preferable, and 3 carbon atoms 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 ). _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) ₂ -etc. Alkyl methylene groups;- 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 -etc. Alkylethylene groups; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ -etc. Alkyltrimethylene groups; -CH (CH ₃ ) Examples thereof include alkylalkylene groups such as alkyltetramethylene groups such as CH ₂ CH ₂ CH _2- , −CH ₂ CH (CH ₃ ) CH ₂ CH _2- and the like. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

The cyclic groups of Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ include -COOR ^XYZ and -OC (= O) R ^XYZ , and R ^XYZ is a lactone-containing cyclic group. Also included are carbonate-containing cyclic groups or -SO ₂ -containing cyclic groups.

Examples of the substituent in the cyclic group of Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a nitro group, and a carbonyl group. And so on.
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 preferred.
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.
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 ( _-CH2- ) constituting the cyclic hydrocarbon group.
Among them, the substituents in the cyclic groups of Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ include an alkyl group, a halogen atom, and an alkyl halide from the viewpoint of compatibility with the component (A). Groups and the like are preferred, and alkyl groups are more preferred.

Chain-like alkyl group which may have a substituent:
The chain-like alkyl group of Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ 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 nonadecyl group, an icosyl group, a henicosyl group and a docosyl group.
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, 1,1-dimethylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1- Examples thereof include an ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group and a 4-methylpentyl group.

Chain alkenyl group which may have a substituent:
The chain alkenyl group of Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ may be either linear or branched, preferably having 2 to 10 carbon atoms. 2 to 5 carbon atoms are more preferable, 2 to 4 carbon atoms are further preferable, and 3 carbon atoms are 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 Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ include an alkoxy group and a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine). Atoms, etc.), alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, cyclic groups in Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , Rz ¹ to Rz ⁴ , and the like. Among them, the substituents in the chain alkyl group or alkenyl group of Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ are halogen atoms and halogens from the viewpoint of compatibility with the component (A). Alkylated groups, the groups listed as the cyclic groups in Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ are preferable, and Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz 1 to Rx 1 to Rx 4 are preferable. The group mentioned as the cyclic group in Rz ⁴ is more preferable.

The hydrocarbon groups in Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ include cyclic groups and substituents which may have a substituent among the above hydrocarbon groups. A chain-like alkyl group may be used.

In the above formula (bd1), Ry ¹ to Ry ² may be coupled to each other to form a ring structure.
The ring structure formed by Ry ¹ to Ry ² shares one side of the six-membered ring in the formula (bd1) (bond between carbon atoms to which Ry ¹ and Ry ² are bonded, respectively), and this ring structure is formed. It may be an alicyclic hydrocarbon or an aromatic hydrocarbon. Further, this ring structure may be a polycyclic structure composed of other ring structures.

The alicyclic hydrocarbons formed by Ry ¹ and Ry ² may be polycyclic or monocyclic. As the monocyclic alicyclic hydrocarbon, monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon, polycycloalkane is preferable. The polycycloalkane preferably has 7 to 30 carbon atoms, and specifically, a polycycloalkane having a polycyclic skeleton of a crosslinked ring system such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecane; Polycycloalkanes having a polycyclic skeleton of a fused ring system such as a cyclic group having a steroid skeleton are more preferable.

The aromatic hydrocarbon ring formed by Ry ¹ to Ry ² is benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic complex in which a part of carbon atoms constituting these aromatic rings is replaced with a hetero atom. Rings and the like can be mentioned. The aromatic hydrocarbon ring formed by Ry ¹ to Ry ² preferably does not contain a heteroatom from the viewpoint of compatibility with the component (A), and has aromas such as benzene, fluorene, naphthalene, anthracene, phenanthrene, and biphenyl. Rings are more preferred.

The ring structure (alicyclic hydrocarbon, aromatic hydrocarbon) formed by Ry ¹ to Ry ² may have a substituent. The substituents here include substituents (eg, alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups) in the cyclic groups of Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ described above. , A hydroxyl group, a nitro group, a carbonyl group, etc.). Among them, as the substituent in the ring structure formed by Ry ¹ to Ry ² , an alkyl group, a halogen atom, a halogenated alkyl group and the like are preferable, and an alkyl group is more preferable, from the viewpoint of compatibility with the component (A).

The ring structure formed by Ry ¹ to Ry ² is more preferably an aromatic hydrocarbon which may have a substituent from the viewpoint of shortening the diffusion of the acid generated by exposure and controlling the diffusion of the acid.

In the above formula (bd1), two or more Rz ¹ to Rz ⁴ may be bonded to each other to form a ring structure. For example, Rz ¹ may form a ring structure with any of Rz ² to Rz ⁴ . Specifically, it shares one side of the six-membered ring in the equation (bd1) (the bond between the carbon atom to which Rz ¹ and Rz ² are bonded and the carbon atom to which Rz ³ and Rz ⁴ are bonded). Examples thereof include a ring structure, a ring structure formed by combining Rz ¹ and Rz ² , a ring structure formed by combining Rz ³ and Rz ⁴ , and the like.
The ring structure formed by two or more of Rz ¹ to Rz ⁴ may be an alicyclic hydrocarbon, an aromatic hydrocarbon, and particularly an aromatic hydrocarbon. preferable. Further, this ring structure may be a polycyclic structure composed of other ring structures.

The alicyclic hydrocarbon formed by two or more of Rz ¹ to Rz ⁴ may be polycyclic or monocyclic. As the monocyclic alicyclic hydrocarbon, monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon, polycycloalkane is preferable. The polycycloalkane preferably has 7 to 30 carbon atoms, and specifically, a polycycloalkane having a polycyclic skeleton of a crosslinked ring system such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecane; Polycycloalkanes having a polycyclic skeleton of a fused ring system such as a cyclic group having a steroid skeleton are more preferable.
A heterocyclic structure in which a part of the carbon atom is substituted with a heteroatom may be used, and a nitrogen-containing heterocycle is particularly preferable, and specific examples thereof include a cyclic imide.

The aromatic hydrocarbon ring formed by two or more of Rz ¹ to Rz ⁴ is 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. The aromatic hydrocarbon ring formed by two or more of Rz ¹ to Rz ⁴ preferably does not contain a heteroatom from the viewpoint of compatibility with the component (A), and preferably contains benzene, fluorene, naphthalene, anthracene, and the like. Aromatic rings such as phenanthrene and biphenyl are more preferable.

The ring structure (alicyclic hydrocarbon, aromatic hydrocarbon) formed by Rz ¹ to Rz ⁴ may have a substituent. The substituents here include substituents (eg, alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups) in the cyclic groups of Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ described above. , A hydroxyl group, a nitro group, a carbonyl group, etc.). Among them, as the substituent in the ring structure formed by Rz ¹ to Rz ⁴ , an alkyl group, a halogen atom, a halogenated alkyl group and the like are preferable, and an alkyl group is more preferable, from the viewpoint of compatibility with the component (A).

The ring structure formed by two or more of Rz ¹ to Rz ⁴ is one side (Rz ¹ and Rz ² ) of the six-membered ring in the equation (bd1) from the viewpoint of the diffusion controllability of the acid generated by exposure. A ring structure that shares a bond between the carbon atom to which Rz ³ and Rz ⁴ are bonded) is preferable, and an aromatic ring structure is more preferable.

In the above formula (bd1), "when the valence allows" is as follows.
That is, when the bond between the carbon atom to which Rz ¹ and Rz ² are bonded and the carbon atom to which Rz ³ and Rz ⁴ are bonded is a single bond, Rz ¹ , Rz ² , Rz ³ and Rz All of ⁴ exist. When the bond between the carbon atom to which Rz ¹ and Rz ² are bonded and the carbon atom to which Rz ³ and Rz ⁴ are bonded is a double bond, only one of Rz ¹ or Rz ² is present. And only one of Rz ³ and Rz ⁴ is present. Further, for example, when Rz ¹ and Rz ³ are bonded to form an aromatic ring structure, Rz ² and Rz ⁴ do not exist.

In the above formula (bd1), two or more of Rx ¹ to Rx ⁴ may be bonded to each other to form a ring structure. For example, Rx ¹ may form a ring structure with any of Rx ² to Rx ⁴ .
The ring structure formed by two or more of Rx ¹ to Rx ⁴ may be an alicyclic hydrocarbon or an aromatic hydrocarbon. Further, this ring structure may be a polycyclic structure composed of other ring structures.

The alicyclic hydrocarbon formed by two or more of Rx ¹ to Rx ⁴ may be polycyclic or monocyclic. As the monocyclic alicyclic hydrocarbon, monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon, polycycloalkane is preferable. The polycycloalkane preferably has 7 to 30 carbon atoms, and specifically, a polycycloalkane having a polycyclic skeleton of a crosslinked ring system such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecane; Polycycloalkanes having a polycyclic skeleton of a fused ring system such as a cyclic group having a steroid skeleton are more preferable.

In the aromatic hydrocarbon ring formed by two of Rx ¹ to Rx ⁴ , benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or a part of the carbon atoms constituting these aromatic rings are replaced with heteroatoms. Examples thereof include the aromatic heterocycles that have been used. The aromatic hydrocarbon ring formed by two of Rx ¹ to Rx ⁴ preferably does not contain a heteroatom from the viewpoint of compatibility with the component (A), and preferably contains benzene, fluorene, naphthalene, anthracene, and phenanthrene. , Biphenyl and the like are more preferred.

The ring structure (alicyclic hydrocarbon, aromatic hydrocarbon) formed by Rx ¹ to Rx ⁴ may have a substituent. The substituents here include substituents (eg, alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups) in the cyclic groups of Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ described above. , A hydroxyl group, a nitro group, a carbonyl group, etc.). Among them, as the substituent in the ring structure formed by Rx ¹ to Rx ⁴ , an alkyl group, a halogen atom, a halogenated alkyl group and the like are preferable, and an alkyl group is more preferable, from the viewpoint of compatibility with the component (A).

As the ring structure formed by two or more of Rx ¹ to Rx ⁴ , alicyclic hydrocarbons are particularly preferable from the viewpoint of acid diffusion controllability.
Further, the ring structure formed by two or more of Rx ¹ to Rx ⁴ is, among other things, at least one of Rx ¹ to Rx ² and Rx ³ to Rx ⁴ from the viewpoint of acid diffusion controllability. It is preferable that at least one of them is bonded to each other to form a crosslinked ring structure, and it is more preferable that the ring structure is an alicyclic hydrocarbon.

Bicyclic structures (Ry ¹ , Ry ² ) when at least one of Rx ¹ to Rx ² and at least one of Rx ³ to Rx ⁴ are coupled to each other to form a ring structure. , Rz ¹ and Rz ² , Rz ³ and Rz ⁴ each have a ring structure including carbon atoms bonded thereto), and the number of carbon atoms constituting the ring structure is preferably 7 to 16.

In the above formula (bd1), at least one of Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² and Rz ¹ to Rz ⁴ has an anion group, and the entire anion portion becomes an n-valent anion. n is an integer of 1 or more.
The component (BD1) is an acid generator component (B) that generates an acid acting on the base material component (A) in the resist composition by selecting an anionic group in the molecule, or by exposure (B). ) Acts as a base component (D) that traps the acid generated from the component (controls the diffusion of the acid).
In the component (BD1), Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ may be the anion groups, respectively. Or, in the (BD1) component, when two or more of Rx ¹ to Rx ⁴ are bonded to each other to form a ring structure, the carbon atom forming the ring structure or the hydrogen atom bonded to the carbon atom is bonded. May be substituted with the anion group. When two or more of Ry ¹ and Ry ² are bonded to each other to form a ring structure, the carbon atom forming the ring structure or the hydrogen atom bonded to the carbon atom is substituted with the anion group. May be good. When two or more of Rz ¹ to Rz ⁴ are bonded to each other to form a ring structure, the carbon atom forming the ring structure or the hydrogen atom bonded to the carbon atom is substituted with the anion group. May be good.

The anion groups of Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ include sulfonic acid anion structure, carboxylic acid anion structure, imide anion structure, methide anion structure, carbon anion structure, borate anion structure, and halogen. Those having an anion structure, a phosphate anion structure, an antimonic acid anion structure, an arsenic acid anion structure and the like can be mentioned. Among these, those having a sulfonic acid anion structure and those having a carboxylic acid anion structure are preferable.

Preferred examples of the anion group having a carboxylic acid anion structure include * -V'10 ^{- COO-} ( ^V'10 is a single bond or an alkylene group having 1 to 20 carbon atoms).

Examples of the anion group having the sulfonic acid anion structure include * ^-V'11 -SO _3- ^{( V'11} is a single bond or an alkylene group having 1 to 20 carbon atoms) and the following general formula (bd1-). The anionic group represented by r-an1) is preferably mentioned.
In the formula (bd1-r-an1), * indicates a bond. * Means that Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ are bonds to the carbon atom to which they are bonded.

［式中、Ｒ^ｂ０１は、炭素数１～５のフッ素化アルキル基又はフッ素原子を表す。Ｖ^ｂ０１は、アルキレン基、フッ素化アルキレン基又は単結合を表す。Ｙ^ｂ０１は、２価の連結基又は単結合を表す。］

[In the formula, R ^b01 represents a fluorinated alkyl group or a fluorine atom having 1 to 5 carbon atoms. V ^b01 represents an alkylene group, a fluorinated alkylene group or a single bond. Y ^b01 represents a divalent linking group or a single bond. ]

In the above formula (bd1-r-an1), R ^b01 represents a fluorinated alkyl group or a fluorine atom having 1 to 5 carbon atoms. In R ^b01 , the perfluoroalkyl group having 1 to 5 carbon atoms is preferably a fluorine atom, and more preferably a fluorine atom.

In the above formula (bd1-r-an1), V ^b01 represents an alkylene group, a fluorinated alkylene group or a single bond.
The alkylene group and the fluorinated alkylene group in V ^b01 preferably have 1 to 4 carbon atoms, respectively, and more preferably 1 to 3 carbon atoms. Examples of the fluorinated alkylene group in V ^b01 include a group in which a part or all of the hydrogen atom of the alkylene group is substituted with a fluorine atom. Among them, V ^b01 is preferably an alkylene group having 1 to 4 carbon atoms, a fluorinated alkylene group having 1 to 4 carbon atoms, or a single bond.

In the formula (bd1-r-an1), Y ^b01 represents a divalent linking group or a single bond.
As the divalent linking group in Y ^b01 , a divalent linking group containing an oxygen atom is preferably mentioned.
When Y ^b01 is a divalent linking group containing an oxygen atom, the Y ^b01 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. An oxygen atom-containing linking group of the system; a combination of the oxygen atom-containing linking group of the non-hydrocarbon system and an alkylene group and the like can be mentioned. 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-8).

［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。］

[In the formula, ^V'101 is a single bond or an alkylene group having 1 to 5 carbon atoms, and ^V'102 is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms. ]

The divalent saturated hydrocarbon group 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, and an alkylene group having 1 to 5 carbon atoms. Is more preferable.

The alkylene group in ^V'101 and ^V'102 may be a linear alkylene group or a branched chain alkylene group, and a linear alkylene group is preferable.
Specific examples of the alkylene group in ^V'101 and ^V'102 are methylene groups [-CH ₂ -];-CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -C (CH ₃ ). _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) ₂ -etc. Alkyl methylene groups; 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 ) Alkyltrimethylene 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.
Further, a part of the methylene group in the alkylene group in ^V'101 or ^V'102 may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is preferably a cyclohexylene group, a 1,5-adamantylene group, or a 2,6-adamantylene group.

As Y ^b01 , 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-6), respectively. Linking groups are more preferred.

Specific examples of the anion group represented by the above formula (bd1-r-an1) include, for example,
When Y ^b01 is a single bond, examples thereof include -CH ₂ CF ₂ SO _3- ^, -CF ₂ CF ₂ SO _3- ^, and fluorinated alkyl sulfonate anions such as trifluoromethane sulfonate anion and perfluorobutane sulfonate anion.
When Y ^b01 is a divalent linking group containing an oxygen atom, an anion group represented by any of the following formulas (bd1-r-an11) to (bd1-r-an13) can be mentioned.

［式中、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の整数である。ｑ”はそれぞれ独立に１～２０の整数である。ｎ”は０または１である。］

[In the formula, 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 alkylene group having 1 to 5 carbon atoms. It is an alkyl group. V "is an independently integer of 0 to 3. q "is an integer of 1 to 20 independently, and n" is 0 or 1. ]

In the formulas (bd1-r-an11) to (bd1-r-an13), 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. The V " ¹⁰¹ is preferably a single bond, an alkylene group having 1 carbon atom (methylene group), or a fluorinated alkylene group having 1 to 3 carbon atoms.

In the formulas (bd1-r-an11) to (bd1-r-an13), R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. In R ¹⁰² , the perfluoroalkyl group having 1 to 5 carbon atoms is preferably a fluorine atom, and more preferably a fluorine atom.

In the formulas (bd1-r-an11) to (bd1-r-an13), v "is an integer of 0 to 3, preferably 0 or 1.
"q" is an integer of 1 to 20, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, still more preferably 1, 2 or 3, and particularly preferably 1 or 2. Is.
"n" is 0 or 1, preferably 0.

The number of anion groups in the (BD1) component may be one, two or more, and preferably one.
The component (BD1) becomes an n-valent anion in the entire anion portion. n is an integer of 1 or more, preferably 1 or 2, and more preferably 1.

As the anion portion in the component (BD1), an anion represented by the following general formula (bd1-an1) is preferable from the viewpoint of acid diffusion controllability.

［式中、Ｒｘ^５～Ｒｘ^６はそれぞれ独立に、置換基を有してもよい炭化水素基又は水素原子を表す。Ｒｘ^７～Ｒｘ^８は、それぞれ独立に、置換基を有してもよい炭化水素基もしくは水素原子を表すか、又は相互に結合して環構造を形成していてもよい。ｐは、１又は２であり、ｐ＝２の場合、複数のＲｘ^７～Ｒｘ^８は相互に異なっていてもよい。Ｒｙ^１～Ｒｙ^２は、それぞれ独立に、置換基を有してもよい炭化水素基もしくは水素原子を表すか、又は相互に結合して環構造を形成していてもよい。

は二重結合又は単結合である。Ｒｚ^１～Ｒｚ^４は、それぞれ独立に、原子価が許容する場合、置換基を有してもよい炭化水素基もしくは水素原子を表すか、又は２個以上が相互に結合して環構造を形成していてもよい。但し、Ｒｘ^５～Ｒｘ^８、Ｒｙ^１～Ｒｙ^２及びＲｚ^１～Ｒｚ^４のうち少なくとも１個はアニオン基を有し、アニオン部全体でｎ価のアニオンとなる。ｎは１以上の整数である。］

[In the formula, Rx ⁵ to Rx ⁶ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent. Rx ⁷ to Rx ⁸ may independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, or may be bonded to each other to form a ring structure. p is 1 or 2, and when p = 2, a plurality of Rx ⁷ to Rx ⁸ may be different from each other. Ry ¹ and Ry ² may independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, or may be bonded to each other to form a ring structure.

Is a double bond or a single bond. Rz ¹ to Rz ⁴ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, if the valence allows, or two or more of them are bonded to each other to form a ring structure. You may be doing it. However, at least one of Rx ⁵ to Rx ⁸ , Ry ¹ to Ry ² and Rz ¹ to Rz ⁴ has an anion group, and the entire anion portion becomes an n-valent anion. n is an integer of 1 or more. ]

In the above formula (bd1-an1), Rx ⁵ to Rx ⁶ independently represent a hydrocarbon group or a hydrogen atom which may have a substituent. The hydrocarbon group which may have a substituent in Rx ⁵ to Rx ⁶ is the above-mentioned description of the hydrocarbon group which may have a substituent in Rx ¹ to Rx ⁴ in the above formula (bd1). Is similar to.

In the above formula (bd1-an1), Rx ⁷ to Rx ⁸ independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, or are bonded to each other to form a ring structure. May be. Such Rx ⁷ to Rx ⁸ are the same as the description of Rx ¹ to Rx ⁴ in the above-mentioned formula (bd1) described above.

In the above formula (bd1-an1), p is 1 or 2, and when p = 2, a plurality of Rx ⁷ to Rx ⁸ may be different from each other. The anion represented by the general formula (bd1-an1) has a bicycloheptane ring structure when p = 1 and a bicyclooctane ring structure when p = 2.

In the above formula (bd1-an1), Ry ¹ to Ry ² independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, or are bonded to each other to form a ring structure. You may. Such Ry ¹ to Ry ² are the same as Ry ¹ to Ry ² in the above-mentioned formula (bd1) described above.
Rz ¹ to Rz ⁴ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, if the valence allows, or two or more of them are bonded to each other to form a ring structure. You may be doing it. Such Rz ¹ to Rz ⁴ are the same as Rz ¹ to Rz ⁴ in the above-mentioned formula (bd1) described above.

However, in the above formula (bd1-an1), at least one of Rx ⁵ to Rx ⁸ , Ry ¹ to Ry ² and Rz ¹ to Rz ⁴ has an anion group and becomes an n-valent anion in the entire anion portion. .. n is an integer of 1 or more.

Among the above, the anion portion in the component (BD1) is an anion represented by p = 2 in the above formula (bd1-an1) from the viewpoint of acid diffusion controllability, that is, the following general formula (bd1-an2). ) Is more preferable.

［式中、Ｒｘ^５～Ｒｘ^６はそれぞれ独立に、置換基を有してもよい炭化水素基又は水素原子を表す。複数のＲｘ^７～Ｒｘ^８は、それぞれ独立に、置換基を有してもよい炭化水素基もしくは水素原子を表すか、又は２個以上が相互に結合して環構造を形成していてもよい。Ｒｙ^１～Ｒｙ^２は、それぞれ独立に、置換基を有してもよい炭化水素基もしくは水素原子を表すか、又は相互に結合して環構造を形成していてもよい。

は二重結合又は単結合である。Ｒｚ^１～Ｒｚ^４は、それぞれ独立に、原子価が許容する場合、置換基を有してもよい炭化水素基もしくは水素原子を表すか、又は２個以上が相互に結合して環構造を形成していてもよい。但し、Ｒｘ^５～Ｒｘ^８、Ｒｙ^１～Ｒｙ^２及びＲｚ^１～Ｒｚ^４のうち少なくとも１個はアニオン基を有し、アニオン部全体でｎ価のアニオンとなる。ｎは１以上の整数である。］

[In the formula, Rx ⁵ to Rx ⁶ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent. Each of the plurality of Rx ⁷ to Rx ⁸ independently represents a hydrocarbon group or a hydrogen atom which may have a substituent, or two or more of them may be bonded to each other to form a ring structure. .. Ry ¹ and Ry ² may independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, or may be bonded to each other to form a ring structure.

Is a double bond or a single bond. Rz ¹ to Rz ⁴ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, if the valence allows, or two or more of them are bonded to each other to form a ring structure. You may be doing it. However, at least one of Rx ⁵ to Rx ⁸ , Ry ¹ to Ry ² and Rz ¹ to Rz ⁴ has an anion group, and the entire anion portion becomes an n-valent anion. n is an integer of 1 or more. ]

In the above formula (bd1-an2), Rx ⁵ to Rx ⁶ , Rx ⁷ to Rx ⁸ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ are Rx ⁵ to Rx ⁶ and Rx in the above formula (bd 1). ⁷ to Rx ⁸ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ are the same.

However, in the above formula (bd1-an2), at least one of Rx ⁵ to Rx ⁸ , Ry ¹ to Ry ² and Rz ¹ to Rz ⁴ has an anion group and becomes an n-valent anion in the entire anion portion. .. n is an integer of 1 or more.

In the above formula (bd1), formula (bd1-an1), and formula (bd1-an2), Ry ¹ to Ry ² are mutual from the viewpoint of shortening the diffusion of the acid generated by exposure and the controllability of the diffusion of the acid. It is preferable that the ring structure is formed by bonding, and the ring structure to be formed is more preferably an aromatic hydrocarbon (aromatic ring, aromatic heterocycle) which may have a substituent.

In the above equations (bd1), (bd1-an1), and (bd1-an2), Rz ¹ to Rz ⁴ are coupled to each other to form a ring structure in terms of the diffusion controllability of the acid generated by exposure. It is preferably formed, and the ring structure to be formed is one side of the six-membered ring in the equation (a carbon atom to which Rz ¹ and Rz ² are bonded and a carbon atom to which Rz ³ and Rz ⁴ are bonded). A ring structure sharing (bonding) is preferable, and aromatic hydrocarbons (aromatic ring, aromatic heterocycle) which may have a substituent are more preferable.

In the above formulas (bd1-an1) and (bd1-an2), Rx ⁷ to Rx ⁸ are coupled to each other in terms of shortening the diffusion of the acid generated by exposure and controlling the diffusion of the acid, and have a ring structure. Is preferable, and the ring structure to be formed is more preferably an aromatic hydrocarbon (aromatic ring, aromatic heterocycle) which may have a substituent.
In the above formula (bd1-an2), the ring structures formed in Rx ⁷ to Rx ⁸ share one side of the six-membered ring in the formula (bonds between the same carbon atoms to which Rx ⁷ and Rx ⁸ are bonded). Aromatic hydrocarbons (aromatic rings, aromatic heterocycles) which may have a substituent are more preferable.

In the whole anion represented by the above formula (bd1-an2), the number of ring structures formed by coupling with each other in each of Rx ⁷ to Rx ⁸ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ is It may be one, two or more, and two or three are preferable.

In particular, as the anion portion in the component (BD1), an anion represented by the following general formula (bd1-an3) is preferably mentioned.

［式中、Ｒｘ^５～Ｒｘ^６はそれぞれ独立に、置換基を有してもよい炭化水素基又は水素原子を表す。

は二重結合又は単結合である。Ｒｚ^１～Ｒｚ^４は、それぞれ独立に、原子価が許容する場合、置換基を有してもよい炭化水素基もしくは水素原子を表すか、又は２個以上が相互に結合して環構造を形成していてもよい。但し、Ｒｘ^５～Ｒｘ^６及びＲｚ^１～Ｒｚ^４のうち少なくとも１個はアニオン基を有し、アニオン部全体でｎ価のアニオンとなる。ｎは１以上の整数である。Ｒ^０２１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、水酸基、カルボニル基又はニトロ基である。ｎ１は１～３の整数である。ｎ１１は０～８の整数である。Ｒ^０２２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、水酸基、カルボニル基又はニトロ基である。ｎ２は１～３の整数である。ｎ２１は０～８の整数である。］

[In the formula, Rx ⁵ to Rx ⁶ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent.

Is a double bond or a single bond. Rz ¹ to Rz ⁴ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, if the valence allows, or two or more of them are bonded to each other to form a ring structure. You may be doing it. However, at least one of Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ has an anion group, and the entire anion portion becomes an n-valent anion. n is an integer of 1 or more. ^R02 1 is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group or a nitro group. n1 is an integer of 1 to 3. n11 is an integer from 0 to 8. R ⁰²² is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group or a nitro group. n2 is an integer of 1 to 3. n21 is an integer from 0 to 8. ]

In the formula (bd1-an3), Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ are the same as Rx ⁵ to Rx ⁶ and Rz 1 to Rz ⁴ in the formula (bd1-an ¹ ), respectively.

In the above formula (bd1-an3), ^R021 is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxy group, a carbonyl group or a nitro group.
As the alkyl group in ^R021 , 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 in ^R021 , 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 used. , Ethoxy groups are most preferred.
Examples of the halogen atom in ^R021 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 R ⁰²¹ , 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 is the halogen. Examples include groups substituted with atoms.
Among them, as ^R021 , an alkyl group, a halogen atom, a halogenated alkyl group and the like are preferable, and an alkyl group is more preferable, from the viewpoint of compatibility with the component (A).

In the above formula (bd1-an3), n1 is an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1.
In the above formula (bd1-an3), n11 is an integer of 0 to 8, preferably an integer of 0 to 4, more preferably 0, 1 or 2, and particularly preferably 0 or 1.

In the above formula (bd1-an3), R ⁰²² is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxy group, a carbonyl group or a nitro group, and examples thereof are the same as those of R ⁰²² . .. Among them, as R ⁰²² , an alkyl group, a halogen atom, a halogenated alkyl group and the like are preferable, and an alkyl group is more preferable, from the viewpoint of compatibility with the component (A).
In the above formula (bd1-an3), n2 is an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1.
In the above formula (bd1-an3), n21 is an integer of 0 to 8, preferably an integer of 0 to 4, more preferably 0, 1 or 2, and particularly preferably 0 or 1.

However, in the above formula (bd1-an3), at least one of Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ has an anion group, and the entire anion portion becomes an n-valent anion. n is an integer of 1 or more.
The anionic group is represented by the above ^- mentioned * ^-V'10 -COO- ( ^V'10 is a single bond or an alkylene group having 1 to 5 carbon atoms) and the general formula (bd1-r-an1). Anionic groups are preferred.

Among the formulas (bd1), formulas (bd1-an1), formulas (bd1-an2), and formulas (bd1-an3), at least one of the above Rz ¹ to Rz ⁴ is excellent in terms of the effect of the present invention. , It is preferable to have an anionic group. When two or more of Rz ¹ to Rz ⁴ are bonded to each other to form a ring structure, the carbon atom forming the ring structure or the hydrogen atom bonded to the carbon atom is substituted with the anion group. You may.

Alternatively, among the above formulas (bd1-an1), formula (bd1-an2), and formula (bd1-an3), at least one of the above ^Rx5 to ^Rx6 is an anion group from the viewpoint of excellent effect of the present invention. It is preferable to have.

Alternatively, among the above formulas (bd1-an1), formula (bd1-an2), and formula (bd1-an3), at least of the above Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ from the viewpoint of excellent effect of the present invention. One preferably has an anionic group.

Specific examples of the anion portion in the compound (BD1) will be described below.

-Regarding the cation portion ((M ^{m +} ) _{1 / m} ) In the above formula (bd1), M ^{m +} represents a cation represented by the following general formula (ca-0). m is an integer of 1 or more.

［式中、Ｒ^ｂ１は、置換基を有してもよいアリール基である。Ｒ^ｂ２～Ｒ^ｂ３は、それぞれ独立に置換基を有してもよいアリール基又は置換基を有してもよいアルキル基である。Ｒ^ｂ２～Ｒ^ｂ３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。ただし、Ｒ^ｂ１～Ｒ^ｂ３の少なくとも１つは、スルホニル基を含む置換基を有する。］

[In the formula, R ^b1 is an aryl group which may have a substituent. R ^b2 to R ^b3 are aryl groups which may independently have a substituent or an alkyl group which may have a substituent. R ^b2 to R ^b3 may be bonded to each other to form a ring together with the sulfur atom in the formula. However, at least one of R ^b1 to R ^b3 has a substituent containing a sulfonyl group. ]

In the above formula (ca-0), examples of the aryl group of R ^b1 to R ^b3 include a group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, phenanthrene, biphenyl, and fluorene. .. Among them, as the aryl group of R ^b1 to R ^b3 , a group obtained by removing one hydrogen atom from benzene or naphthalene (phenyl group or naphthyl group) is preferable, and a group obtained by removing one hydrogen atom from benzene (phenyl group) is preferable. Is more preferable.

In the above formula (ca-0), the alkyl group of R ^b2 to R ^b3 may be linear, branched or cyclic.

Chain-like alkyl group which may have a substituent:
The chain-like alkyl group of R ^b2 to R ^b3 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 nonadecyl group, an icosyl group, a henicosyl group and a docosyl group.
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.

Cyclic alkyl group which may have a substituent:
The cyclic alkyl group of R ^b2 to R ^b3 preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 5 to 10 carbon atoms. Specifically, for example, a group obtained by removing one or more hydrogen atoms from a monocycloalkane; a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as a bicycloalkane, a tricycloalkane, or a tetracycloalkane. Can be mentioned. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. Examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.
In the above formula (ca-0), at least one of R ^b2 to R ^b3 is preferably an aryl group which may have a substituent, and any of them is an aryl group which may have a substituent. It is more preferable to have.

In the above formula (ca-0), when R ^b2 to R ^b3 are bonded to each other to form a ring together with the sulfur atom in the formula, a hetero atom such as a sulfur atom, an oxygen atom or a nitrogen atom, or a carbonyl group, It may be bonded via a functional group such as -SO-, -COO-, -CONH- or _-N (RN)-(the _RN is 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 formed ring include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a phenoxatiin ring, a tetrahydrothiophenium ring, and a tetrahydrothio. Examples include a pyranium ring.

In the formula (ca-0), at least one of R ^b1 to R ^b3 has a substituent containing a sulfonyl group.
Examples of the substituent containing a sulfonyl group include -SO ₂ -R ^b4 (R ^b4 is a linear or branched alkyl group which may have a substituent, and an alicyclic which may have a substituent. Examples thereof include a monovalent group represented by a type hydrocarbon group or an aromatic hydrocarbon group which may have a substituent. The substituent containing a sulfonyl group is -SO ₂ -R ^b4 (R ^b4 is a linear or branched alkyl group which may have a substituent, and an alicyclic type which may have a substituent. When it is a monovalent group represented by a hydrocarbon group or an aromatic hydrocarbon group which may have a substituent) and is bonded to an aryl group of R ^b1 , the substitution position is Although not particularly limited, it is preferably a meta-position and / or a para-position from the viewpoint of production. Similarly, when R ^b2 to R ^b3 are aryl groups that may have a substituent, the substitution position is not particularly limited, but it is preferably a meta position and / or a para position from the viewpoint of production. Is preferable.

Examples of the linear or branched alkyl group of R ^b4 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 the like. The methyl group or the ethyl group is preferable, and the methyl group is more preferable.
Substituents that the linear or branched alkyl group of R ^b4 may have include a halogen atom, a halogenated alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxy group, and a carbonyl group. Groups, carboxy groups and the like can be mentioned.
The alicyclic hydrocarbon group of R ^b4 preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and may be a polycyclic type or a monocyclic type. 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 cyclobutane, 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 12 carbon atoms, specifically. Examples thereof include adamantan, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.
Examples of the substituent that the alicyclic hydrocarbon group of R ^b4 may have include the same group as Ra ⁰⁵ described above.
Examples of the aromatic hydrocarbon group of R ^b4 include a group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, phenanthrene, biphenyl, and fluorene. Among them, as the aryl group of R ^b1 to R ^b3 , a group obtained by removing one hydrogen atom from benzene or naphthalene (phenyl group or naphthyl group) is preferable, and a group obtained by removing one hydrogen atom from benzene (phenyl group) is preferable. Is more preferable.
Examples of the substituent that the aromatic hydrocarbon group of R ^b4 may have include the same group as Ra ⁰⁵ described above.
Among them, as R ^b4 , a linear or branched alkyl group or an aromatic hydrocarbon group is preferable, and a methyl group or a phenyl group is more preferable.

The sulfonyl group of the cation represented by the general formula (ca-0) is a divalent group in which one of the carbon atoms of the ring formed by the mutual bonding of R ^b2 to R ^b3 together with the sulfur atom in the formula is substituted. It may be a sulfonyl group of. The divalent sulfonyl group may be -SO _2- , -SO _3- , -SO ₂ NH-, -SO _{2 N} (RN)-, etc., other than the sulfonyl group (-SO _2- ). It may exist as another functional group or a divalent group bonded via an atom. In this case, the ring in which R ^b2 to R ^b3 are bonded to each other and formed together with the sulfur atom in the formula is not particularly limited, and may or may not have an aromatic ring. When the aromatic ring is not contained, the ring formed includes a 1,4-dithiane 1,1-dioxide ring skeleton. When an aromatic ring is contained, it is preferably a condensed two-ring system or a condensed three-ring system containing one or more benzene rings. In the case of a fused bicyclic system, for example, a condensed bicyclic system containing a benzo [1,3] dithiol 1,1-dioxide skeleton is preferable. In the case of a fused three-ring system, for example, a fused three-ring system containing a thianthrene 5,5-dioxide skeleton and the like is preferably mentioned.

In the formula (ca-0), at least one of R ^b1 to R ^b3 is preferably an aryl group having a substituent containing a sulfonyl group as the substituent.
In the formula (ca-0), at least one of R ^b1 to R ^b3 is an aryl group having a substituent containing a sulfonyl group as the substituent at the meta and / or para positions, or R ^b2 . ~ R ^b3 is an aryl group which may have a substituent, and R ^b2 to R ^b3 are substituted with one of the carbon atoms of the ring formed together with the sulfur atom in the formula by bonding with each other 2 It preferably contains a valence sulfonyl group.

In the above formula (ca-0), the aryl groups of R ^b1 to R ^b3 may have a substituent other than the substituent containing the sulfonyl group. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a halogen atom (fluorine atom, bromine atom, chlorine atom), an alkyl halide group having 1 to 5 carbon atoms, a carbonyl group, a cyano group, an amino group and a carbon number of carbon atoms. Examples thereof include an aryl group of 6 to 20 and a group represented by the following formulas (ca-r-1) to (ca-r-7), respectively.

［式中、Ｒ’^２０１はそれぞれ独立に、水素原子、置換基を有していてもよい環式基、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。］

[In the formula, each ^R'201 independently has 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 chain alkenyl group which may be used. ]

In the formulas (ca-r-1) to (ca-r-7), a cyclic group which may have a substituent of ^R'201 , a chain alkyl group which may have a substituent, or The description of the chain alkenyl group which may have a substituent is described as Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ (hereinafter, “Rx ¹ to Rx ⁴ ”) in the above formula (bd1). Etc.), which may have a substituent (cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent). It is the same as the description about the chain alkenyl group which may have.

In the above formula (ca-0), as the substituent other than the substituent containing the sulfonyl group that the aryl group of R ^b1 to R ^b3 may have, a halogen atom or an alkyl halide group having 1 to 5 carbon atoms is used. Preferred, a fluorine atom or a trifluoromethyl group is more preferred.

The number of sulfonyl groups contained in the cation represented by the general formula (ca-0) is not particularly limited, and is preferably 1 to 4, more preferably 1 to 3, and 1 or 2. It is more preferable that the number is individual. When the number of substituents containing a sulfonyl group is 2 or more, one of R ^b1 to R ^b3 may have a substituent containing 2 or more sulfonyl groups, but R ^b1 to R ^b3 are 1 respectively. It is more preferable that each of them is substituted with a substituent containing a sulfonyl group.
Further, in the above formula (ca-0), the number of substituents other than the substituents including the sulfonyl group that the aryl groups of R ^b1 to R ^b3 may have is preferably 0 to 8, preferably 0 to 6. Is more preferable, and 0 to 4 are even more preferable.

Specific examples of suitable cations represented by the above formula (ca-0) include cations represented by the following formulas (ca-0-1) to (ca-0-10).

Among the above-mentioned (BD1) components, the above-mentioned compounds are suitable as the acid generator component (B) (hereinafter, also referred to as “(B1) component”) that generates an acid acting on the (A) component. , An anion represented by the formulas (bd1-an1) to (bd1-an3), and an anion group represented by the above general formula (bd1-r-an1) (more preferably, the formula (bd1-r-an11). An anion having (anion group represented by any of (bd1-r-an13)) (more preferably, anion represented by any of (bd1-an3-1) to (bd1-an3-15)). And various combinations of the cation represented by the formula (ca-0) (more preferably, the cation represented by any of (ca-0-1) to (ca-0-10)). be able to. Specific examples of the component (B1) are given below, but the present invention is not limited thereto.

In the resist composition of the present embodiment, the component (B1) may be used alone or in combination of two or more.
In the resist composition of the present embodiment, the content of the component (B1) is preferably 5 to 65 parts by mass, more preferably 5 to 55 parts by mass with respect to 100 parts by mass of the component (A). It is preferably 10 to 45 parts by mass, more preferably 15 to 40 parts by mass.
When the content of the component (B1) is equal to or higher than the lower limit of the above-mentioned preferable range, the lithography characteristics such as sensitivity, resolution performance, defect reduction, LWR (linewise roughness) reduction, and shape are further improved in resist pattern formation. improves. On the other hand, when it is not more than the upper limit of the preferable range, 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 is further enhanced.

Further, among the above-mentioned (BD1) components, the base component (D) that traps (controls the diffusion of the acid) the acid generated from the (B) component by exposure (hereinafter, this is also referred to as “(D1) component”). Suitable compounds are the above-mentioned anions represented by the formulas (bd1-an1) to (bd1-an3), in which * ^-V'10 -COO- ^{( V'10} is a single bond or 1 carbon atom. An anion having an anion group represented by ~ 20 alkylene group) or the above * ^-V'11 -SO _3- ⁽ V' ¹¹ is a single bond or an alkylene group having 1 to 20 carbon atoms). (More preferably, an anion represented by any of (bd1-an3-21) to (bd1-an3-24)) and a cation represented by the formula (ca-0) (more preferably, (ca-). Various combinations of cations) represented by any of 0-1) to (ca-0-10) can be mentioned. Specific examples of the component (D1) are given below, but the present invention is not limited thereto. Specific examples of are given below.

In the resist composition of the present embodiment, the component (D1) may be used alone or in combination of two or more.
In the resist composition of the present embodiment, the content of the component (D1) is preferably 1 to 35 parts by mass, more preferably 2 to 25 parts by mass, and 3 to 20 parts by mass with respect to 100 parts by mass of the component (A). The unit is more preferable.
When the content of the component (D1) is at least the lower limit of the preferable range, 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 of the preferable range, it is possible to balance with other components and various lithography characteristics are improved.

<Arbitrary ingredient>
The resist composition of the present embodiment may further contain a component (arbitrary component) other than the above-mentioned component (A) and compound (BD1) (component (B1), component (D1)).
Examples of such an optional component include (B2) component, (D2) component, (D3) component, (E) component, (F) component, (S) component and the like shown below.

≪ (B2) component ≫
The resist composition of the present embodiment may contain an acid generator component (hereinafter referred to as “(B2) component”) other than the above-mentioned component (B1) as long as the effect of the present invention is not impaired.
The component (B2) 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, oxime sulfonate-based acid generators; bisalkyl or bisarylsulfonyldiazomethanes, and diazomethane-based poly (bissulfonyl) diazomethanes. Acid generators; nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, disulfon-based acid generators and the like.

Examples of the onium salt-based acid generator include a compound represented by the following general formula (b-1) (hereinafter, also referred to as “(b-1) component”) 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”). It is assumed that the component (b-1) does not contain the compound corresponding to the above-mentioned component (B1).

［式中、Ｒ^１０１、Ｒ^１０４～Ｒ^１０８はそれぞれ独立に、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。Ｒ^１０４、Ｒ^１０５は、相互に結合して環を形成していてもよい。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。Ｙ^１０１は単結合、又は酸素原子を含む２価の連結基である。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 also a good chain alkenyl group. R ¹⁰⁴ and R ¹⁰⁵ may be coupled to each other to form a ring. R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom. V ¹⁰¹ to V ¹⁰³ are independently single bonds, alkylene groups or fluorinated alkylene groups, respectively. L ¹⁰¹ to L ¹⁰² are independently single bonds or oxygen atoms, respectively. L ¹⁰³ to L ¹⁰⁵ are independently single bonds, -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 part formula (b-1) of 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 a substituent. It is a chain alkenyl group which may have a group. The description of R ¹⁰¹ will be substituted in Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , Rz ¹ to Rz ⁴ (hereinafter referred to as “Rx ¹ to Rx ⁴ and the like”) in the above formula (bd1). A hydrocarbon group which may have a group (a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl which may have a substituent. It is the same as the explanation about the group).
Among them, 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; the general formulas (a2-r-1), (a2-r-3) to (a2-r). The lactone-containing cyclic group represented by -7); the _—SO2 -containing cyclic group represented by the general formulas (a5-r-1) to (a5-r-4), respectively, is preferable.

In the 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 such an oxygen atom include linking groups represented by the above general formulas (y-al-1) to (y-al-8).
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 general formulas (y-al-1) to (y-al-5), respectively. Linking groups are more preferred.

In the 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 the hydrogen atom of the alkylene group in V ¹⁰¹ is replaced 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 the 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 of the component (b-1) include fluorinated alkyl sulfonate anions such as trifluoromethanesulfonate anion and perfluorobutane sulfonate anion when Y ¹⁰¹ is a single bond ^; When it 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、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、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１～２０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 which may have a substituent, and a monovalent heterocyclic group represented by the above chemical formulas (r-hr-1) to (r-hr-6), respectively. A cyclic group or a chain-like alkyl group which may have a substituent. R " ¹⁰² is an aliphatic cyclic group which may have a substituent, the general formula (a2-r-1). , (A2-r-3) to (a2-r-7), respectively, or the above-mentioned general formulas (a5-r-1) to (a5-r-4), respectively. -SO ₂ -containing cyclic group. R " ¹⁰³ is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkenyl group which may have a substituent. V " ¹⁰¹ is 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 1 to 20 independently, and n "is an integer of 0 or 1."

Aliphatic cyclic groups which may have substituents of R " ¹⁰¹ , R" ¹⁰² and R " ¹⁰³ are exemplified as cyclic aliphatic hydrocarbon groups in Rx ¹ to Rx ⁴ and the like in the above formula (bd1). As the substituent, the same group as the substituent which may replace the cyclic aliphatic hydrocarbon group in Rx ¹ to Rx ⁴ and the like in the above formula (bd1) can be mentioned. ..

The aromatic cyclic group which may have a substituent in R " ¹⁰³ is a group exemplified as an aromatic hydrocarbon group in the cyclic hydrocarbon group in Rx ¹ to Rx ⁴ and the like in the above formula (bd1). It is preferable. Examples of the substituent include the same substituents which may replace the aromatic hydrocarbon group in Rx ¹ to Rx ⁴ and the like in the formula (bd1).

The chain-like alkyl group which may have a substituent in R " ¹⁰¹ is preferably the group exemplified as the chain-like alkyl group in Rx ¹ to Rx ⁴ and the like in the above formula (bd1). The chain alkenyl group which may have the substituent in ¹⁰³ is preferably the group exemplified as the chain alkenyl group in Rx ¹ to Rx ⁴ and the like in the above formula (bd1).

-Anion part of component (b-2) In formula (b-2), R ¹⁰⁴ and R ¹⁰⁵ are independent cyclic groups that may have substituents and chains that may have substituents, respectively. An alkyl group or a chain alkenyl group which may have a substituent, respectively, and a cyclic group which may have a substituent in Rx ¹ to Rx ⁴ and the like in the above formula (bd1), respectively. , A chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. Further, 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 even more 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 good within the range of the carbon number. 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, which is preferable. The ratio of fluorine atoms in the chain-shaped 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 each independently a single bond, an alkylene group, or a fluorinated alkylene group, and each of them is the same as 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 part formula (b-3) of the component (b-3), R ¹⁰⁶ to R ¹⁰⁸ are independently a cyclic group which may have a substituent and a chain which may have a substituent. It is a chain-like alkenyl group which may have a substituent or a substituent, and may have a substituent in Rx ¹ to Rx ⁴ and the like in the above formula (bd1), respectively. , A chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.
L ¹⁰³ to L ¹⁰⁵ are each independently single-bonded, -CO- or -SO _2- .

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

Preferred cation portions (( ^{M'm +} ) _{1 / m} ) include organic cations represented by the following general formulas (ca-1) to (ca-4), 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い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、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、又は置換基を有していてもよい－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 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ²¹⁰ may have 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 a substituent. -SO ₂ -containing cyclic group. L ²⁰¹ represents -C (= O)-or -C (= O) -O-. Y ²⁰¹ independently represents an arylene group, an alkylene group or an alkenylene group. x is 1 or 2. W ²⁰¹ represents a linking group of (x + 1) valence. ]

The aryl group in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² is the same as the aryl group of R ^b1 in the above formula (ca-0).
The alkyl groups in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² are the same as the alkyl groups of R ^b2 to R ^b3 in the above formula (ca-0).
The alkenyl group in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² preferably has 2 to 10 carbon atoms.
Examples of the substituents that R ²⁰¹ to R ²⁰⁷ and R ²¹⁰ to R ²¹² may have include an alkyl group, a halogen atom, an alkyl halide group, a carbonyl group, a cyano group, an amino group and an aryl group. Groups represented by the general formulas (ca-r-1) to (ca-r-7) can be mentioned.

When 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, heteroatoms such as sulfur atom, oxygen atom, and nitrogen atom, and heteroatoms such as sulfur atom and nitrogen atom are formed. Carbonyl group, -SO-, -SO _2- , -SO _3- , -COO-, -CONH- or _-N (RN)-(the _RN is an alkyl group having 1 to 5 carbon atoms), etc. It may be bonded via a functional group of. 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 formed ring include, for example, thiophene ring, thiazole ring, benzothiophene ring, thianthrene ring, benzothiophene ring, dibenzothiophene ring, 9H-thioxanthene ring, thioxanthone ring, thianthrene ring, phenoxatiin ring, 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 may have 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 a substituent. -SO ₂ -containing 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). Is more preferred.

Y ²⁰¹ independently represents an arylene group, an alkylene group or an alkenylene 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 (b1-a1).
Examples of the alkylene group and the alkaneylene group in Y ²⁰¹ include a chain alkyl group in R ¹⁰¹ in the above formula (b1-a1) 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). Examples thereof include divalent hydrocarbon groups which may be used. 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 above formula (ca-1) include (ca-0-1) to (ca-0-10) and the following formulas (ca-1-1) to (ca-1). Examples thereof include cations represented by -1-71).

［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 diphenyliodonium cation, bis (4-tert-butylphenyl) iodonium cation and the like.

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

Among the above, the cation portion ((M'm ⁺ ) _{1 / m} ) is preferably a cation represented by the general formula (ca-1), and is represented by the formulas (ca-1-1) to (ca-1-71). The cations represented by each are more preferable.

In the resist composition of the present embodiment, the component (B2) may be used alone or in combination of two or more.
When the resist composition contains the component (B2), the content of the component (B2) in the resist composition is preferably 50 parts by mass or less with respect to 100 parts by mass of the component (A), preferably 1 to 40 parts by mass. Is more preferable, and 5 to 30 parts by mass is further preferable.
By setting the content of the component (B2) in the above range, pattern formation is sufficiently performed.

≪ (D2) component ≫
The component (D2) is a base component, which is a photodisintegrating base that is decomposed by exposure and loses acid diffusion controllability (however, excluding those corresponding to the above component (D1)).
By using a resist composition containing the component (D2), the contrast between the exposed portion and the unexposed portion of the resist film can be further improved when forming a resist pattern.

The component (D2) 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 (d2-1) (hereinafter, “(d2-1) component”). The compound represented by the following general formula (d2-2) (hereinafter referred to as "(d2-2) component") and the compound represented by the following general formula (d2-3) (hereinafter referred to as "(d2-)"). 3) One or more compounds selected from the group consisting of "components") are preferable.
The components (d2-1) to (d2-3) 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 quencher occurs in the unexposed part of the resist film. Acts as.

［式中、Ｒｄ^１～Ｒｄ^４は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。但し、一般式（ｄ２－２）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が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価のオニウムカチオンである。］

[In the formula, Rd ¹ to Rd ⁴ are a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. Is. 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 general formula (d2-2). 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 onium cation. ]

{(D2-1) component}
-In the anion part formula (d2-1), Rd ¹ may have a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. These are chain alkenyl groups, and examples thereof include those similar to Rx ¹ to Rx ⁴ in the above formula (bd1), respectively.
Among these, Rd ¹ is an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain-like group which may have a substituent. Alkyl groups are preferred. Substituents that these groups may have include hydroxyl groups, oxo groups, alkyl groups, aryl groups, fluorine atoms, fluorinated alkyl groups, and the above general formulas (a2-r-1) to (a2-r-7). ), A lactone-containing cyclic group, 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.
Preferred examples of the aromatic hydrocarbon group include a polycyclic structure containing a phenyl group, a naphthyl group, and a bicyclooctane skeleton (for example, a polycyclic structure composed of a ring structure of a bicyclooctane skeleton and a ring structure other than the ring structure). Be done.
The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
The chain-like 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 the atom other than the fluorine atom include an oxygen atom, a sulfur atom, a nitrogen atom 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 the hydrogen atom constituting the linear alkyl group is preferable. It is particularly preferable that it is a fluorinated alkyl group (linear perfluoroalkyl group) in which all are substituted with a fluorine atom.

A preferable specific example of the anion portion of the component (d2-1) is shown below.

-In the cation part equation (d2-1), M'm ⁺ is an m-valent onium cation.
Examples of the M'm ⁺ onium cation include those similar to the above general formulas (ca-1) to (ca-4).
As the component (d2-1), one type may be used alone, or two or more types may be used in combination.

{(D2-2) component}
-In the anion part formula (d2-2), Rd ² may 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, and examples thereof include those similar to Rx ¹ to Rx ⁴ in the above formula (bd1).
However, it is assumed that the fluorine atom is not bonded (fluorine-substituted) to the carbon atom adjacent to the S atom in Rd ² . As a result, the anion of the component (d2-2) becomes an appropriate weak acid anion, and the quenching ability as the component (D2) 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-like 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 adamantan, norbornan, isobornan, tricyclodecane, tetracyclododecane and the like (may have a substituent); one or more from camphor and the like. It is more preferable that the group is a group excluding the hydrogen atom of.
The hydrocarbon group of Rd ² may have a substituent, and the substituent may be a hydrocarbon group (aromatic hydrocarbon group, aliphatic ring-type group, chain) in Rd ¹ of the above formula (d2-1). Examples thereof include the same substituents that the alkyl group may have.

A preferable specific example of the anion portion of the component (d2-2) is shown below.

-In the cation part formula (d2-2), M'm ⁺ is an m-valent onium cation, which is the same as M'm ⁺ in the above formula (d2-1).
As the component (d2-2), one type may be used alone, or two or more types may be used in combination.

{(D2-3) component}
-In the anion part formula (d2-3), Rd ³ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain which may have a substituent. Examples of the alkenyl group are the same as those of Rx ¹ to Rx ⁴ in the above formula (bd1), and are a cyclic group containing a fluorine atom, a chain alkyl group, or a chain alkenyl group. Is preferable. Of these, a fluorinated alkyl group is preferable, and the same group as the fluorinated alkyl group of Rd ¹ is more preferable.

In the formula (d2-3), Rd ⁴ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain which may have a substituent. Examples of the alkenyl group include those similar to Rx ¹ to Rx ⁴ in the above formula (bd1).
Of these, an alkyl group, an alkoxy group, an alkenyl group, and a cyclic group which may have a substituent are 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.

Examples of the alkenyl group in Rd ⁴ include those similar to those of Rx ¹ to Rx ⁴ in the above formula (bd 1), and vinyl group, propenyl group (allyl group), 1-methylpropenyl group, 2-methylpropenyl group and the like. preferable. 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.

Examples of the cyclic group in Rd ⁴ include those similar to Rx ¹ to Rx ⁴ and the like in the above formula (bd1), and cyclopentane, cyclohexane, adamantan, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like. An alicyclic group obtained by removing one or more hydrogen atoms from an alkane, 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 (d2-3), Yd ¹ is a single bond or divalent linking group.
The divalent linking group in Yd ¹ is not particularly limited, but is divalent including a divalent hydrocarbon group (aliphatic hydrocarbon group, aromatic hydrocarbon group) which may have a substituent and a hetero atom. Examples include the linking group of. Each of these contains 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 ^x1 in the above formula (a10-1). Examples are similar to the valence linking group.
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 (d2-3) is shown below.

-In the cation part formula (d2-3), M'm ⁺ is an m-valent onium cation, which is the same as M'm ⁺ in the above formula (d2-1).
As the component (d2-3), one type may be used alone, or two or more types may be used in combination.

As the component (D2), only one of the above components (d2-1) to (d2-3) may be used, or two or more of them may be used in combination.
When the resist composition contains the component (D2), the content of the component (D2) in the resist composition is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A), and 0. 5 to 8 parts by mass is more preferable, and 1 to 6 parts by mass is further preferable.
When the resist composition contains the component (D2), among the entire base component (D) that traps the acid generated from the component (B) by exposure (controls the diffusion of the acid) in the resist composition, ( The content of the D2) component is not particularly limited and may be appropriately adjusted in the range of 0% by mass or more to 100% by mass. When the content of the component (D2) 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, it can be balanced with other components, and various lithography characteristics are improved.

(D2) Ingredient manufacturing method:
The method for producing the component (d2-1) and the component (d2-2) is not particularly limited, and the component (d2-1) and the component (d2-2) can be produced by a known method.
Further, the method for producing the component (d2-3) is not particularly limited, and for example, the component (d2-3) is produced in the same manner as described in Japanese Patent Publication No. US2012-0149916.

≪ (D3) component ≫
The component (D3) is a basic component and is a nitrogen-containing organic compound component that acts as an acid diffusion control agent in the resist composition (however, excluding those corresponding to the above-mentioned (D1) component and (D2) component). Is.

The component (D3) is not particularly limited as long as it acts as an acid diffusion control agent and does not correspond to the components (D1) and (D2), and is composed of, for example, an anion portion and a cation portion. Examples include compounds and aliphatic amines.

Examples of the compound composed of the anion portion and the cation portion in the component (D3) include those in which the cation portion in the above components (d2-1) to (d2-3) is an ammonium cation. As the ammonium cation here, NH ₄₊ or a cation in which H bonded to the nitrogen atom thereof is replaced with a hydrocarbon group which may have a hetero atom ⁽ first to quaternary ammonium cation) or a nitrogen atom thereof. Examples thereof include cyclic cations forming a ring together with the ring.

As the aliphatic amine, a secondary aliphatic amine or a tertiary aliphatic amine is 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 substituted 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 heteroatom. 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, piperazine and the like.
The aliphatic polycyclic amine preferably has 6 to 10 carbon atoms, and specifically, 1,5-diazabicyclo [4.3.0] -5-nonene 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-hydroxyethoxy) ethyl} amine ) Ethoxy} ethyl] amine, triethanolamine triacetate and the like, and triethanolamine triacetate is preferable.

Further, as the component (D3), 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 (D3), one type may be used alone, or two or more types may be used in combination.
When the resist composition contains the component (D3), the component (D3) in the resist composition 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). By setting the above range, it is possible to balance with other components and various lithography characteristics are improved.

<< Component (E): At least one compound selected from the group consisting of an organic carboxylic acid, an oxo acid of phosphorus and a derivative thereof >>
The resist composition of the present embodiment comprises an organic carboxylic acid, an oxo acid of phosphorus and a derivative thereof as arbitrary components for the purpose of preventing deterioration of sensitivity, improving the shape of the resist pattern, stability over time, and the like. At least one compound (E) selected from the group (hereinafter referred to as "component (E)") can be contained.
As the organic carboxylic acid, for example, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
Examples of 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 phosphorus oxo acid include an ester in which the hydrogen atom of the oxo acid is replaced with a hydrocarbon group, and examples of the hydrocarbon group include 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).

≪ (F) component: Fluorine additive component ≫
The resist composition of the present embodiment may contain a fluorine additive component (hereinafter referred to as "(F) component") in order to impart water repellency to the resist film or to improve 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 formula (f1-1) can be mentioned. The polymer is a polymer (homopolymer) 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). It is preferable that the structural unit (f1) is a copolymer of the structural unit derived from acrylic acid or methacrylic acid and the structural unit (a1). 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). A structural unit derived from a meta) acrylate is preferred.

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

[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 of 1 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), examples of the halogen atom of Rf ¹⁰² and Rf ¹⁰³ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferable. Examples of the alkyl group having 1 to 5 carbon atoms of Rf ¹⁰² and Rf ¹⁰³ include the same as the above-mentioned alkyl group having 1 to 5 carbon atoms of R, and a methyl group or an ethyl group is preferable. Examples of the halogenated alkyl group having 1 to 5 carbon atoms of Rf ¹⁰² and Rf ¹⁰³ include a group in which a part or all of hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with a halogen atom. Be done. 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. 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 1 to 5, preferably an integer of 1 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, in 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 them, as Rf ¹⁰¹ , a fluorinated hydrocarbon group having 1 to 6 carbon atoms is more preferable, and a trifluoromethyl group, -CH ₂ -CF ₃ , -CH ₂ -CF ₂ -CF ₃ , and -CH (CF ₃ ) are more preferable. ) ₂ , -CH ₂ -CH ₂ -CF ₃ , -CH ₂ -CH ₂ -CF ₂ -CF ₂ -CF ₂ -CF ₃ are particularly preferable.

The mass average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography) of the component (F) is preferably 1000 to 50,000, more preferably 5000 to 40,000, and most preferably 10,000 to 30,000. When it is not more than the upper limit 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 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 1.2 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).

≪ (S) component: organic solvent component ≫
The resist composition of 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 said ester bond. Derivatives of polyhydric alcohols such as monomethyl ethers, monoethyl ethers, monopropyl ethers, monoalkyl ethers such as monobutyl ethers, or compounds having an ether bond such as monophenyl ethers [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, phenetol, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, Examples thereof include aromatic organic solvents such as xylene, simene and mesityrene, dimethylsulfoxide (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, a mixed solvent in which PGMEA and a polar solvent are mixed is also preferable. The compounding 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 to 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 appropriately set according to the coating film thickness at a concentration that can be applied to a substrate or the like. 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 of the present embodiment further contains an additive that is more miscible, for example, an additional resin for improving the performance of the resist film, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, and an antihalation agent. , Dyes and the like can be appropriately added and contained.

The resist composition of the present embodiment contains the above-mentioned component (A), the component (BD1), and, if necessary, the above-mentioned optional component.
For example, when the component (BD1) is used as the component (B1), a resist composition containing the component (A), the component (B1), and the component (D2) or the component (D3) is preferably mentioned. For example, when the component (BD1) is used as the component (D1), a resist composition containing the component (A), the component (B2), and the component (D1) is preferably mentioned.
Further, for example, when the component (BD1) is used as the component (B1) and the component (D1), a resist composition containing the component (A), the component (B1), and the component (D1) is preferable. Can be mentioned.

The resist composition of the present embodiment described above contains the compound (BD1) represented by the general formula (bd1). The (BD1) component has a specific structure (bulky structure) in which the anion portion is mainly composed of hydrocarbons, so that the hydrophobicity is relatively enhanced. As a result, the compatibility between the compound (BD1) and the base material component (A) becomes high, the solubility in an organic solvent is good, and the acid diffusivity in the resist film is appropriately controlled.
Further, this (BD1) component has a cation portion represented by the general formula (ca-0). Since the cation moiety represented by the general formula (ca-0) has a substituent containing a sulfonyl group, the reactivity is enhanced. In addition, the developability is good. By containing the (BD1) component composed of the anion portion and the cation portion, according to the resist composition of the embodiment, the lithography characteristics (roughness reduction, defect reduction, etc.) can be further improved and the sensitivity can be increased. It is presumed.

Further, when the resist composition of the embodiment is used, the uniformity of the compound (BD1) is enhanced in the resist film to be formed, so that a resist pattern having a good shape with high resolution and reduced roughness can be easily formed.

(Resist pattern forming method)
The resist pattern forming method according to the second aspect of the present invention includes a step of forming a resist film on a support using the resist composition of the above-described embodiment, a step of exposing the resist film, and a step of exposing the resist film. It is a method having a step of developing a resist film of No. 1 and forming a resist pattern.
As an embodiment of such a resist pattern forming method, for example, a resist pattern forming method performed as follows can be mentioned.

First, the resist composition of the above-described embodiment is applied onto a support with a spinner or the like, and a bake (post-apply bake (PAB)) treatment is preferably performed for 40 to 120 seconds under temperature conditions of, for example, 80 to 150 ° C. Is applied for 60 to 90 seconds to form a resist film.
Next, the resist film is exposed through a mask (mask pattern) on which a predetermined pattern is formed by using an exposure device such as an electron beam drawing device or an EUV exposure device, or an electron beam that does not pass through the mask pattern. After performing selective exposure by drawing or the like by direct irradiation, a baking (post-exposure baking (PEB)) treatment is performed, for example, under a temperature condition of 80 to 150 ° C. for 40 to 120 seconds, preferably 60 to 90 seconds.
Next, the resist film is developed. In the case of the alkaline developing process, the developing process is performed using an alkaline developing solution, and in the case of the solvent developing process, a developing solution containing an organic solvent (organic developing solution) is used.
After the development treatment, a rinsing treatment is preferably performed. In the case of the alkaline development process, the rinsing treatment is preferably a water rinse using pure water, and in the case of the solvent development process, it is preferable to use a rinsing solution containing an organic solvent.
In the case of the solvent development process, after the development treatment or the rinsing treatment, a treatment for removing the developing solution or the rinsing solution adhering to the pattern with a supercritical fluid may be performed.
Dry after development or rinsing. In some cases, a baking process (post-baking) may be performed after the development process.
In this way, the resist pattern can be formed.

The support is not particularly limited, and conventionally known ones can be used, and examples thereof include a substrate for electronic components and a support having a predetermined wiring pattern formed therein. More specifically, a silicon wafer, a metal substrate such as copper, chromium, iron, or aluminum, a glass substrate, or 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 with 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 multilayer structure having three or more layers provided with (metal thin film, etc.) (three-layer resist method).

The wavelength used for exposure is not particularly limited, and may be ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV ₍ extreme ultraviolet rays), VUV (vacuum ultraviolet rays), EB (electron rays), X-rays, soft X-rays, etc. It can be done using radiation. The resist composition is highly useful for KrF excimer laser, ArF excimer laser, EB or EUV, more useful for ArF excimer laser, EB or EUV, and useful for EB or EUV. Especially expensive. That is, the resist pattern forming method of the present embodiment is a particularly useful method when the step of exposing the resist film includes an operation of exposing the resist film to EUV (extreme ultraviolet) or EB (electron beam). ..

The exposure method of the resist film may be normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or immersion exposure (Liquid Immersion Lithography).
In immersion exposure, the space between the resist film and the lens at the lowest position of the exposure apparatus is previously filled with a solvent (immersion medium) having a refractive index larger than the refractive index of air, and exposure (immersion exposure) is performed in that state. This is the 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 fluorinated inert liquid include a fluorinated compound such as C ₃ HCl ₂ F ₅ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , C ₅ H ₃ F ₇ as a main component. 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. When the fluorine-based inert liquid has a boiling point in the above range, it is preferable 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 perflooloalkyl compound include a perfluoroalkyl ether compound and a perfluoroalkylamine compound.
Further, specifically, as the perfluoroalkyl ether compound, perfluoro (2-butyl-tetrahydrofuran) (boiling point 102 ° C.) can be mentioned, and as the perfluoroalkylamine compound, perfluorotributylamine (perfluorotributylamine) can be mentioned. Boiling point 174 ° C.) can be mentioned.
As the immersion medium, water is preferably used from the viewpoints of cost, safety, environmental problems, versatility and the like.

Examples of the alkaline developer used in the developing process in the alkaline developing process include a 0.1 to 10% by mass tetramethylammonium hydroxide (TMAH) aqueous solution.
The organic solvent contained in the organic developer used in the developing process in the solvent developing process may be any known organic solvent as long as it can dissolve the component (A) (component (A) before exposure). It can be selected as appropriate. Specific examples thereof include ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, polar solvents such as ether solvents, hydrocarbon solvents and the like.
The ketone solvent is an organic solvent containing CC (= O) -C in its structure. The ester solvent is an organic solvent containing CC (= O) -OC in the structure. The alcohol solvent is an organic solvent containing an alcoholic hydroxyl group in its structure. The "alcoholic hydroxyl group" means a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group. The nitrile-based solvent is an organic solvent containing a nitrile group in its structure. The amide-based solvent is an organic solvent containing an amide group in its structure. The ether solvent is an organic solvent containing COC in its structure.
Among the organic solvents, there are organic solvents containing a plurality of functional groups that characterize each of the above solvents in the structure, but in that case, the organic solvent corresponds to any solvent type containing the functional groups of the organic solvent. It shall be. For example, diethylene glycol monomethyl ether shall fall under any of the alcohol-based solvents and ether-based solvents in the above classification.
The hydrocarbon-based solvent is a hydrocarbon solvent which is composed of a hydrocarbon which may be halogenated and has no substituent other than 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 preferable.
Among the above, the organic solvent contained in the organic developer is preferably a polar solvent, preferably a ketone solvent, an ester solvent, a nitrile solvent and the like.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone and methylethylketone. , Methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, γ-butyrolactone, methylamylketone (2-heptanone) and the like. Among these, methylamylketone (2-heptanone) is preferable as the ketone solvent.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxy acetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol mono. Propyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate , 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3 － Propyl, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, propionic acid Ethyl, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate , Propyl-3-methoxypropionate and the like. Among these, butyl acetate is preferable as the ester solvent.

Examples of the nitrile-based solvent include acetonitrile, propionitril, valeronitrile, butyronitril and the like.

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

The developing process can be carried out by a known developing method. For example, a method of immersing a 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), spreading the developer on the support rotating at a constant speed while scanning the developer spray nozzle. Examples include a method of continuing (dynamic dispense method).

As the organic solvent contained in the rinse solution used for the rinse treatment after the development process in the solvent development process, for example, among the organic solvents listed as the organic solvents used in the organic developer, those having difficulty in dissolving the resist pattern are appropriately selected. Can be used. Usually, at least one solvent selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent and an ether solvent is used. Among these, at least one selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent and an amide solvent is preferable, and at least one selected from an alcohol solvent and an ester solvent is preferable. More preferably, an alcohol solvent is particularly preferable.
The alcohol solvent used in the rinsing solution is preferably a monohydric alcohol having 6 to 8 carbon atoms, and the monohydric alcohol may be linear, branched or cyclic. Specific examples thereof include 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, benzyl alcohol and the like. Be done. Among these, 1-hexanol, 2-heptanol and 2-hexanol are preferable, and 1-hexanol and 2-hexanol are more preferable.
Any one of these organic solvents may be used alone, or two or more thereof may be used in combination. Further, it may be used by mixing with an organic solvent other than the above or water. However, in consideration of development characteristics, the blending amount of water in the rinsing liquid is preferably 30% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and further preferably 3% by mass, based on the total amount of the rinsing liquid. The following are particularly preferred.
A known additive can be added to the rinse solution, if necessary. Examples of the additive include a surfactant. Examples of the surfactant include the same as described above, and a nonionic surfactant is preferable, and a nonionic fluorine-based surfactant or a nonionic silicon-based surfactant is more preferable.
When the surfactant is blended, the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, preferably 0.01 to 0.5% by mass, based on the total amount of the rinse solution. % Is more preferable.

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).

In the resist pattern forming method of the present embodiment described above, since the resist composition according to the first aspect described above is used, high sensitivity and better lithography characteristics (roughness) are used when forming a resist pattern. It is possible to form a resist pattern (reduction, etc.).

(Method for manufacturing compounds)
The method for producing a compound (BD1) composed of an anion portion and a cation portion represented by the general formula (bd1) is a compound represented by the following general formula (bp-1) (hereinafter, "compound (bp-1)". ) ”) Is oxidized to obtain a compound represented by the following general formula (b1-1) (hereinafter referred to as“ compound (b1-1) ”).

［式中、Ｒ^ｐ１は、置換基を有してもよいアリール基であり、Ｒ^ｐ２～Ｒ^ｐ３は、それぞれ独立に置換基を有してもよいアリール基又は置換基を有してもよいアルキル基である。Ｒ^ｐ２～Ｒ^ｐ３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。ただし、Ｒ^ｐ１～Ｒ^ｐ３の少なくとも１つは、前記置換基として－ＳＲ^ｐ４で表される基を有するアリール基又はアルキル基である。Ｒ^ｐ４は、アルキル基である。Ｘｐ^－は対アニオンである。］

[In the formula, R ^p1 is an aryl group which may have a substituent, and R ^p2 to R ^p3 may have an aryl group or a substituent which may independently have a substituent. It is an alkyl group. R ^p2 to R ^p3 may be bonded to each other to form a ring together with the sulfur atom in the formula. However, at least one of R ^p1 to R ^p3 is an aryl group or an alkyl group having a group represented by -SR ^p4 as the substituent. R ^p4 is an alkyl group. Xp ^- is a counter anion. ]

［式中、Ｒ^ｂ１１は、置換基を有してもよいアリール基であり、Ｒ^ｂ１２～Ｒ^ｂ１３は、それぞれ独立に置換基を有してもよいアリール基又は置換基を有してもよいアルキル基である。Ｒ^ｂ１２～Ｒ^ｂ１３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。ただし、Ｒ^ｂ１１～Ｒ^ｂ１３の少なくとも１つは、前記置換基として－ＳＯ_２－Ｒ^ｐ４で表される基を有するアリール基又はアルキル基である。Ｒ^ｐ４は、アルキル基である。Ｘｐ^－は対アニオンである。］

[In the formula, R ^b11 is an aryl group which may have a substituent, and R ^b12 to R ^b13 may have an aryl group or a substituent which may independently have a substituent. It is an alkyl group. R ^b12 to R ^b13 may be bonded to each other to form a ring together with the sulfur atom in the formula. However, at least one of R ^b11 to R ^b13 is an aryl group or an alkyl group having a group represented by _-SO2 -R ^p4 as the substituent. R ^p4 is an alkyl group. Xp ^- is a counter anion. ]

The aryl group which may have a substituent of R ^p1 in the compound (bp-1) is the same as the description of the aryl group which may have a substituent of R ^b1 in the above formula (ca-0). be.
In the formula (bp-1), the aryl group which may have a substituent of R ^p2 to R ^p3 or the alkyl group which may have a substituent is R ^b2 to R b2 in the above formula (ca-0). It is the same as the description of the aryl group which may have a substituent of R ^b3 or the alkyl group which may have a substituent.

In the formula (bp-1), at least one of R ^p1 to R ^p3 is an aryl group or an alkyl group having a group represented by -SR ^p4 as the substituent. R ^p4 is an alkyl group.
-In the group represented by SR ^p4 , the alkyl group of R ^p4 is preferably a linear or branched alkyl group. Specific examples of the linear or branched alkyl group 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, and a neopentyl group. However, a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
Further, in the case where R ^p2 to R ^p3 are bonded to each other to form a ring with the sulfur atom in the formula in the group represented by -SR ^p4 , the ring is further formed with the group represented by -SR ^p4 . When formed, the group represented by -SR ^p4 is a divalent group obtained by removing one hydrogen atom from the alkyl group of R ^p4 or a divalent group of -S- (that is, -SR ^p4'-). Rings may be formed (as R ^p4'is an alkylene group or a single bond).

In the above formula (bp-1), examples of the counter anion of Xp ⁻ include a halogen anion (Cl ⁻ , Br ⁻ , I ⁻ ), a carboxylic acid anion (acetate anion, etc.), RpSO _3- , ^and the like. .. Rp is an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) or 1 to 5 carbon atoms. It is a fluorinated alkyl group of 5, preferably a trifluoromethyl group.

In the above formula (b1-1), the aryl group which may have a substituent of R ^b11 is the same as the description of the aryl group which may have a substituent of R ^b1 in the above formula (ca-0). Is.
In the formula (b1-1), the aryl group which may have a substituent of R ^b12 to R ^b13 or the alkyl group which may have a substituent is R ^b2 to R b2 in the above formula (ca-0). It is the same as the description of the aryl group which may have a substituent of R ^b3 or the alkyl group which may have a substituent.

In the formula (b1-1), at least one of R ^b11 to R ^b13 is an aryl group or an alkyl group having a group represented by _-SO2 -R ^p4 as the substituent.
The substituent containing a halogen atom in R ^b11 to R ^b13 is the same as the description of the substituent containing a halogen atom in R ^b1 to R ^b3 in the above formula (ca-0).
In the group represented by _-SO2 -R ^p4 , the alkyl group of R ^p4 is the alkyl of R ^p4 of "group represented by -SR ^p4 " in R ^p1 to R ^p3 in the above formula (bp-1). It is the same as the explanation of the group.

In the formula (b1-1), the pair anion of Xp ⁻ is the same as the description of the pair anion of Xp ⁻ in the formula (bp-1).

The method for oxidizing the compound (bp-1) is not particularly limited, and for example, an oxidation reaction (for example, oxonone) in which the compound (bp- ₁ ) is reacted with a potassium peroxymonosulfate salt (2KHSO ₅ , KHSO ₄ , K2 SO ₄ ) is allowed to react. Oxidation) and the like.
The solvent used for the oxidation reaction is not particularly limited, and examples thereof include at least one selected from water or an alcohol solvent such as methanol, ethanol, and isopropanol.
The reaction temperature of the oxidation reaction is not particularly limited, but is preferably 0 to 50 ° C, more preferably 5 to 40 ° C.
The reaction time of the oxidation reaction is not particularly limited, but is preferably 1 to 72 hours, more preferably 2 to 60 hours.
As the compound (bp-1), a commercially available compound may be used, or a compound synthesized by a known production method may be used.

The compound (b1-1) has a compound (BD1) having an anion by a salt exchange reaction with a precursor (a precursor having an anion portion in the above general formula (bd1)) such as an ammonium salt having a desired anion. ) Can be obtained.

A precursor such as an ammonium salt having the desired anion (precursor having an anion portion in the above general formula (bd1)) can be produced, for example, as follows.
For example, as shown in the reaction formula below, an alkene or alkyne ((1) in the reaction formula below) is added to a conjugated diene ((2) in the reaction formula below) to form a ring structure ((1) in the reaction formula below). 3)) A method using the Diels-Alder reaction can be mentioned. Specifically, the desired cation was introduced into the product (intermediate) produced by the Diels-Alder reaction to obtain a precursor by introducing a desired anion group, and then the desired cation was introduced by a salt exchange reaction (BD1). Ingredients are obtained. Alternatively, a Diels-Alder reaction is carried out using an alkene, an alkyne or a conjugated diene containing a substituent derived from a desired anionic group (a substituent into which a desired anionic group can be introduced) to obtain an intermediate, and then the desired substance is obtained. Anionic groups can be introduced to obtain precursors.

The conjugated diene is appropriately selected according to the target compound ((BD1) component), and for example, anthracene or a derivative thereof, triptycene or a derivative thereof may be used.
The method for introducing an anionic group is, for example, a method using an esterification reaction; an ammonium salt having an anionic group introduced with a tosyl group and a lithium compound having a ring structure of an anionic moiety skeleton (derived from the Deals-Alder reaction). Examples thereof include a method using a reaction, or a method in which an intermediate containing a halogen atom is sulfinated to obtain a sulfinate and then oxidized to obtain a sulfonate.

When an esterification reaction is used as a method for introducing an anionic group, for example, a compound represented by the above general formula (bd1) [a compound having an anionic group represented by the general formula (bd1-r-an1), Y ^b01 = -C (= O) -O-] can be mentioned in the production method of the embodiment including the first and second steps shown below.
An anion group represented by the general formula (bd1-r-an1) and having Y ^b01 = -C (= O) -O- is represented by the general formula (b1-r-an10). Anion group ". The target compound produced by the production method of the embodiment including the first and second steps is referred to as compound (B1-0).
As the raw material used in each step, a commercially available raw material may be used, or a synthetic raw material may be used.
The organic solvent used in the first and second steps may be any solvent as long as the compound used in each step can be dissolved and does not react with those compounds. For example, dichloromethane, dichloroethane, chloroform, tetrahydrofuran, N, N -Includes dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, propionitrile and the like.

-First step In the first step, the intermediate and the compound (I) are dissolved in an organic solvent (dichloromethane or the like), and the reaction is carried out in the presence of a base. Then, the precursor (Bpre) is obtained by performing filtration, concentration and the like.

［式中、Ｒ^ｂ０１及びＶ^ｂ０１は、上記式（ｂｄ１－ｒ－ａｎ１）中のＲ^ｂ０１及びＶ^ｂ０１とそれぞれ同様である。（Ｍ_１”^ｍ＋）_１／ｍは、アンモニウムカチオンである。Ｒｘ^５、Ｒｘ^６、Ｒｚ^１～Ｒｚ^４、Ｒ^０２１、ｎ１、ｎ１１、Ｒ^０２２、ｎ２及びｎ２１は、上記式（ｂｄ１－ａｎ３）中のＲｘ^５、Ｒｘ^６、Ｒｚ^１～Ｒｚ^４、Ｒ^０２１、ｎ１、ｎ１１、Ｒ^０２２、ｎ２及びｎ２１とそれぞれ同様である。但し、Ｒｘ^５～Ｒｘ^６及びＲｚ^１～Ｒｚ^４のうち少なくとも１個は一般式（ｂ１－ｒ－ａｎ１０）で表されるアニオン基を有し、アニオン部全体でｎ価のアニオンとなる。ｎは１以上の整数である。］

[In the formula, R ^b01 and V ^b01 are the same as R ^b01 and V ^b01 in the above formula (bd1-r-an1), respectively. (M ₁ " ^{m +} ) _{1 / m} is an ammonium cation. Rx ⁵ , Rx ⁶ , Rz ¹ to Rz ⁴ , R ⁰²¹ , n1, n11, R ⁰²² , n2 and n21 are the above formulas (bd1-an3). The same applies to Rx ⁵ , Rx ⁶ , Rz ¹ to Rz ⁴ , R ⁰²¹ , n1, n11, R ⁰²² , n2, and n21, respectively, except that at least one of Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ . Each has an anion group represented by the general formula (b1-r-an10) and becomes an n-valent anion in the entire anion portion. N is an integer of 1 or more.]

Examples of the base added in the first step include organic bases such as triethylamine, 4-dimethylaminopyridine, pyridine, ethyldiisopropylaminocarbodiimide (EDCI) hydrochloride, dicyclohexylcarboxyimide (DCC), diisopropylcarbodiimide, and carbodiimidazole; Examples thereof include inorganic bases such as sodium hydride, K ₂ CO ₃ , and Cs ₂ CO ₃ .
The cation portion of the compound (I) may be an ammonium cation derived from an aliphatic amine or an ammonium cation derived from an aromatic amine.

The amount of compound (I) to be used is preferably about 1 to 3 equivalents, more preferably 1 to 2 equivalents, relative to the intermediate.
The reaction temperature is preferably 0 to 50 ° C, more preferably 5 to 40 ° C.

-Second step In the second step, the precursor (Bpre) and the salt exchange compound (II) (specifically, for example, the above compound (b1-1)) are mixed with water, dichloromethane, acetonitrile, chloroform and the like. The reaction is carried out under a solvent to obtain the desired compound (B1-0) by salt exchange between the precursor (Bpre) and the organic cation in the compound (II).

［式中、Ｒ^ｂ０１及びＶ^ｂ０１は、上記式（ｂ１－ｒ－ａｎ１０）中のＲ^ｂ０１及びＶ^ｂ０１とそれぞれ同様である。（Ｍ_１”^ｍ＋）_１／ｍは、アンモニウムカチオンである。Ｒｘ^５、Ｒｘ^６、Ｒｚ^１～Ｒｚ^４、Ｒ^０２１、ｎ１、ｎ１１、Ｒ^０２２、ｎ２及びｎ２１は、上記式（ｂｄ１－ａｎ３）中のＲｘ^５、Ｒｘ^６、Ｒｚ^１～Ｒｚ^４、Ｒ^０２１、ｎ１、ｎ１１、Ｒ^０２２、ｎ２及びｎ２１とそれぞれ同様である。但し、Ｒｘ^５～Ｒｘ^６及びＲｚ^１～Ｒｚ^４のうち少なくとも１個は一般式（ｂ１－ｒ－ａｎ１０）で表されるアニオン基を有し、アニオン部全体でｎ価のアニオンとなる。ｎは１以上の整数である。Ｚ^－は、非求核性イオンである。（Ｍ^ｍ＋）_１／ｍは、ｍ価の有機カチオンであり、ここでは、上記式（ｃａ－０）で表されるカチオンと同様である。］

[In the formula, R ^b01 and V ^b01 are the same as R ^b01 and V ^b01 in the above formula (b1-r-an10), respectively. (M ₁ " ^{m +} ) _{1 / m} is an ammonium cation. Rx ⁵ , Rx ⁶ , Rz ¹ to Rz ⁴ , R ⁰²¹ , n1, n11, R ⁰²² , n2 and n21 are the above formulas (bd1-an3). The same applies to Rx ⁵ , Rx ⁶ , Rz ¹ to Rz ⁴ , R ⁰²¹ , n1, n11, R ⁰²² , n2, and n21, respectively, except that at least one of Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ . Each has an anion group represented by the general formula (b1-r-an10) and becomes an n-valent anion in the entire anion portion. N is an integer of 1 or more. Z ^- is a non-nucleophilic ion. (M ^{m +} ) _{1 / m} is an m-valent organic cation, which is the same as the cation represented by the above formula (ca-0) here.]

As ^Z- , for example, halogen ions such as bromine ion and chloride ion; an ion that can be an acid having a lower acidity than the precursor (Bpre), BF _4- ^, AsF _6- ^, SbF _6- ^, PF _6- ^or ClO. ₄ ^- etc.
The reaction temperature is preferably about 0 to 100 ° C, more preferably about 0 to 50 ° C.
The reaction time varies depending on the reactivity between the precursor (Bpre) and the salt exchange compound (II), the reaction temperature, etc., but is usually preferably 10 minutes or more and 24 hours or less, more preferably 10 minutes or more and 12 hours or less. preferable.

After the salt exchange reaction is completed, the compound in the reaction solution may be isolated and purified. Conventionally known methods can be used for isolation and purification, and for example, concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography and the like can be appropriately combined and used.
The structures of the compounds obtained as described above are: ¹ H-nuclear magnetic resonance (NMR) spectroscopy, ¹³ C-NMR spectroscopy, ¹⁹ F-NMR spectroscopy, infrared absorption (IR) spectroscopy, mass spectrometry (MS). ) Method, elemental analysis method, X-ray crystal diffraction method and other general organic analysis methods can be used for identification.

The intermediate is appropriately selected according to the target compound (B1-0), and examples thereof include products obtained by the Diels-Alder reaction represented by the following reaction formula. Anthracene or a derivative thereof can be used for (starting material 1) in the following reaction formula. As the (starting material 2) in the following reaction formula, a compound having an ethylenic double bond such as an acrylic acid ester can be used.
Further, examples of the intermediate include triptycene or a derivative thereof.

［式中、Ｒｘ_１’～Ｒｘ _４’は、前記Ｒｘ^１～Ｒｘ^４と同様である。Ｒｙ_１’～Ｒｙ_２’は、前記Ｒｙ^１～Ｒｙ^２と同様である。

は三重結合又は二重結合である。

は二重結合又は単結合である。Ｒｚ_１’～Ｒｚ_４’は、前記Ｒｚ^１～Ｒｚ^４と同様である。但し、Ｒｘ_１’～Ｒｘ_４’、Ｒｙ_１’～Ｒｙ_２’及びＲｚ_１’～Ｒｚ_４’のうち少なくとも１個は、前記アニオン基を導入し得る、脱離基を含む基である。］

[In the formula, Rx ^1'to Rx ^{4'are the same as those of Rx 1} _to Rx ₄ . Ry _1'to Ry ^2'are the same as those of Ry ¹ to Ry ₂ .

Is a triple bond or a double bond.

Is a double bond or a single bond. Rz _1'to Rz ^4'are the same as those of Rz ¹ to Rz ₄ . However, at least _one of Rx 1'to Rx ₄ ', Ry _1'to Ry _2'and Rz _1'to Rz _4'is a group containing a leaving group into which the anion group can be introduced. ]

Examples of the group containing a leaving group into which an anionic group can be introduced include a halogen atom, a group containing a halogen atom, and a group having a substituent (hydroxyl group, carboxy group, etc.) capable of dehydration condensation.

When an esterification reaction is used as a method for introducing an anionic group, examples of the group containing the leaving group include substituents capable of dehydration condensation. For example, the intermediate in the reaction formula shown in the first step preferably has a substituent (hydroxyl group, carboxy group, etc.) capable of dehydration condensation. In this first step, the esterification reaction is carried out to obtain an ammonium sulfonic acid salt which is a precursor (Bpre).

When a reaction between an ammonium salt having an anionic group into which a tosyl group has been introduced and a lithium compound having a ring structure of an anionic part skeleton (derived from the Deals-Alder reaction) is used as a method for introducing an anionic group, the above-mentioned desorption group is used. Examples of the group containing a halogen atom include a halogen atom and a group containing a halogen atom, and a bromine atom is preferable. An intermediate containing a halogen atom (preferably a bromine atom) is Li-dilated into a Li compound, and then reacted with an ammonium salt having an anionic group introduced with a tosyl group to obtain an ammonium sulfonic acid salt as a precursor.

As a method for introducing an anionic group, when an intermediate containing a halogen atom is sulphinized to obtain a sulfinate and then oxidized to obtain a sulfonate, the group containing the desorbing group is used. , Halogen atom, or a group containing a halogen atom, preferably a bromine atom. An intermediate containing a halogen atom (preferably a bromine atom) is converted into an ammonium sulfinate salt by using a sulfinating agent in the presence of an amine, and further reacted with an oxidizing agent to obtain an ammonium sulfonic acid salt as a precursor. obtain.

The target compound ((BD1) component) can be obtained by performing salt exchange in the second step described above for each precursor ammonium sulfonic acid salt.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
In this embodiment, the compound represented by the chemical formula (1) is referred to as “compound (1)”, and the compounds represented by other chemical formulas are also referred to in the same manner.

<Manufacturing of compounds>
(Manufacturing Example 1)
Thiantrene-5-oxide (18.8 g, 81 mmol) and trimethylsilyltrifluoromethanesulfonate (36 g, 163 mmol) were dissolved in THF (47 g), and bromobenzene (12.7 g, 81 mmol) and magnesium (2.0 g,) were dissolved therein. A THF solution of phenylmagnesium bromide prepared by a conventional method using (81 mmol) and THF (90 g) was added dropwise in a range where the in-system temperature did not exceed −5 ° C. After completion of the dropping, the reaction was continued for 1 hour at room temperature to complete the reaction. The reaction mixture was added to ultrapure water (150 g) over 1 hour, dichloromethane (170 g) was added, and the mixture was stirred for 30 minutes, and then the aqueous layer was removed. After washing the organic layer with ultrapure water (150 g) three times, the organic layer was added dropwise to MTBE (methyl tert-butyl ether, 1700 g), and the precipitated solid was filtered. Intermediate 1 was obtained by drying the filtrate under reduced pressure (24.7 g, yield = 68.9%).

(Manufacturing Example 2)
Intermediate 1 (6.6 g, 15 mmol) is dissolved in a mixed solution of ultrapure water (25 g) and methanol (75 g), and Oxone® (registered trademark) (13.8 g, 22 mmol, molecular formula: 2KHSO ₅ · KHSO ₄ · K ₂ SO ₄ , molecular weight: 614.76)) was added, and the mixture was stirred at room temperature for 48 hours. The reaction solution was filtered, ultrapure water (50 g) and dichloromethane (200 g) were added, and the mixture was stirred for 30 minutes, and then the aqueous layer was removed. After washing with saturated aqueous sodium hydrogen sulfite solution (50 g) and washing with ultrapure water (150 g) three times, the organic layer was added dropwise to MTBE (500 g), and the precipitated solid was filtered. The filtrate was dried under reduced pressure to give compound A (4.7 g, yield = 65.4%).

(Production example of compound (B1-1))
Compound A (4.4 g, 9.3 mmol) and anion precursor Bpre-a (5.7 g, 9.3 mmol) are dissolved in dichloromethane (50 g), ultrapure water (50 g) is added, and 30 at room temperature. Reacted for minutes. After completion of the reaction, the aqueous phase was removed, and then the organic phase was washed 4 times with ultrapure water (50 g). The organic phase was concentrated to dryness using a rotary evaporator to obtain compound (B1-1) (6.8 g, yield = 93.4%).

(Production example of other compounds)
It is shown below in the same manner as in the above-mentioned "Production example of compound (B1-1)" except that the combination of the following compounds B to J and the following compounds Bpre-b to Bpre-h is changed. Compound (B1-2) to compound (B1-13), compound (D1-1), and compound (D1-2) were obtained, respectively.

NMR measurement was performed on each of the obtained compounds, and the structure was identified from the following analysis results.

Compound (B1-1): Combination of compound A and compound Bpre-a
¹ H-NMR (DMSO, 400MHz): δ (ppm) = 8.49 (d, ArH, 2H), 8.00-8.22 (m, ArH, 6H), 7.84-7.96 (m, ArH, 3H), 7.78 (d, ArH, 2H), 7.01-7.47 (m, ArH, 8H), 4.72 (s, CH, 1H), 4.43 (s, CH, 1H), 4.23, (t, CH2, 2H), 2.95-3.02 (m, CH, 1H), 2.63-2.73, (m, CF2CH2, 2H), 1.86-2.07 (m, CH2, 2H)
¹⁹ F-NMR (DMSO, 376MHz): δ (ppm) = -111.3, -117.4

Compound (B1-2): Combination of compound B and compound Bpre-a
¹ H-NMR (DMSO, 400MHz): δ (ppm) = 8.62 (d, ArH, 2H), 8.05 (d, ArH, 2H), 7.82-7.98 (m, ArH, 4H), 7.50-7.66 (m, ArH, 2H), 7.01-7.47 (m, ArH, 10H), 4.72 (s, CH, 1H), 4.43 (s, CH, 1H), 4.23, (t, CH2, 2H), 3.51 (s, CH3, 3H), 2.95-3.02 (m, CH, 1H), 2.63-2.73, (m, CF2CH2, 2H), 1.86-2.07 (m, CH2, 2H).
¹⁹ F-NMR (DMSO, 376MHz): δ (ppm) = -111.3, -117.4

Compound (B1-3): Combination of compound C and compound Bpre-a
¹ H-NMR (DMSO, 400MHz): δ (ppm) = 8.76 (s, ArH, 1H), 8.59-8.64 (m, ArH, 1H), 8.42 (t, ArH 2H), 8.03-8.19 (m, ArH) , 5H), 7.81 (t, ArH, 2H), 7.69 (t, ArH, 1H), 7.01-7.47 (m, ArH, 8H), 4.72 (s, CH, 1H), 4.43 (s, CH, 1H) , 4.23, (t, CH2, 2H), 3.51 (s, CH3, 3H), 2.95-3.02 (m, CH, 1H), 2.63-2.73, (m, CF2CH2, 2H), 1.86-2.07 (m, CH2) , 2H)
¹⁹ F-NMR (DMSO, 376MHz): δ (ppm) = -111.3, -117.4

Compound (B1-4): Combination of compound D and compound Bpre-b
¹ H-NMR (DMSO, 400MHz): δ (ppm) = 7.74-7.90 (m, 19H, ArH), 7.01-7.47 (m, ArH, 8H), 4.70 (d, OCH (lactone), 1H), 4.58 (t, COOCH (lactone), 1H), 4.50 (d, CH, 2H), 4.22, (t, COOCH2, 2H), 3.32 (m, CH (lactone), 1H), 3.20 (t, COCH, 2H) , 2.63-2.73, (m, CF2CH2, CH (lactone) 4H), 1.60-2.20 (m, CH2 (lactone), 4H)
¹⁹ F-NMR (DMSO, 376MHz): δ (ppm) = -111.3, -117.6

Compound (B1-5): Combination of compound E and compound Bpre-c
¹ H-NMR (DMSO, 400MHz): δ (ppm) = 8.60-8.80 (m, ArH, 5H), 8.41 (d, ArH, 2H), 8.28 (d, ArH, 2H), 8.06 (t, ArH, 2H), 7.00-7.48 (m, ArH, 8H), 4.70 (s, CH, 1H), 4.40 (s, CH, 1H), 3.52 (s, CH3, 6H), 3.15-3.22 (m, CF2CH, 1H) ), 1.95-2.15 (m, CH2, 2H)
¹⁹ F-NMR (DMSO, 376MHz): δ (ppm) = -61.2, -111.3, -117.4

Compound (B1-6): Combination of compound F and compound Bpre-d
¹ H-NMR (DMSO, 400MHz): δ (ppm) = 7.98-8.07 (m, ArH, 6H), 7.94 (t, ArH, 1H), 7.83 (t, ArH, 2H), 7.68-7.82 (m, ArH, 6H), 6.60-6.80 (m, ArH, 6H), 5.54 (s, CH, 1H), 3.52 (s, CH3, 6H), 2.42-2.47 (t, CF2CH2, 2H)
¹⁹ F-NMR (DMSO, 376MHz): δ (ppm) = -102.3, -103.9, -105.6

Compound (B1-7): Combination of compound G and compound Bpre-d
¹ H-NMR (DMSO, 400MHz): δ (ppm) = 7.74-7.90 (m, ArH, 14H), 7.68-7.82 (m, ArH, 6H), 6.60-6.80 (m, ArH, 6H), 5.54 ( s, CH, 1H), 3.51 (s, CH3, 3H), 2.42-2.47 (t, CF2CH2, 2H)
¹⁹ F-NMR (DMSO, 376MHz): δ (ppm) = -103.9, -105.6

Compound (B1-8): Combination of compound H and compound Bpre-d
¹ H-NMR (DMSO, 400MHz): δ (ppm) = 8.47 (d, ArH, 2H), 7.82-7.90 (m, ArH, 4H), 7.70-7.80 (m, ArH, 2H), 7.45-7.69 ( m, ArH, 10H), 6.60-6.80 (m, ArH, 6H), 5.54 (s, CH, 1H), 4.58 (d, CH2, 1H), 4.01 (d, CH2, 1H), 3.51 (s, CH3 , 3H), 2.42-2.47 (t, CF2CH2, 2H)
¹⁹ F-NMR (DMSO, 376MHz): δ (ppm) = -103.9, -105.6

Compound (B1-9): Combination of compound I and compound Bpre-d
¹ H-NMR (DMSO, 400MHz): δ (ppm) = 8.62 (d, ArH, 2H), 8.05 (d, ArH, 2H), 7.82-7.98 (m, ArH, 10H), 7.23-7.66 (m, ArH, 4H), 6.60-6.80 (m, ArH, 6H), 5.54 (s, CH, 1H), 3.51 (s, CH3, 3H), 2.42-2.47 (t, CF2CH2, 2H)
¹⁹ F-NMR (DMSO, 376MHz): δ (ppm) = -103.9, -105.6

Compound (B1-10): Combination of compound J and compound Bpre-e
¹ H-NMR (DMSO, 400MHz): δ (ppm) = 8.50 (d, ArH, 2H), 8.37 (d, ArH, 2H), 7.93 (t, ArH 2H), 7.55-7.75 (m, ArH 6H) , 7.01-7.47 (m, ArH, 8H), 4.62 (d, CH, 2H), 3.56 (t, NCH2, 2H), 3.51 (s, CH3, 3H), 3.14 (t, COCH, 2H), 2.63- 2.73 (m, CF2CH2, 2H)
¹⁹ F-NMR (DMSO, 376MHz): δ (ppm) = -111.3, -117.6

Compound (B1-11): Combination of compound F and compound Bpre-f
¹ H-NMR (DMSO, 400MHz): δ (ppm) = 7.98-8.07 (m, ArH, 6H), 7.94 (t, ArH, 1H), 7.83 (t, ArH, 2H), 7.01-7.47 (m, ArH, 8H), 5.08 (m, CFCH, 1H), 4.71 (s, CH, 1H), 4.42 (s, CH, 1H), 4.23 (m, CH2, 2H), 3.52 (s, CH3, 6H), 2.90 (m, CH, 1H), 2.45 (m, CFCH, 1H), 1.82-2.07 (m, CH2, CFCH, 3H)
¹⁹ F-NMR (DMSO, 376MHz): δ (ppm) = -102.3, -112.5, -121.2, -203.2

Compound (B1-12): Combination of compound F and compound Bpre-g
¹ H-NMR (DMSO, 400MHz): δ (ppm) = 7.98-8.07 (m, ArH, 6H), 7.94 (t, ArH, 1H), 7.83 (t, ArH, 2H), 7.01-7.45 (m, ArH, 8H), 4.71 (s, CH, 1H), 4.44 (S, CH, 1H), 4.31 (s, CH2, 2H), 3.52 (s, CH3, 6H), 2.93-3.00 (m, CH, 1H) ), 1.87-2.07 (m, CH2, 1H), 0.98-1.03 (m, CH, 1H)
¹⁹ F-NMR (DMSO, 376MHz): δ (ppm) = -102.3, -107.9

Compound (B1-13): Combination of compound F and compound Bpre-a
¹ H-NMR (DMSO, 400MHz): δ (ppm) = 7.98-8.07 (m, ArH, 6H), 7.94 (t, ArH, 1H), 7.83 (t, ArH, 2H), 7.01-7.47 (m, ArH, 8H), 4.72 (s, CH, 1H), 4.43 (s, CH, 1H), 4.23, (t, CH2, 2H), 3.52 (s, CH3, 6H), 2.95-3.02 (m, CH, 1H), 2.63-2.73, (m, CF2CH2, 2H), 1.86-2.07 (m, CH2, 2H)
¹⁹ F-NMR (DMSO, 376MHz): δ (ppm) = -102.3, -111.3, -117.4

Compound (D1-1): Combination of compound G and compound Bpre-h
¹ H-NMR (DMSO, 400MHz): δ (ppm) = 7.74-7.90 (m, 14H, ArH), 7.00-7.48 (m, ArH, 8H), 4.68 (s, CH, 1H), 4.41 (s, CH, 1H), 3.51 (s, CH3, 3H), 2.95-3.02 (m, CH, 1H), 1.85-2.04 (m, CH2, 2H)

Compound (D1-2): Combination of compound E and compound Bpre-h
¹ H-NMR (DMSO, 400MHz): δ (ppm) = 8.60-8.80 (m, ArH, 5H), 8.41 (d, ArH, 2H), 8.28 (d, ArH, 2H), 8.06 (t, ArH, 2H), 7.00-7.48 (m, ArH, 8H), 4.68 (s, CH, 1H), 4.41 (s, CH, 1H), 3.52 (s, CH3, 6H), 2.95-3.02 (m, CH, 1H) ), 1.85-2.04 (m, CH2, 2H)
¹⁹ F-NMR (DMSO, 376MHz): δ (ppm) = -61.2

<Preparation of resist composition>
(Examples 1 to 16, Comparative Examples 1 to 11)
Each component shown in Tables 1 and 2 was mixed and dissolved to prepare a resist composition of each example.

In Tables 1 and 2, each abbreviation has the following meaning. The value in [] is the blending amount (part by mass).
(A) -1: A polymer compound represented by the following chemical formula (A1) -1. The polymer compound (A) -1 was obtained by radical polymerization using a monomer for inducing a constituent unit constituting the polymer compound at a predetermined molar ratio. For this polymer compound (A) -1, the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 7000, and the molecular weight dispersion (Mw / Mn) is 1.72. ¹³ The copolymerization composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m / n = 30/60/10.

(A) -2: A polymer compound represented by the following chemical formula (A1) -2. The polymer compound (A) -2 was obtained by radical polymerization using a monomer for inducing a constituent unit constituting the polymer compound at a predetermined molar ratio. For this polymer compound (A) -2, the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 6800, and the molecular weight dispersion (Mw / Mn) was 1.65. ¹³ The copolymerization composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m / n = 30/60/10.

(A) -3: A polymer compound represented by the following chemical formula (A1) -3. The polymer compound (A) -3 was obtained by radical polymerization using a monomer for inducing a constituent unit constituting the polymer compound at a predetermined molar ratio. For this polymer compound (A) -3, the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 7100, and the molecular weight dispersion (Mw / Mn) is 1.69. ¹³ The copolymerization composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m = 50/50.

(A) -4: A polymer compound represented by the following chemical formula (A1) -4. The polymer compound (A) -4 was obtained by radical polymerization using a monomer for inducing a constituent unit constituting the polymer compound at a predetermined molar ratio. For this polymer compound (A) -4, the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 7200, and the molecular weight dispersion (Mw / Mn) is 1.71. ¹³ The copolymerization composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m = 50/50.

(B1) -1 to (B1) -13: Each acid generator comprising the above compounds (B1-1) to (B1-13).

(B2) -1: An acid generator composed of the following compound (B2-1).
(B2) -2: An acid generator composed of the following compound (B2-2).
(B2) -3: An acid generator composed of the following compound (B2-3).
(B2) -4: An acid generator composed of the following compound (B2-4).
(B2) -5: An acid generator comprising the following compound (B2-5).
(B2) -6: An acid generator composed of the following compound (B2-6).
(B2) -7: An acid generator comprising the following compound (B2-7).
(B2) -8: An acid generator comprising the following compound (B2-8).
(B2) -9: An acid generator comprising the following compound (B2-9).
(B2) -10: An acid generator comprising the following compound (B2-10).

(D1) -1 to (D1) -2: Each acid diffusion control agent composed of the above compounds (D1-1) to (D1-2).
(D2) -1: An acid diffusion control agent composed of a compound represented by the following chemical formula (D2-1).
(D2) -2: An acid diffusion control agent composed of a compound represented by the following chemical formula (D2-2).
(D2) -3: An acid diffusion control agent composed of a compound represented by the following chemical formula (D2-3).
(S) -1: Propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 60/40 (mass ratio) mixed solvent.

<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,). Drawing (exposure) was performed as "LS pattern"). Then, a post-exposure heating (PEB) treatment was performed at 100 ° 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.).
Then, 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 LS pattern of the target size is formed was determined by the resist pattern forming method. This is shown in Tables 3 to 4 as "Eop (μC / cm ² )".

[Defect evaluation]
Each of the resist compositions of each example was applied onto an 8-inch silicon substrate at 1500 rpm using a spinner, prebaked (PAB) at a temperature of 110 ° C. for 60 seconds on a hot plate, and dried. A resist film having a film thickness of 50 nm was formed.
With respect to the formed resist film, the total number of defects (total number of defects) in the wafer was measured using a surface defect observation device (manufactured by KLA Corporation, product name: Surfscan SP2).
In the evaluation of defects, when the number of defects in the resist film formed by using the resist composition of Comparative Example 1 is 1.0, the evaluation results are shown in Tables 3 to 4 as "Defect" according to the following evaluation criteria. rice field.
Evaluation criteria ○: 0.5 or less △: Over 0.5 to 1.0 or less ×: Over 1.0

[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 obtained. This is shown in Tables 3 to 4 as "LWR (nm)".
"3σ" is a standard deviation obtained from the measurement results of 400 line positions measured in the longitudinal direction of the line using a scanning electron microscope (acceleration voltage 800V, trade name: S-9380, manufactured by Hitachi High-Technologies). A triple value (3σ) of (σ) indicates “LWR” (unit: nm).
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.

[Evaluation of marginal resolution]
The minimum space width of the pattern to be resolved when the LS pattern is formed by gradually reducing the exposure amount from the limit resolution in the above Eop, specifically, the optimum exposure amount Eop, is determined by the scanning electron microscope S-. It was obtained using 9380 (manufactured by Hitachi High Technology). The results are shown in Tables 3 to 4 as "limit resolution (nm)".

From the results shown in Tables 3 to 4, according to the resist composition of the example to which the present invention was applied, high sensitivity was achieved in the formation of the resist pattern, roughness and defects were reduced, and resolution was improved. It can be confirmed that a resist pattern having a good shape can be formed.

Claims (11)

A resist composition that generates an acid upon exposure and whose solubility in a developing solution changes due to the action of the acid.
Substrate component (A) whose solubility in a developing solution changes due to the action of acid, and
A compound (BD1) composed of an anion portion and a cation portion represented by the following general formula (bd1),
A resist composition containing.

[In the formula, Rx ¹ to Rx ⁴ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, or even if two or more of them are bonded to each other to form a ring structure. good. Ry ¹ and Ry ² combine with each other to form an aromatic hydrocarbon ring .

Is a double bond or a single bond. Rz ¹ to Rz ⁴ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, if the valence allows, or two or more of them are bonded to each other to form a ring structure. You may be doing it. However, two or more of Rz ¹ to Rz ⁴ are bonded to each other to form an aromatic hydrocarbon ring. However, at least one of Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² , and Rz ¹ to Rz ⁴ has an anion group, and the entire anion portion becomes an n-valent anion. n is an integer of 1 or more. m is an integer of 1 or more, and M ^{m +} represents a cation represented by the following general formula (ca-0). ]

[In the formula, R ^b1 is an aryl group which may have a substituent. R ^b2 to R ^b3 are aryl groups which may independently have a substituent or an alkyl group which may have a substituent. R ^b2 to R ^b3 may be bonded to each other to form a ring together with the sulfur atom in the formula. However, at least one of R ^b1 to R ^b3 has a substituent containing a sulfonyl group. ] The resist composition according to claim 1, wherein at least one of Rx ¹ to Rx ² and at least one of Rx ³ to Rx ⁴ are bonded to each other to form a ring structure. The resist composition according to claim 1 or 2, wherein the anion portion in the compound (BD1) is an anion represented by the following general formula (bd1-an1).

[In the formula, Rx ⁵ to Rx ⁶ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent. Rx ⁷ to Rx ⁸ may independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, or may be bonded to each other to form a ring structure. p is 1 or 2, and when p = 2, a plurality of Rx ⁷ to Rx ⁸ may be different from each other. Ry ¹ and Ry ² combine with each other to form an aromatic hydrocarbon ring .

Is a double bond or a single bond. Rz ¹ to Rz ⁴ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, if the valence allows, or two or more of them are bonded to each other to form a ring structure. You may be doing it. However, two or more of Rz ¹ to Rz ⁴ are bonded to each other to form an aromatic hydrocarbon ring. However, at least one of Rx ¹ to Rx ⁴ , Ry ¹ to Ry ² and Rz ¹ to Rz ⁴ has an anion group, and the entire anion portion becomes an n-valent anion. n is an integer of 1 or more. ] The resist composition according to claim 3, wherein the anion portion in the compound (BD1) is an anion represented by the following general formula (bd1-an2).

[In the formula, Rx ⁵ to Rx ⁶ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent. Each of the plurality of Rx ⁷ to Rx ⁸ independently represents a hydrocarbon group or a hydrogen atom which may have a substituent, or two or more of them may be bonded to each other to form a ring structure. .. Ry ¹ and Ry ² combine with each other to form an aromatic hydrocarbon ring .

Is a double bond or a single bond. Rz ¹ to Rz ⁴ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, if the valence allows, or two or more of them are bonded to each other to form a ring structure. You may be doing it. However, two or more of Rz ¹ to Rz ⁴ are bonded to each other to form an aromatic hydrocarbon ring. However, at least one of Rx ⁵ to Rx ⁸ , Ry ¹ to Ry ² and Rz ¹ to Rz ⁴ has an anion group, and the entire anion portion becomes an n-valent anion. n is an integer of 1 or more. ] The resist composition according to claim 3 or 4 , wherein the Rx ⁷ to Rx ⁸ are bonded to each other to form a ring structure. The resist composition according to any one of claims 1 to 5 , wherein at least one of Rz ¹ to Rz ⁴ has an anionic group. The resist composition according to any one of claims 3 to 6 , wherein at least one of Rx ⁵ to Rx ⁶ has an anionic group. The sulfonyl group of the cation represented by the general formula (ca-0) is a divalent group in which one of the carbon atoms of the ring formed by the mutual bonding of R ^b2 to R ^b3 together with the sulfur atom in the formula is substituted. The resist composition according to any one of claims 1 to 7 , which is the sulfonyl group of the above. The sulfonyl group of the cation represented by the general formula (ca-0) is _−SO2 -R ^b4 (R ^b4 is a linear or branched alkyl group which may have a substituent, substituted. Any of claims 1 to 8 , which is a monovalent group represented by an alicyclic hydrocarbon group which may have a group or an aromatic hydrocarbon group which may have a substituent). The resist composition according to item 1. A step of forming a resist film using the resist composition according to any one of claims 1 to 9 on a support, a step of exposing the resist film, and a step of developing the exposed resist film. A resist pattern forming method comprising a step of forming a resist pattern. The resist pattern forming method according to claim 10 , wherein in the step of exposing the resist film, EUV (extreme ultraviolet) or EB (electron beam) is exposed to the resist film.