JP2010222339A - Positive resist composition, method for forming resist pattern and compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new compound useful for a resist composition, a positive resist composition containing the compound, and a method for forming a resist pattern by using the positive resist composition. <P>SOLUTION: The positive resist composition comprises: a substrate component (A) wherein solubility in an alkali developing solution is increased by action of an acid; and an acid generator component (B) that generates acid by exposure to light. The substrate component (A) comprises a compound (A1) represented by formula (A1-1) [wherein P is a group obtained by removing (n<SB>12</SB>+1) pieces of -OH from a polyhydric phenol compound having a molecular weight of 500-2,500; R<SP>1</SP>is an acid-dissociable dissolution inhibiting group; R<SP>2</SP>is a non-acid-dissociable group; and n<SB>12</SB>is an integer of 1-3]. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel compound useful for a resist composition, particularly a chemically amplified positive resist composition, a positive resist composition containing the compound, and a resist pattern forming method.

In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, pattern miniaturization has been rapidly progressing due to advances in lithography technology.
As a technique for miniaturization, the wavelength of an exposure light source is generally shortened. Specifically, conventionally, ultraviolet rays typified by g-line and i-line have been used, but now mass production of semiconductor elements using a KrF excimer laser or an ArF excimer laser has started. In addition, studies have been made on F ₂ excimer lasers, electron beams, EUV (extreme ultraviolet rays), X-rays, and the like having shorter wavelengths than these excimer lasers.
Along with the shortening of the wavelength of the exposure light source, the resist material is required to be improved in lithography characteristics such as sensitivity to the exposure light source and resolution capable of reproducing a pattern with a fine dimension.
As a resist material satisfying such requirements, a chemically amplified resist containing a base material component capable of forming a film and an acid generator component that generates an acid upon exposure and whose solubility in an alkali developer changes upon exposure. It has been known. The chemically amplified resist includes a negative type in which the solubility in an alkali developer is reduced by exposure, and a positive type in which the solubility in an alkali developer is increased by exposure.

Conventionally, a polymer is used as a base component of a chemically amplified resist. For example, in the case of a positive type, the solubility in an alkali developer is increased mainly by the action of an acid (acid generated from an acid generator). Resin is used (for example, refer to Patent Document 1). When selective exposure is performed on a resist film formed using a resist composition containing such a resin and an acid generator component, an acid is generated from the acid generator component in the exposed area, and the acid acts to The solubility of the resin in the alkali developer increases, and as a result, the exposed portion of the resist film becomes soluble in the alkali developer.
However, when a pattern is formed using such a chemically amplified resist, there is a problem that roughness is generated on the upper surface of the pattern or the surface of the side wall. For example, the roughness of the resist pattern side wall surface, that is, the line edge roughness (LER) causes distortion around the hole in the hole pattern and variation in the line width in the line and space pattern. Since there is a risk of adverse effects, improvements are required. However, the polymer generally used as the base material component has a large molecular size (average square radius per molecule) of around several nanometers. In the development process of pattern formation, the dissolution behavior of the resist with respect to the developing solution is usually performed in units of one molecular component of the base material. Therefore, as long as a polymer is used as the base material component, further reduction in roughness is extremely difficult.
In order to solve such a problem, a resist using a low molecular material as a base material component has been proposed as a material aiming at low roughness. For example, Non-Patent Documents 1 and 2 propose low molecular weight materials having an alkali-soluble group such as a hydroxyl group or a carboxy group, part or all of which are protected with an acid dissociable, dissolution inhibiting group. Patent Document 2 proposes a low molecular weight material in which the carboxy group of a phenol compound having a specific structure having a carboxy group is protected with an acid dissociable, dissolution inhibiting group.

JP 2003-241385 A JP 2008-19235 A

T.A. Hirayama, D .; Shiono, H .; Hada and J.H. Onodera: J.M. Photopolym. Sci. Technol. 17 (2004), p435 Jim-Baek Kim, Hyo-Jin Yun, Young-Gil Kwon: Chemistry Letters (2002), p1064-1065.

In recent years, with the progress of miniaturization of resist patterns and shortening of the wavelength of the exposure light source, the resist composition is required to further improve various lithography properties such as resolution and sensitivity. In particular, improvement of roughness has become an important issue along with improvement of resolution. For example, in lithography using an electron beam or EUV, since the target is to form a fine pattern of several tens of nanometers, extremely low roughness exceeding the current pattern roughness is required.
In this regard, it is expected that the resist composition using the low molecular weight material as a base material component as described above has a small molecular size of the base material component and can reduce roughness compared to the case of using a polymer. However, even if the low molecular weight material as described above is used as the base material component, there are limits to the reduction of roughness and the improvement of resolution.
Further, when a low molecular weight material is used as a base component of a resist composition, there is a problem that heat resistance is lower than when a polymer is used. For example, in the case of a chemically amplified resist, post-exposure baking is performed at the time of forming a resist pattern, and thus heat resistance applicable to this is required.
The present invention has been made in view of the above circumstances, and is a novel compound useful as a resist composition, a positive resist composition containing the compound, and a resist pattern using the positive resist composition It is an object to provide a forming method.

As a result of intensive studies to solve the above problems, the inventors of the present invention protected only one of a plurality of —OH with an acid dissociable, dissolution inhibiting group in the specific phenol compound, and the remaining —OH. Of these, the present inventors have found that the above problems can be solved by a compound in which 1 to 3 of them are protected with an acid non-dissociable group, thereby completing the present invention.
That is, the first aspect of the present invention is a positive resist containing a base component (A) whose solubility in an alkaline developer is increased by the action of an acid and an acid generator component (B) which generates an acid upon exposure. A composition comprising:
The base material component (A) contains a compound (A1) represented by the following general formula (A1-1), which is a positive resist composition.

［式中、Ｐは、分子量５００〜２５００の多価フェノール化合物から（ｎ_１２＋１）個の−ＯＨを除いた基であり、Ｒ^１は酸解離性溶解抑制基であり、Ｒ^２は酸非解離性基であり、ｎ_１２は１〜３の整数である。］

[Wherein, P is a group obtained by removing (n ₁₂ +1) -OH from a polyhydric phenol compound having a molecular weight of 500 to 2500, R ¹ is an acid dissociable, dissolution inhibiting group, and R ² is an acid non-acid group. a dissociative _{group, n 12} is an integer of 1-3. ]

According to a second aspect of the present invention, there is provided a step of forming a resist film on a support using the positive resist composition of the first aspect, a step of exposing the resist film, and an alkali development of the resist film. And a resist pattern forming method including a step of forming a resist pattern.
A third aspect of the present invention is a compound represented by the following general formula (A1-1).

［式中、Ｐは、分子量５００〜２５００の多価フェノール化合物から（ｎ_１２＋１）個の−ＯＨを除いた基であり、Ｒ^１は酸解離性溶解抑制基であり、Ｒ^２は酸非解離性基であり、ｎ_１２は１〜３の整数である。］

[Wherein, P is a group obtained by removing (n ₁₂ +1) -OH from a polyhydric phenol compound having a molecular weight of 500 to 2500, R ¹ is an acid dissociable, dissolution inhibiting group, and R ² is an acid non-acid group. a dissociative _{group, n 12} is an integer of 1-3. ]

In the present specification and claims, “aliphatic” is a relative concept with respect to aromatics, and is defined to mean groups, compounds, etc. that do not have aromaticity.
Unless otherwise specified, the “alkyl group” includes linear, branched and cyclic monovalent saturated hydrocarbon groups.
Unless otherwise specified, the “alkylene group” includes linear, branched and cyclic divalent saturated hydrocarbon groups.
The “halogenated alkyl group” is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms, and the “halogenated alkylene group” is the part of or all of the hydrogen atoms in the alkylene group is a halogen atom. The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
“Exposure” is a concept including general irradiation of radiation.

  According to the present invention, it is possible to provide a novel compound useful for a positive resist composition, a positive resist composition containing the compound, and a resist pattern forming method using the positive resist composition.

≪Positive resist composition≫
The positive resist composition of the present invention comprises a base component (A) (hereinafter referred to as component (A)) whose solubility in an alkaline developer is increased by the action of an acid, and an acid generator that generates an acid upon exposure. Contains component (B) (hereinafter referred to as component (B)).
In the positive resist composition, when an acid is generated from the component (B) by exposure, the solubility of the component (A) in an alkaline developer is increased by the action of the acid. Therefore, when a resist film made of the positive resist composition is selectively exposed in the formation of a resist pattern, or when post-exposure heating is performed in addition to exposure, the exposed portion increases in solubility in an alkaline developer while remaining unexposed. Since the exposed portion does not change the solubility in an alkali developer, a positive resist pattern is formed by alkali development.

<(A) component>
“Substrate component” means an organic compound having film-forming ability.
As the component (A), an organic compound having a molecular weight of 500 or more is usually used. When the molecular weight is 500 or more, it has a sufficient film forming ability and can easily form a nano-level resist pattern.
“Organic compounds having a molecular weight of 500 or more” are roughly classified into non-polymers and polymers.
As the non-polymer, those having a molecular weight of 500 or more and less than 4000 are usually used. Hereinafter, the term “low molecular compound” refers to a non-polymer having a molecular weight of 500 or more and less than 4000.
As the polymer, those having a molecular weight of 2000 or more are usually used. Hereinafter, the term “resin” refers to a polymer having a molecular weight of 2000 or more. In the case of a resin, a polystyrene-reduced mass average molecular weight by GPC (gel permeation chromatography) is used as the “molecular weight”.

[Compound (A1)]
The positive resist composition of the present invention contains a compound (A1) represented by the following general formula (A1-1) (hereinafter referred to as “component (A1)”) as the component (A).
In short, the component (A1) is a polyhydric phenol compound having a molecular weight of 500 to 2500 (corresponding to a compound in which R ¹ and R ² in the formula (A1-1) are both hydrogen atoms). One —OH is substituted with —OR ¹ , and 1 to 3 —OH is substituted with —OR ² .

［式中、Ｐは、分子量５００〜２５００の多価フェノール化合物から（ｎ_１２＋１）個の−ＯＨを除いた基であり、Ｒ^１は酸解離性溶解抑制基であり、Ｒ^２は酸非解離性基であり、ｎ_１２は１〜３の整数である。］

[Wherein, P is a group obtained by removing (n ₁₂ +1) -OH from a polyhydric phenol compound having a molecular weight of 500 to 2500, R ¹ is an acid dissociable, dissolution inhibiting group, and R ² is an acid non-acid group. a dissociative _{group, n 12} is an integer of 1-3. ]

In formula (A1-1), R ¹ is an acid dissociable, dissolution inhibiting group.
The “acid dissociable, dissolution inhibiting group” has an acid dissociation property that is dissociated by the action of an acid generated from the component (B), and suppresses the solubility of the component (A1) in the alkaline developer before the dissociation. It is a group having an alkali dissolution inhibiting property that is hardly soluble in an alkali developer. Therefore, in a positive resist composition in which the component (A1) is blended with the component (B), when acid is generated from the component (B) by exposure, R ¹ is dissociated by the action of the acid, and the component (A1) Changes from poorly soluble to soluble in an alkaline developer.
The acid dissociable, dissolution inhibiting group is not particularly limited, and among those conventionally proposed for hydroxystyrene-based resins, (meth) acrylate-based resins and the like used in chemically amplified resist compositions for KrF and ArF. It can be appropriately selected and used.
As the acid dissociable, dissolution inhibiting group, a group that forms a cyclic or chain tertiary alkyl ester with a carboxy group of (meth) acrylic acid; an acetal type acid dissociable, dissolution inhibiting group such as an alkoxyalkyl group is widely known. It has been. “(Meth) acrylate” means one or both of an acrylate having a hydrogen atom bonded to the α-position and a methacrylate having a methyl group bonded to the α-position. “(Meth) acrylic acid ester” means one or both of an acrylic acid ester having a hydrogen atom bonded to the α-position and a methacrylic acid ester having a methyl group bonded to the α-position.
Here, the “tertiary alkyl ester” is an ester formed by replacing a hydrogen atom of a carboxy group with a chain or cyclic alkyl group, and the carbonyloxy group (—C (O)). A structure in which the tertiary carbon atom of the chain or cyclic alkyl group is bonded to the terminal oxygen atom of -O-). In this tertiary alkyl ester, when an acid acts, a bond is cut between an oxygen atom and a tertiary carbon atom.
The chain or cyclic alkyl group may have a substituent.
Hereinafter, a group that is acid dissociable by constituting a carboxy group and a tertiary alkyl ester is referred to as a “tertiary alkyl ester type acid dissociable, dissolution inhibiting group” for convenience.

Examples of the tertiary alkyl ester type acid dissociable, dissolution inhibiting group include aliphatic branched acid dissociable, dissolution inhibiting groups and tertiary alkyl ester type acid dissociable, dissolution inhibiting groups containing an aliphatic cyclic group. .
“Aliphatic branched” means having a branched structure having no aromaticity.
The structure of the “aliphatic branched acid dissociable, dissolution inhibiting group” is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but is preferably a hydrocarbon group. The hydrocarbon group may be either saturated or unsaturated, but is usually preferably saturated.
Examples of the aliphatic branched acid dissociable, dissolution inhibiting group include a group represented by -C (R ⁷¹ ) (R ⁷² ) (R ⁷³ ). ^Wherein, R 71 ^{to R 73} each independently represents a linear alkyl group of 1 to 5 carbon atoms. The group represented by —C (R ⁷¹ ) (R ⁷² ) (R ⁷³ ) preferably has 4 to 8 carbon atoms, and specifically includes a tert-butyl group, a tert-pentyl group, and a tert-heptyl group. Groups and the like.

The “aliphatic cyclic group” means a monocyclic group or a polycyclic group having no aromaticity.
The aliphatic cyclic group may or may not have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).
The basic ring structure of the aliphatic cyclic group excluding a substituent is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but is preferably a hydrocarbon group. The “hydrocarbon group” may be either saturated or unsaturated, but is usually preferably saturated.
The aliphatic cyclic group is preferably a polycyclic group.
Examples of the aliphatic cyclic group include polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes that may be substituted with the above-described substituents or may be unsubstituted. Examples thereof include groups in which one or more hydrogen atoms have been removed. More specifically, a monocycloalkane such as cyclopentane or cyclohexane, or a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, dicyclodecane, tricyclodecane, or tetracyclododecane. Can be mentioned.
Examples of the tertiary alkyl ester-type acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group include (i) carbon bonded to an adjacent oxygen atom on the ring skeleton of a monovalent aliphatic cyclic group. A group in which an alkyl group is bonded to the atom to form a tertiary carbon atom; (ii) a monovalent aliphatic cyclic group and a branched alkylene having a tertiary carbon atom bonded thereto Groups and the like.
(I) Specific examples of the group in which an alkyl group is bonded to a carbon atom bonded to an adjacent oxygen atom on the ring skeleton of a monovalent aliphatic cyclic group to form a tertiary carbon atom include And groups represented by the following general formulas (21-1) to (21-9).
(Ii) Specific examples of the group having an aliphatic cyclic group and a branched alkylene having a tertiary carbon atom bonded thereto include, for example, the following general formulas (22-1) to (22-6) ) And the like.

［式中、Ｒ^１４はアルキル基であり、ｇは０〜８の整数である。］

^{Wherein, R 14} represents an alkyl group, g is an integer of 0-8. ]

［式中、Ｒ^１５およびＲ^１６は、それぞれ独立にアルキル基である。］

[Wherein, R ¹⁵ and R ¹⁶ each independently represents an alkyl group. ]

The alkyl group for R ^{14 to} R ¹⁶ may be linear, branched or cyclic, and is preferably a linear or branched alkyl group. In particular, an alkyl group having 1 to 5 carbon atoms is preferable, and specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group. Groups 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.
g is preferably an integer of 0 to 3, more preferably an integer of 1 to 3, and still more preferably 1 or 2.

The “acetal-type acid dissociable, dissolution inhibiting group” is generally bonded to an oxygen atom by substituting a hydrogen atom at the terminal of an alkali-soluble group such as a carboxy group or a hydroxyl group. When an acid is generated by exposure, the acid acts to break the bond between the acetal acid dissociable, dissolution inhibiting group and the oxygen atom to which the acetal acid dissociable, dissolution inhibiting group is bonded.
Examples of the acetal type acid dissociable, dissolution inhibiting group include a group represented by the following general formula (p1).

［式中、Ｒ^１’，Ｒ^２’はそれぞれ独立して水素原子または炭素数１〜５のアルキル基を表し、ｎは０〜３の整数を表し、Ｙは直鎖状、分岐状または環状のアルキル基であって、その構造中にヘテロ原子を含んでもよい。］

[Wherein, R ¹ ′ and R ² ′ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n represents an integer of 0 to 3, and Y represents a linear, branched or cyclic group. And the structure may contain a heteroatom. ]

In the above formula, n is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 0.
Examples of the alkyl group having 1 to 5 carbon atoms of R ¹ ′ and R ² ′ include the same alkyl groups as those described above for R ^{14 to} R ^16. A methyl group or an ethyl group is preferable, and a methyl group is most preferable.
In the present invention, it is preferable that at least one of R ¹ ′ and R ² ′ is a hydrogen atom. That is, the group represented by the formula (p1) is preferably a group represented by the following general formula (p1-1).

［式中、Ｒ^１’、ｎ、Ｙは上記と同様である。］

[Wherein R ¹ ′, n and Y are the same as described above. ]

The alkyl group of Y may contain a hetero atom in the structure. That is, in the alkyl group as Y, part or all of the hydrogen atoms may be substituted with a group containing a hetero atom (including the case of the hetero atom itself), and a part of the carbon atom of the alkyl group is hetero. It may be substituted with an atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom, and a fluorine atom.
The group containing a hetero atom may be a hetero atom itself, or may be a group composed of a hetero atom and a carbon atom and / or a hydrogen atom, such as an alkoxy group.
Examples of the alkyl group in which part or all of the hydrogen atoms are substituted with a group containing a hetero atom include, for example, a fluorinated alkyl group having 1 to 5 carbon atoms in which part or all of the hydrogen atoms are substituted with fluorine atoms A group in which two hydrogen atoms bonded to the same carbon atom are replaced by one oxygen atom (that is, a group having a carbonyl group (C═O)), two hydrogen atoms bonded to the same carbon atom are And a group substituted with a sulfur atom (that is, a group having a thiocarbonyl group (C = S)).
Examples of the group in which part of the carbon atoms of the alkyl group is substituted with a group containing a hetero atom include, for example, an example in which the carbon atom is substituted with a nitrogen atom (for example, a branch containing —CH ₂ — in the structure thereof) A group in which —CH ₂ — is substituted with —NH— in a chain-like or cyclic alkyl group, or examples in which a carbon atom is substituted with an oxygen atom (for example, a branched structure containing —CH ₂ — in its structure) Or a group in which the —CH ₂ — is substituted with —O— in a cyclic alkyl group).

The linear alkyl group as Y preferably has 1 to 5 carbon atoms, and specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. , Preferably a methyl group or an ethyl group.
The branched alkyl group as Y preferably has 4 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms. Specific examples include an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, and a tert-pentyl group, and a tert-butyl group is preferable.
When Y is a linear or branched alkyl group, specific examples of the group represented by the formula (p1) include, for example, a 1-ethoxyethyl group, a 1-ethoxymethyl group, and a 1-methoxyethyl group. 1-methoxymethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-n-butoxyethyl group, 1-pentafluoroethoxyethyl group, 1-trifluoromethoxyethyl group, 1-trifluoromethoxymethyl group Etc.

The cyclic alkyl group as Y preferably has 3 to 20 carbon atoms, more preferably 4 to 14 carbon atoms, and most preferably 5 to 12 carbon atoms.
The structure of the basic ring (basic ring excluding the substituent) in the cyclic alkyl group may be monocyclic or polycyclic, and is particularly preferably polycyclic because it is excellent in the effects of the present invention. The basic ring may be a hydrocarbon ring composed of carbon and hydrogen, or may be a heterocycle in which a part of carbon atoms constituting the hydrocarbon ring is substituted with a heteroatom. In the present invention, the basic ring is particularly preferably a hydrocarbon ring. Specific examples of the hydrocarbon ring include monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane. Specific examples include monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among these, adamantane, norbornane, tricyclodecane, and tetracyclododecane are preferable, and adamantane is particularly preferable.
These basic rings may or may not have a substituent on the ring. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms, and an oxygen atom (= O). As this alkyl group, C1-C5 linear or branched alkyl groups, such as a methyl group and an ethyl group, are mentioned. When the basic ring has a substituent, the number of substituents is preferably 1 to 3, and more preferably 1. Here, “having a substituent on the ring” means that a hydrogen atom bonded to a carbon atom constituting the basic ring is substituted with a substituent.
Examples of the cyclic alkyl group for Y include groups in which one hydrogen atom has been removed from these basic rings.
When Y is a cyclic alkyl group, specific examples of the group represented by the formula (p1) include groups represented by the following formulas (p1-1) to (p1-20).

［式中、Ｒ^１’ は前記と同じである。］

[Wherein R ¹ ′ is the same as defined above. ]

  Among the above, a group represented by the following general formula (p1-21) including formulas (p1-13), (p1-14), (p1-19) and (p1-20), or a formula (p1 The group represented by the following formula (p1-22) including -15) and (p1-16) is preferable.

［式中、Ｒ^１’は前記と同じであり、ｎ”およびｍ”はそれぞれ独立に０〜２の整数であり、Ｗは２原子の水素原子または酸素原子である。］

[Wherein, R ¹ ′ is the same as defined above, n ″ and m ″ are each independently an integer of 0 to 2, and W is a hydrogen atom or an oxygen atom of 2 atoms. ]

Most preferably, n ″ and m ″ are 0 or 1.
^{_{-CHR 1 '-O- (CH 2)}} n " in the adamantyl group - the binding position of are not particularly limited, 1-position or 2-position of the adamantyl group.

  Examples of the acetal type acid dissociable, dissolution inhibiting group also include a group represented by the following general formula (p2).

［式中、Ｒ^１７、Ｒ^１８はそれぞれ独立して直鎖状または分岐鎖状のアルキル基または水素原子であり、Ｒ^１９は直鎖状、分岐鎖状または環状のアルキル基である。または、Ｒ^１７およびＲ^１９がそれぞれ独立に直鎖状または分岐鎖状のアルキレン基であって、Ｒ^１７の末端とＲ^１９の末端とが結合して環を形成していてもよい。］

[Wherein, R ¹⁷ and R ¹⁸ each independently represent a linear or branched alkyl group or a hydrogen atom, and R ¹⁹ represents a linear, branched or cyclic alkyl group. Alternatively, R ¹⁷ and R ¹⁹ may be each independently a linear or branched alkylene group, and the end of R ^{17 and} the end of R ¹⁹ may be bonded to form a ring. ]

In R ¹⁷ and R ¹⁸ , the alkyl group preferably has 1 to 15 carbon atoms, may be linear or branched, and is preferably an ethyl group or a methyl group, and most preferably a methyl group. In particular, it is preferable that one of R ¹⁷ and R ¹⁸ is a hydrogen atom and the other is a methyl group.
R ¹⁹ is a linear, branched or cyclic alkyl group, preferably having 1 to 15 carbon atoms, and may be any of linear, branched or cyclic.
When R ¹⁹ is linear or branched, it preferably has 1 to 5 carbon atoms, more preferably an ethyl group or a methyl group, and most preferably an ethyl group.
When R ¹⁹ is cyclic, it preferably has 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, one or more polycycloalkanes such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group, are included. Examples include a group excluding a hydrogen atom. Specific examples include monocycloalkanes such as cyclopentane and cyclohexane, and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among them, a group obtained by removing one or more hydrogen atoms from adamantane is preferable.
In the above formula, R ¹⁷ and R ¹⁹ are each independently a linear or branched alkylene group (preferably an alkylene group having 1 to 5 carbon atoms), and the end of R ^{19 and} the end of R ¹⁷ And may be combined.
In this case, the R ^17, R ^19, the oxygen atom to which R ¹⁹ is bonded, the cyclic group is formed by the carbon atom having the oxygen atom and R ¹⁷ are bonded. The cyclic group is preferably a 4-7 membered ring, and more preferably a 4-6 membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.

In the present invention, R ¹ is represented by the formulas (21-1) to (21-9), (22-1) to (21-6), and (p1-1) to (p1-22) described above. It is preferable that it is an acid dissociable, dissolution inhibiting group having a cyclic group, such as a group having excellent effects of the present invention. When R ¹ is an acid dissociable, dissolution inhibiting group having a cyclic group, the alkali dissolution inhibiting property is higher than that in a chain form, so that the solubility of the component (A1) in an alkaline developer is lowered. Therefore, when the component (A1) is added to the positive resist composition, the resistance of the resist film formed using the positive resist composition to the alkali developer in the unexposed portion is increased, and as a result, exposure is performed. The difference in solubility (dissolution contrast) between the part and the unexposed part in the alkaline developer is increased, and the resolution is improved.
R ¹ is particularly preferably a tertiary alkyl ester-type acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group, and has a tertiary carbon atom on the ring skeleton of the monovalent aliphatic cyclic group. The group is more preferable, the group represented by any one of the formulas (22-1) to (22-6) is more preferable, and the group represented by the formula (22-1) is most preferable.

In Formula (A1-1), R ² is an acid non-dissociable group, and n ₁₂ is an integer of 1 to 3. That is, the component (A1) has 1 to 3 R ² in its structure. Thereby, effects such as control of the dissolution rate in the developer and control of heat resistance in the overheating step after exposure, etc. are obtained.
Here, the “acid non-dissociable group” means a group having no acid dissociability that is dissociated by the action of an acid generated from the component (B). In the component (A1), when an acid is generated from the component (B), the structure of —O—R ² does not change even if the acid acts.
R ² is, for example, a primary alkyl group; a secondary alkyl group; a cyclic tertiary alkyl group, and a substituent is not bonded to a tertiary carbon atom bonded to an adjacent oxygen atom. A tertiary alkyl group; an aryl group; an arylalkyl group; a halogenated alkyl group; a halogenated aryl group; a halogenated arylalkyl group;
Examples of the primary alkyl group include —CH ₂ —R ¹¹ (R ¹¹ is a hydrogen atom or an alkyl group).
Alkyl group R ¹¹ may be any of primary to tertiary, also linear, branched, or cyclic, or a combination thereof. Examples of the combination, for example, ^{-R 11 '-R 11 "(wherein, R 11'} is a straight or branched alkylene ^{group, R 11"} is a cyclic alkyl group.) Include It is done. Examples of the cyclic alkyl group for R ¹¹ ″ include those similar to the cyclic secondary alkyl group and cyclic tertiary alkyl group described later.
The total number of carbon atoms in the alkyl group of R ¹¹ is 1 to 20 is preferred.
As the secondary alkyl group, —CH (R ¹² ) —R ¹³ (R ¹² and R ¹³ are each independently an alkyl group, and R ¹² and R ¹³ are bonded to each other to form a ring. May be included).
Examples of the alkyl group for R ¹² and R ¹³ include the same alkyl groups as those described above for R ¹¹ .
R ¹² and R ¹³ may be bonded to each other to form a ring. In this case, —CH (R ¹² ) —R ¹³ is a cyclic secondary alkyl group. Examples of the cyclic secondary alkyl group include groups in which one hydrogen atom has been removed from one secondary carbon atom on the ring skeleton of a monocycloalkane such as cyclopentane or cyclohexane; bicycloalkane, tricycloalkane, And a group obtained by removing one hydrogen atom from one of secondary carbon atoms on the ring skeleton of polycycloalkane such as tetracycloalkane. More specifically, examples of the polycycloalkane include adamantane, norbornane, isobornane, dicyclodecane, tricyclodecane, and tetracyclododecane.
As the cyclic tertiary alkyl group, for example, among the polycycloalkanes mentioned as the ring which R ¹² and R ¹³ may be bonded to each other, a tertiary carbon atom is a ring skeleton. And a group obtained by removing one hydrogen atom from the tertiary carbon atom of the polycycloalkane.
In the cyclic secondary alkyl group or tertiary alkyl group, a substituent may be bonded to a carbon atom other than the carbon atom bonded to the adjacent oxygen atom. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).
Although it does not specifically limit as said aryl group, For example, a C6-C20 aryl group is mentioned. The aryl group preferably has 6 to 15 carbon atoms, and specifically includes a phenyl group, a tolyl group, a xylyl group, a mesityl group, a phenethyl group, a naphthyl group, and the like. Of these, a phenyl group and a naphthyl group are preferable. A substituent may be bonded to the aryl group. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).
Examples of the arylalkyl group, e.g., ^{-R 11} '-A ^{L (wherein, R 11'} is a straight or branched alkylene group, ^{A L} is an aryl group.) Are exemplified. ^{Wherein, R 11} 'is as defined above. The A ^L, are the same as those of the above aryl group.
Examples of the halogen atom in the halogenated alkyl group, halogenated aryl group or halogenated arylalkyl group include a fluorine atom, a bromine atom and a chlorine atom, and a fluorine atom is particularly preferable. The alkyl group, aryl group, and arylalkyl group in the halogenated alkyl group, halogenated aryl group, and halogenated arylalkyl group are respectively the primary to tertiary alkyl group, aryl group, and arylalkyl group described above. The same thing is mentioned.

Among the above, R ² preferably includes a cyclic group in its structure. Among these, a primary alkyl group, a cyclic secondary alkyl group, a cyclic tertiary alkyl group or an arylalkyl group in which R ¹¹ is a cyclic alkyl group or —R ¹¹ ′ -R ¹¹ ″ is preferable.
Among these, those containing a polycyclic group as a cyclic group are preferable, and particularly those containing at least one selected from a tricyclodecanyl group, an adamantyl group, a tetracyclododecanyl group, an isobornyl group, and a norbornyl group. In terms of industrial availability, it is preferable.
As R ² , those represented by the following formulas (41) to (46) are particularly preferable. In these groups, among the carbon atoms constituting the ring in the formula, the adjacent R ¹⁰ (the oxygen atom to which R ² is bonded when R ¹⁰ is a single bond) or the tertiary bonded to R ¹⁰ ″ A linear or branched alkyl group having 1 to 5 carbon atoms may be bonded to a carbon atom other than carbon atoms.
In formulas (41) to (45), R ¹⁰ is preferably a single bond or a methylene group. In formula (46), R ¹⁰ ″ is preferably a methylene group.

［式中、Ｒ^１０は単結合または炭素数１〜１０の直鎖状のアルキレン基であり、Ｒ^１０”は炭素数１〜１０の直鎖状のアルキレン基である。］

[Wherein, R ¹⁰ represents a single bond or a linear alkylene group having 1 to 10 carbon atoms, and R ¹⁰ ″ represents a linear alkylene group having 1 to 10 carbon atoms.]

In formula (A1-1), P represents a polyhydric phenol compound having a molecular weight of 500 to 2500 (hereinafter, the polyhydric phenol compound may be referred to as “unprotected body”) to (n ₁₂ +1) —OH. Is a group excluding.
When the molecular weight of the unprotected body is 500 or more, the film-forming ability is improved and a nano-level resist pattern is easily formed. The molecular weight is preferably 700 or more, and more preferably 1000 or more. Further, when the molecular weight is 2500 or less, the resolution is improved, the roughness is reduced, and a resist pattern having a good shape can be formed. The molecular weight is preferably 2200 or less, and more preferably 2000 or less.
The molecular weight of the unprotected body is, for example, the structure of the unprotected body by ¹ H-nuclear magnetic resonance (NMR) spectrum method, ¹³ C-NMR spectrum method, ¹⁹ F-NMR spectrum method, infrared absorption (IR) spectrum method, It can be confirmed by a general organic analysis method such as mass spectrometry (MS) method, elemental analysis method, X-ray crystal diffraction method, and can be calculated from the structure.
Here, in the present specification and claims, “polyhydric phenol compound” means a compound having two or more phenolic hydroxyl groups. “Phenolic hydroxyl group” means a hydroxyl group directly bonded to an aromatic ring such as a benzene ring or a naphthalene ring. That is, the “polyhydric phenol compound” has an aromatic ring to which a hydroxyl group is bonded. The polyhydric phenol compound may have an aromatic ring to which a hydroxyl group is not bonded. As an aromatic ring which a polyhydric phenol compound has, a benzene ring is particularly preferable.

The number of phenolic hydroxyl groups in the unprotected body is preferably 2 or more, and the number of all —OH in the unprotected body is (n ₁₂ +1) or more. “Number of total —OH” indicates the total number of phenolic hydroxyl groups and hydroxyl groups other than phenolic hydroxyl groups (for example, carboxylic acid hydroxyl groups described later), and the unprotected body represents hydroxyl groups other than phenolic hydroxyl groups. If not, the number of phenolic hydroxyl groups alone is the “total number of —OH”. The upper limit of “the total number of —OH” varies depending on the skeleton of the unprotected body and is not particularly limited.

The unprotected body may have a hydroxyl group other than the phenolic hydroxyl group. That is, it may have a hydroxyl group that is not directly bonded to the aromatic ring.
As the hydroxyl group other than the phenolic hydroxyl group, a hydroxyl group bonded to a carbonyl group (that is, —OH in a carboxy group (—COOH), hereinafter referred to as a carboxylic acid hydroxyl group) is preferable. That is, the unprotected body preferably has a carboxy group.

When the unprotected body has a carboxy group, the carboxy group may be directly bonded to the aromatic ring of the unprotected body or may be bonded via a linking group.
Examples of the linking group (linking group for linking an aromatic ring and a carboxy group) include, for example, a hydrocarbon group which may have a substituent and a group containing a hetero atom (hereinafter referred to as a hetero atom-containing linking group). ) And the like.
The hydrocarbon group in the “optionally substituted hydrocarbon group” may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

The aliphatic hydrocarbon group in the “hydrocarbon group optionally having substituent (s)” may be saturated or unsaturated, and is usually preferably saturated.
More specifically, examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.
The “linear or branched aliphatic hydrocarbon group” preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and 1 to 5 carbon atoms. Is particularly preferred and 1 or 2 is most preferred.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group [—CH ₂ —], an ethylene group [— (CH ₂ ) ₂ —], a trimethylene group [ — (CH ₂ ) ₃ —], tetramethylene group [— (CH ₂ ) ₄ —], pentamethylene group [— (CH ₂ ) ₅ —] and the like can be mentioned.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - Alkylethylene groups such as CH (CH ₃ ) CH ₂ —, —CH (CH ₃ ) CH (CH ₃ ) —, —C (CH ₃ ) ₂ CH ₂ —, —CH (CH ₂ CH ₃ ) CH ₂ —; Alkyl trimethylene groups such as —CH (CH ₃ ) CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) CH ₂ —; —CH (CH ₃ ) CH ₂ CH ₂ CH ₂ —, —CH ₂ CH (CH _{3) CH} 2 CH ₂ - alkyl, such as alkyl tetramethylene group such as Such as an alkylene group, and the like. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
In the linear or branched aliphatic hydrocarbon group, part or all of the hydrogen atoms in the hydrocarbon group may be substituted with groups or atoms other than hydrogen atoms. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).
Examples of the “aliphatic hydrocarbon group containing a ring” include a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and the cyclic aliphatic hydrocarbon group described above. And a group that is bonded to the terminal of the chain-like aliphatic hydrocarbon group or intervenes in the middle of the chain-like aliphatic hydrocarbon group.
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 group, a group in which two hydrogen atoms have been removed from a monocycloalkane having 3 to 6 carbon atoms is preferable, and examples of the monocycloalkane include cyclopentane and cyclohexane. As the polycyclic group, a group in which two hydrogen atoms are removed from a polycycloalkane having 7 to 12 carbon atoms is preferable. Specific examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, tetra And cyclododecane.
The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).

Examples of the aromatic hydrocarbon group in the “hydrocarbon group which may have a substituent” include groups obtained by removing two hydrogen atoms from a hydrocarbon containing an aromatic hydrocarbon ring in the structure thereof. . Specifically, a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon ring (arylene group), and the arylene group is bonded to the terminal of the linear or branched aliphatic hydrocarbon group described above. And groups in which the arylene group is interposed in the middle of the above-described linear or branched aliphatic hydrocarbon group.
Examples of the aromatic hydrocarbon ring include a benzene ring, a biphenyl ring, a fluorene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring.
In the aromatic hydrocarbon ring, a part of carbon atoms constituting the ring may be substituted with a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom.
In the aromatic hydrocarbon ring, part or all of the hydrogen atoms may be substituted with a substituent (a group or atom other than a hydrogen atom).

Examples of the substituent for part or all of the hydrogen atoms of the aromatic hydrocarbon ring include a hydroxyl group, an alkyl group, an aryl group, an alkoxy group and an aryloxy group, a halogen atom, a halogenated alkyl group, and an oxygen atom (═O ) And the like.
The alkyl group as the substituent is not particularly limited, and may be linear, branched or cyclic.
The linear alkyl group preferably has 1 to 5 carbon atoms, and specifically includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Or it is preferable that it is an ethyl group.
The branched alkyl group preferably has 4 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms. Specific examples include an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, and a tert-pentyl group. The cyclic alkyl group preferably has 3 to 20 carbon atoms, more preferably 4 to 14 carbon atoms, and particularly preferably 5 to 12 carbon atoms.
The structure of the basic ring (basic ring excluding a substituent) in the cyclic alkyl group may be monocyclic or polycyclic. The basic ring may be a hydrocarbon ring composed of carbon and hydrogen, or may be a heterocycle in which a part of carbon atoms constituting the hydrocarbon ring is substituted with a heteroatom as described later. Good. Specific examples of the hydrocarbon ring include monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane. Specific examples include monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. These basic rings may or may not have a substituent composed of a hydrocarbon group on the ring. Examples of the hydrocarbon group include linear or branched alkyl groups having 1 to 5 carbon atoms such as a methyl group and an ethyl group. When the basic ring has a substituent, the number of substituents is preferably 1 to 3, and more preferably 1. Here, “having a substituent” is as described in the description of R1.

The aryl group as the substituent is not particularly limited, but preferably has 6 to 15 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a phenethyl group, and a naphthyl group. . Of these, a phenyl group is more preferable.
Examples of the alkoxy group as the substituent include a group in which an oxygen atom (—O—) is bonded to the alkyl group.
Examples of the aryloxy group as the substituent include a group in which an oxygen atom (—O—) is bonded to the aryl group.

The alkyl group, aryl group, alkoxy group and aryloxy group as the substituent may each contain a substituent other than a hydrocarbon group or a hetero atom in the structure. For example, some or all of hydrogen atoms in an alkyl group, aryl group, alkoxy group and aryloxy group may be substituted with a group containing a hetero atom (including a hetero atom itself). A part of carbon atoms in the group, alkoxy group and aryloxy group may be substituted with a hetero atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom, and a fluorine atom.
Examples of those in which part or all of the hydrogen atoms are substituted with a group containing a hetero atom include, for example, hydroxyl groups, alkoxy groups, and fluorinations having 1 to 5 carbon atoms in which part or all of the hydrogen atoms are substituted with fluorine atoms. Examples thereof include those substituted with a group consisting of a hetero atom and a carbon atom and / or a hydrogen atom, such as an alkyl group.
Examples of the hydrogen atom in which part or all of the hydrogen atoms are substituted with the heteroatom itself include, for example, those in which two hydrogen atoms bonded to the same carbon atom are substituted with one oxygen atom (that is, a carbonyl group (C And those having two hydrogen atoms bonded to the same carbon atom replaced by one sulfur atom (that is, those having a thiocarbonyl group (C = S)).
Examples of the carbon atom partially substituted with a heteroatom include, for example, those having —CH ₂ — in the structure thereof, wherein —CH ₂ — is substituted with —NH—, —O— And the like substituted with.
The substituent other than the hydrocarbon group may be other than the above-described group containing a hetero atom.

Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the halogenated alkyl group as the substituent include groups in which part or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms.

The “heteroatom” in the “heteroatom-containing linking group” is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a sulfur atom, and a nitrogen atom.
Examples of the hetero atom-containing linking group include an oxygen atom (ether bond; —O—), a sulfur atom (thioether bond; —S—), and —NH— (H is substituted with a substituent such as an alkyl group or an acyl group. A non-hydrocarbon group such as carbonyloxy group (—COO—), carbonyl group (—CO—), amide bond (—CONH—), carbonate bond (—OCOO—); A combination of a hydrogen group and the hydrocarbon group is exemplified.

When the unprotected body has a carboxy group, the unprotected body preferably has a group represented by the following general formula (z1) or (z2).
The group represented by the formula (z1) or (z2) is preferably bonded to the aromatic ring in the unprotected body via an oxygen atom (—O—).

［式中、Ｒ^３は置換基を有していてもよい炭化水素基であり、Ｒ^４は２価の連結基である。］

[Wherein R ³ is a hydrocarbon group which may have a substituent, and R ⁴ is a divalent linking group. ]

As the hydrocarbon group for R ^3, include those similar to the "optionally substituted hydrocarbon group" mentioned in the "aromatic ring and the linking group connecting the carboxyl group".
Among these, a linear alkylene group or an aromatic hydrocarbon group which may have a substituent is preferable.
The substituent that the aromatic hydrocarbon group may have is preferably at least one selected from a hydroxyl group, a halogen atom, an alkyl group, an aryl group, an alkoxy group, and an aryloxy group.
The aromatic hydrocarbon group preferably includes a benzene ring or a naphthalene ring as an aromatic ring, and particularly preferably includes a benzene ring.
R ³ is particularly preferably a group represented by the following general formula (31) or (32).

［式中、ｅは１〜５の整数であり、ｆは０〜５の整数である。］

[In formula, e is an integer of 1-5, f is an integer of 0-5. ]

In formula (31), e is preferably an integer of 1 to 3, more preferably 1 or 2, and most preferably 1.
In formula (32), f is preferably an integer of 0 to 3, more preferably 1 or 2, and most preferably 1.
A substituent may be bonded to the benzene ring in formula (32). Examples of the substituent include the same groups as those described above as the substituent that the aromatic hydrocarbon group may have. The number of substituents in the benzene ring is preferably 0 to 4, more preferably 0 or 1, and most preferably 0. When the number of the substituents is 2 or more, the plurality of substituents may be the same as or different from each other. The bonding position of the substituent to the benzene ring is not particularly limited.

When R ^{3 in} formula (z1) or (z2) is a group represented by formula (32), the bonding position of — (CH ₂ ) _f — with respect to the benzene ring in formula (32), —COOH or — The bonding position of COO—R ⁴ —COOH is not particularly limited, but — (CH ₂ ) _f — and —COOH or —COO—R ⁴ —COOH are bonded to each other in the para position. It is preferable.

In formula (z2), examples of the divalent linking group for R ⁴ include those similar to the above-mentioned “linking group for linking an aromatic ring and a carboxy group”. Among these, a hydrocarbon group which may have a substituent is preferable. Examples of the hydrocarbon group include the same groups as those described above for R ³ .

Specific examples of unprotected bodies (with no -OH removed) include, for example, low molecular weights known as sensitizers and heat resistance improvers in non-chemically amplified g-line and i-line resists. A phenol compound is mentioned. As the low molecular weight phenol compound, specifically,
Bis (4-hydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -3,4-dihydroxyphenylmethane, bis (3-cyclohexyl-4) -Hydroxy-6-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) -3,4-dihydroxyphenylmethane, 1- [1- (4-hydroxyphenyl) Isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, bis (2,3-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4 -Trihydroxyphenyl-4'-hydroxyphenylmethane, 2- (2,3,4-trihydroxy Phenyl) -2- (2 ′, 3 ′, 4′-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ′, 4′-dihydroxyphenyl) propane, 2- (4 -Hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) -2- (3'-fluoro-4'-hydroxyphenyl) propane, 2- (2, 4-dihydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4′-hydroxyphenyl) propane, and 2- (2,3,3) Bisphenol type compounds such as 4-trihydroxyphenyl) -2- (4′-hydroxy-3 ′, 5′-dimethylphenyl) propane;
Tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, Bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5- Dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3-hydroxyphenylmethane, Bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyl Nylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4- Hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) ) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenyl Methane and bis (5-cyclohexyl-4- Proxy-2-methylphenyl) -3,4-trisphenol compounds such dihydroxyphenyl methane;
Linear types such as 2,4-bis (3,5-dimethyl-4-hydroxybenzyl) -5-hydroxyphenol and 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol Trinuclear phenolic compounds;
1,1-bis [3- (2-hydroxy-5-methylbenzyl) -4-hydroxy-5-cyclohexylphenyl] isopropane, bis [2,5-dimethyl-3- (4-hydroxy-5-methylbenzyl) ) -4-hydroxyphenyl] methane, bis [2,5-dimethyl-3- (4-hydroxybenzyl) -4-hydroxyphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl)- 4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5-ethylphenyl] methane, bis [3- (3,5-diethyl- 4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4- Loxy-5-ethylphenyl] methane, bis [2-hydroxy-3- (3,5-dimethyl-4-hydroxybenzyl) -5-methylphenyl] methane, bis [2-hydroxy-3- (2-hydroxy-) 5-methylbenzyl) -5-methylphenyl] methane, bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane, and bis [2,5-dimethyl-3- Linear tetranuclear phenolic compounds such as (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane;
2,4-bis [2-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4-bis [4-hydroxy-3- (4-hydroxybenzyl) -5 -Methylbenzyl] -6-cyclohexylphenol and linear types such as 2,6-bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxybenzyl] -4-methylphenol Linear polyphenol compounds such as pentanuclear phenol compounds;
1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene and 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] Polynuclear branched compounds such as -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene; 2 of formalin condensates of phenols such as phenol, m-cresol, p-cresol or xylenol ~ 12 nuclei;
Calixarene such as calix [n] arene (n is 3 to 20, n is the number of phenol units) which is a cyclic oligomer formed by condensation of phenol and formaldehyde;
Calix resorcinarenes, which are cyclic oligomers produced by condensation of resorcinol and paraaldehyde;
Etc.

In the present invention, the unprotected body preferably has a structure in which 2 or 3 benzene rings are bonded via one carbon atom. When the unprotected body has such a structure, heat resistance, solubility in organic solvents, etching resistance, and the like are improved.
Among them, it is preferable to have at least one structure in which three benzene rings are bonded via one carbon atom, that is, a triphenylmethane structure, because the above effect is excellent.
When the unprotected body has a triphenylmethane structure, the number of triphenylmethane structures contained in one molecule is excellent in the above effects, easy to obtain, and heat resistant (one is insufficient in heat resistance) 2 to 6 are preferable, and 2 to 4 are more preferable, from the viewpoint of the advantage that the molecular size gives to the roughness characteristics (the smaller molecular weight is more advantageous).

The unprotected body preferably has a triphenylmethane structure having at least one phenolic hydroxyl group (hereinafter sometimes referred to as OH-containing triphenylmethane structure) as the triphenylmethane structure.
The number of phenolic hydroxyl groups in one OH-containing triphenylmethane structure is preferably 1 to 5, and more preferably 2 to 3.
The OH-containing triphenylmethane structure preferably further has at least one carboxy group. In this case, the number of carboxy groups in one OH-containing triphenylmethane structure is preferably 1 to 4, more preferably 1 or 2, and most preferably 1.
Of the three benzene rings constituting one OH-containing triphenylmethane structure, it is preferable that one benzene ring has a carboxy group and the other two benzene rings do not have a carboxy group.
When the unprotected body has a plurality of triphenylmethane structures, at least one of the plurality of triphenylmethane structures is preferably an OH-containing triphenylmethane structure, and all of them are OH-containing triphenylmethane structures. Most preferred.

As a preferable specific example of an unprotected body having a structure in which two benzene rings are bonded via one carbon atom, for example,
Compound (I-21) represented by the following general formula (I-21); a compound in which part of the hydrogen atoms of the hydroxyl group in the compound (I-21) is substituted with an alkyl group having 1 to 10 carbon atoms ( I-21 ′); compound (I-22) represented by the following general formula (I-22); a part of hydrogen atoms of the hydroxyl group in the compound (I-22) is an alkyl group having 1 to 10 carbon atoms And the like (I-22 ′) substituted with, and the like.

［式中、Ｒ^２０１〜Ｒ^２０６は、それぞれ独立に、炭素数１〜１０のアルキル基または芳香族炭化水素基であって、その構造中にヘテロ原子を含んでもよく；ｄ’、ｇ’はそれぞれ独立に１以上の整数であり、ｈ’は０以上の整数であり、かつｄ’＋ｇ’＋ｈ’が５以下であり；ｅ’、ｉ’はそれぞれ独立に１以上の整数であり、ｊ’は０以上の整数であり、かつｅ’＋ｉ’＋ｊ’が４以下であり；ｆ’、ｋ’はそれぞれ独立に１以上の整数であり、ｌ’は０以上の整数であり、かつｆ’＋ｋ’＋ｌ’が５以下であり；ｑ’は１〜２０の整数である。］

[Wherein, R ^{201 to} R ²⁰⁶ each independently represents an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group, and may contain a hetero atom in the structure thereof; d ′ and g ′ are Each independently represents an integer of 1 or more, h ′ is an integer of 0 or more, and d ′ + g ′ + h ′ is 5 or less; e ′ and i ′ are each independently an integer of 1 or more, j 'Is an integer of 0 or more, and e' + i '+ j' is 4 or less; f 'and k' are each independently an integer of 1 or more, l 'is an integer of 0 or more, and f '+ K' + l 'is 5 or less; q' is an integer of 1-20. ]

［式中、Ｒ^３０１〜Ｒ^３０６は、それぞれ独立に、炭素数１〜１０のアルキル基または芳香族炭化水素基であって、その構造中にヘテロ原子を含んでもよく；ａ”、ｅ”はそれぞれ独立に１以上の整数であり、ｆ”は０以上の整数であり、かつａ”＋ｅ”＋ｆ”が５以下であり；ｂ”、ｈ”はそれぞれ独立に１以上の整数であり、ｇ”は０以上の整数であり、かつｂ”＋ｈ”＋ｇ”が５以下であり；ｃ”、ｉ”はそれぞれ独立に１以上の整数であり、ｊ”は０以上の整数であり、かつｃ”＋ｉ”＋ｊ”が５以下であり；ｄ”は１以上の整数であり、ｋ”、ｌ”はそれぞれ独立に０以上の整数であり、かつｄ”＋ｋ”＋ｌ”が３以下である。］

[Wherein R ^{301 to} R ³⁰⁶ are each independently an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group, and the structure thereof may include a hetero atom; a ″, e ″ are Each independently represents an integer of 1 or more, f ″ is an integer of 0 or more, and a ″ + e ″ + f ″ is 5 or less; b ″ and h ″ are each independently an integer of 1 or more, g "" Is an integer greater than or equal to 0, and b "+ h" + g "is less than or equal to 5; c" and i "are each independently an integer greater than or equal to 1, j" is an integer greater than or equal to 0, and c "+ I" + j "is 5 or less; d" is an integer of 1 or more, k "and l" are each independently an integer of 0 or more, and d "+ k" + l "is 3 or less. ]

In the general formula (I-21), the alkyl group in R ^{201 to} R ²⁰⁶ is preferably a linear or branched alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 5 to 6 carbon atoms. . 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. A chain or branched alkyl group is exemplified, and among these, a methyl group is preferable. Examples of the cyclic alkyl group include a cyclohexyl group and a cyclopentyl group, and a cyclohexyl group is preferable.
The aromatic hydrocarbon group for R ²⁰¹ to R ^206, preferably an aromatic hydrocarbon group having 6 to 15 carbon atoms, for example, a phenyl group, a tolyl group, a xylyl group, mesityl group, phenethyl group, and naphthyl group can be mentioned It is done.
These alkyl groups or aromatic hydrocarbon groups may contain a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom in the structure.
In the formula ^{(1-21), if R 201} there are a plurality, it may be ^{R 201} the plurality of respectively the same or different. The same applies to R ^{202 to} R ²⁰⁶ .
d ′ and g ′ are preferably 1 or 2.
h ′ is preferably 0 or 1.
e ′ and i ′ are preferably 1 or 2.
j ′ is preferably 0 or 1.
l ′ is preferably 0 or 1.
q ′ is preferably an integer of 2 to 10.
In formula (I-21), the value of d ′ + e ′ × q ′ + f ′, that is, the number of phenolic hydroxyl groups in compound (I-21) is preferably 2 to 16, and particularly preferably 3 to 12.
As compound (I-21), a commercially available product may be used, or it may be synthesized by a known method.

Compound (I-21 ′) is a compound in which part of the hydrogen atoms of the hydroxyl group of Compound (I-21) is substituted with an alkyl group having 1 to 10 carbon atoms.
The alkyl group may be linear, branched or cyclic, and is a linear or branched alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 5 to 6 carbon atoms. Is preferred. 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. A chain or branched alkyl group is exemplified, and among these, a methyl group is preferable. Examples of the cyclic alkyl group include a cyclohexyl group and a cyclopentyl group, and a cyclohexyl group is preferable.
Compound (I-21 ′) can be produced by substituting part of the hydrogen atoms of the hydroxyl group of Compound (I-21) with an alkyl group having 1 to 10 carbon atoms by a known method.

In general formula (I-22) above, the alkyl groups and aromatic hydrocarbon groups of R ^{301 to} R ³⁰⁶ are the alkyl groups and aromatic carbon groups of R ^{201 to} R ²⁰⁶ in formula (I-21), respectively. The thing similar to a hydrogen group is mentioned.
In Formula (I-22), it is preferable that R ^{301 to} R ³⁰⁶ are all alkyl groups having 1 to 5 carbon atoms.
In the formula ^{(1-22), if R 301} there are a plurality, it may be ^{R 301} the plurality of respectively the same or different. The same applies to R ^{302 to} R ³⁰⁶ .
It is preferable that a ″ and e ″ are each independently 1 or 2.
f ″ is preferably 0 or 1.
It is preferable that b ″ and h ″ are each independently 1 or 2.
g ″ is preferably 0 or 1.
Preferably c ″ and i ″ are each independently 1 or 2.
j ″ is preferably 0 or 1.
d ″ is preferably 1 or 2.
It is preferable that k ″ and l ″ are each independently 0 or 1.
In the formula (I-22), the value of a ″ + b ″ + c ″ + d ″, that is, the number of phenolic hydroxyl groups in the compound (I-22) is preferably 2 to 16, and particularly preferably 3 to 12.
As compound (I-22), a commercially available product may be used, or the compound (I-22) may be synthesized by a known method.

Compound (I-22 ′) is a compound in which part of the hydrogen atoms of the hydroxyl group of Compound (I-22) is substituted with an alkyl group having 1 to 10 carbon atoms.
The alkyl group is the same as the alkyl group having 1 to 10 carbon atoms that substitutes part of the hydrogen atom of the hydroxyl group of the compound (I-21) in the description of the compound (I-21 ′). Things.
Compound (I-22 ′) can be produced by substituting a part of the hydrogen atoms of the hydroxyl group of compound (I-22) with an alkyl group having 1 to 10 carbon atoms by a known method.

  Preferable specific examples of the unprotected body having a triphenylmethane structure include, for example, a compound (I-31) represented by the following general formula (I-31); a hydrogen atom of a hydroxyl group in the compound (I-31) And a compound (I-31 ′) in which a part of the atoms is substituted with an alkyl group having 1 to 10 carbon atoms.

［式中、ｎ_１１は１〜５の整数であり；Ａは（ｎ_１１＋１）価の連結部であり；ａおよびｎ１はそれぞれ独立に１以上の整数であり、ｎ２およびｎ５はそれぞれ独立に０以上の整数であり、かつａ＋ｎ１＋ｎ２＋ｎ５が５以下であり；ｂは１以上の整数であり、ｎ３およびｎ４はそれぞれ独立に０以上の整数であり、かつｂ＋ｎ３＋ｎ４が４以下であり；ｃは１以上の整数であり、ｎ６およびｎ７はそれぞれ独立に０以上の整数であり、かつｃ＋ｎ６＋ｎ７が４以下であり；Ｒ^１０１〜Ｒ^１０７はそれぞれ独立に炭素数１〜１０のアルキル基または芳香族炭化水素基であって、その構造中にヘテロ原子を含んでもよく；Ｚ^１およびＺ^２は、それぞれ独立に、水素原子、下記一般式（ｚ１）で表される基、または下記一般式（ｚ２）で表される基である。］

[Wherein n ₁₁ is an integer of 1 to 5; A is a (n ₁₁ +1) -valent linking moiety; a and n 1 are each independently an integer of 1 or more, and n 2 and n 5 are each independently N is an integer of 0 or more, and a + n1 + n2 + n5 is 5 or less; b is an integer of 1 or more, n3 and n4 are each independently an integer of 0 or more, and b + n3 + n4 is 4 or less; c is 1 or more N6 and n7 are each independently an integer of 0 or more, and c + n6 + n7 is 4 or less; R ^{101 to} R ¹⁰⁷ are each independently an alkyl group or an aromatic hydrocarbon group having 1 to 10 carbon atoms Table Z ¹ and Z ² are each independently a hydrogen atom, a group represented by the following general formula (z1) or the following general formula (z2),; a is may contain a hetero atom in the structure Is a group. ]

［式中、Ｒ^３は置換基を有していてもよい炭化水素基であり、Ｒ^４は２価の連結基である。］

[Wherein R ³ is a hydrocarbon group which may have a substituent, and R ⁴ is a divalent linking group. ]

Wherein _{(I-31), n 11} is an integer of 1 to 5. That is, compound (I-31) is a compound having 2 to 6 triphenylmethane structures in its skeleton. By having such a structure, it has excellent film forming ability, high heat resistance, and various lithography characteristics.
n ₁₁ is preferably an integer of 1 to 3, most preferably 1.

Wherein (I-31), A is a connecting portion of the _(n 11 +1) number.
The connecting portion is not particularly limited. Preferable examples of the connecting portion include a (n ₁₁ +1) -valent hydrocarbon group which may have a substituent.
The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
The “aliphatic hydrocarbon group” 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 and an aliphatic hydrocarbon group having a ring in the structure.

The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8, more preferably 1 to 6, and particularly preferably 1 to 5 Preferably 1 or 2 is most preferred.
The linear aliphatic hydrocarbon group is preferably a saturated hydrocarbon group. For example, as a divalent linear saturated hydrocarbon group (linear alkylene group), specifically, methylene group [—CH ₂ —], ethylene group [— (CH ₂ ) ₂ —], trimethylene group [— (CH ₂ ) ₃ —], tetramethylene group [— (CH ₂ ) ₄ —], pentamethylene group [— (CH ₂ ) ₅ —] and the like can be mentioned. Examples of the trivalent or tetravalent linear saturated hydrocarbon group include groups in which one or two hydrogen atoms are further removed from the linear alkylene group.
The branched aliphatic hydrocarbon group is preferably a saturated hydrocarbon group. For example, as a divalent branched saturated hydrocarbon group (branched alkylene group), specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH _{3) ) 2 -, - C (CH} 3) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as Alkylethylene groups such as —CH (CH ₃ ) CH ₂ —, —CH (CH ₃ ) CH (CH ₃ ) —, —C (CH ₃ ) ₂ CH ₂ —, —CH (CH ₂ CH ₃ ) CH ₂ —; _{; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such _{as; -CH (CH 3) CH 2} CH 2 CH 2 -, - CH 2 CH ( CH _{3) CH} 2 CH ₂ - aralkyl, such as alkyl tetramethylene group such as Ruarukiren group, and the like. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms. Examples of the trivalent or tetravalent branched saturated hydrocarbon group include groups obtained by further removing one or two hydrogen atoms from the branched alkylene group.
The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Here, the term “having a substituent” for a hydrocarbon group means that part or all of the hydrogen atoms in the hydrocarbon group are substituted with groups or atoms other than hydrogen atoms. Examples of the substituent include a hydroxyl group, a carboxy group, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (═O).

Examples of the aliphatic hydrocarbon group containing a ring include a cyclic aliphatic hydrocarbon group (a group obtained by removing (n ₁₁ +1) hydrogen atoms from an aliphatic hydrocarbon ring), and the cyclic aliphatic hydrocarbon group, Examples thereof include a group bonded to the terminal of the linear or branched aliphatic hydrocarbon group described above or interposed in the middle of the linear or branched aliphatic hydrocarbon group.
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 group, a group in which two hydrogen atoms have been removed from a monocycloalkane having 3 to 6 carbon atoms is preferable, and examples of the monocycloalkane include cyclopentane and cyclohexane. As the polycyclic group, a group in which two hydrogen atoms are removed from a polycycloalkane having 7 to 12 carbon atoms is preferable. Specific examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, tetra And cyclododecane.
The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).

Examples of the “aromatic hydrocarbon group” include groups obtained by removing (n ₁₁ +1) hydrogen atoms from a hydrocarbon containing an aromatic hydrocarbon ring in the structure. Specifically, a group obtained by removing (n ₁₁ +1) hydrogen atoms from an aromatic hydrocarbon ring (aromatic cyclic group), and the aromatic cyclic group is the chain aliphatic hydrocarbon group described above. Examples thereof include a group bonded to the terminal or intervening in the middle of a chain-like aliphatic hydrocarbon group.
Examples of the aromatic hydrocarbon ring include a benzene ring, a biphenyl ring, a fluorene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a pyrene ring.
In the aromatic hydrocarbon group, a part of carbon atoms constituting the group may be substituted with a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom.

The aromatic hydrocarbon group may or may not have a substituent. Here, the aromatic hydrocarbon group having a substituent means that part or all of the hydrogen atoms of the unsubstituted aromatic hydrocarbon group are substituted with a substituent (a group or atom other than a hydrogen atom). Means.
The substituent that the aromatic hydrocarbon group may have is preferably at least one selected from a hydroxyl group, a halogen atom, an alkyl group, an aryl group, an alkoxy group, and an aryloxy group.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The alkyl group as the substituent is not particularly limited, and may be linear, branched or cyclic.
The linear alkyl group preferably has 1 to 5 carbon atoms, and specifically includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Or it is preferable that it is an ethyl group.
The branched alkyl group preferably has 4 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms. Specific examples include an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, and a tert-pentyl group.
The cyclic alkyl group preferably has 3 to 20 carbon atoms, more preferably 4 to 14 carbon atoms, and particularly preferably 5 to 12 carbon atoms.
The structure of the basic ring (basic ring excluding a substituent) in the cyclic alkyl group may be monocyclic or polycyclic. The basic ring may be a hydrocarbon ring composed of carbon and hydrogen, and as described later, a heterocyclic ring in which a part of carbon atoms constituting the hydrocarbon ring is substituted with a heteroatom. Also good. Specific examples of the hydrocarbon ring include monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane. Specific examples include monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. These basic rings may or may not have a substituent composed of a hydrocarbon group on the ring. Examples of the hydrocarbon group include linear or branched alkyl groups having 1 to 5 carbon atoms such as a methyl group and an ethyl group. When the basic ring has a substituent, the number of substituents is preferably 1 to 3, and more preferably 1.
The aryl group as the substituent is not particularly limited, but preferably has 6 to 15 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a phenethyl group, and a naphthyl group. Of these, a phenyl group is more preferable.
Examples of the alkoxy group as the substituent include a group in which the alkyl group is bonded to an oxygen atom (—O—).
Examples of the aryloxy group as the substituent include a group in which the aryl group is bonded to an oxygen atom (—O—).

The alkyl group and aryl group as the substituent may each contain a group or atom other than the hydrocarbon group in the structure. Further, the alkyl group in the alkoxy group as the substituent and the aryl group in the aryloxy group may each contain a group or atom other than the hydrocarbon group in the structure.
For example, some or all of the hydrogen atoms in these alkyl groups and aryl groups may be substituted with groups containing heteroatoms (including heteroatoms themselves), and carbons in the alkyl groups and aryl groups may be substituted. A part of the atoms may be substituted with a group containing a hetero atom (including a hetero atom itself).
Examples of the hetero atom in the “group containing a hetero atom” for substituting a hydrogen atom include an oxygen atom, a sulfur atom, a nitrogen atom, and a fluorine atom.
Examples of those in which part or all of the hydrogen atoms are substituted with a group containing a hetero atom include, for example, hydroxyl groups, alkoxy groups, and fluorinations having 1 to 5 carbon atoms in which part or all of the hydrogen atoms are substituted with fluorine atoms. Examples thereof include those substituted with a group consisting of a hetero atom and a carbon atom and / or a hydrogen atom, such as an alkyl group.
Examples of the hydrogen atom in which part or all of the hydrogen atoms are substituted with the heteroatom itself include, for example, one in which two hydrogen atoms bonded to the same carbon atom are substituted with one oxygen atom (that is, a carbonyl group (C═O ), And those in which two hydrogen atoms bonded to the same carbon atom are substituted with one sulfur atom (that is, those having a thiocarbonyl group (C═S)).
Examples of the carbon atom partially substituted with a group containing a hetero atom include, for example, a group containing —CH ₂ — in the structure, wherein the —CH ₂ — is substituted with the hetero atom-containing linking group. Things. Examples of the hetero atom-containing linking group include an oxygen atom (ether bond; —O—), a sulfur atom (thioether bond; —S—), and —NH— (H is substituted with a substituent such as an alkyl group or an acyl group. ), Carbonyloxy group (—COO—), carbonyl group (—CO—), amide bond (—CONH—), carbonate bond (—OCOO—) and the like.
The substituent other than the hydrocarbon group may be other than the above-described group containing a hetero atom.

In the formula (1-31), when A is a hydrocarbon group which may have a substituent, the hydrocarbon group particularly includes a linear or branched aliphatic hydrocarbon group, a structure An aliphatic hydrocarbon group containing a ring therein or an aromatic hydrocarbon group is preferred.
For example, when n ₁₁ is 1, that is, when A is a divalent linking part, the linking part includes a linear or branched alkylene group, a cyclic aliphatic hydrocarbon group, or an aromatic carbon group. A hydrogen group is preferable, and a linear or branched alkylene group or an aromatic hydrocarbon group is particularly preferable. Among these, a group represented by the following general formula (A2-1) is preferable.

［式中、Ｚ^３は水素原子、前記一般式（ｚ１）で表される基、または前記一般式（ｚ２）で表される基であり；Ｒ^１０８、Ｒ^１０９はそれぞれ独立に炭素数１〜１０のアルキル基または芳香族炭化水素基であって、その構造中にヘテロ原子を含んでもよく；ｎ８、ｎ９はそれぞれ独立に０以上の整数であり、ｄは１以上の整数であり、かつｎ８＋ｎ９＋ｄは１〜４の整数であり、ｎ_１０は０〜５の整数である。］

[Wherein, Z ³ is a hydrogen atom, a group represented by the general formula (z1), or a group represented by the general formula (z2); R ¹⁰⁸ and R ¹⁰⁹ are each independently a group having 1 to 10 alkyl groups or aromatic hydrocarbon groups which may contain heteroatoms in the structure; n8 and n9 are each independently an integer of 0 or more, d is an integer of 1 or more, and n8 + n9 + d is an integer from 1 to _{4, n 10} represents an integer of 0 to 5. ]

In formula (A2-1), examples of the alkyl group or aromatic hydrocarbon group for R ¹⁰⁸ and R ¹⁰⁹ include the same alkyl groups or aromatic hydrocarbon groups for R ^{101 to} R ¹⁰⁷ described above.
The alkyl group or aromatic hydrocarbon group of R ^{101 to} R ¹⁰⁷ may contain a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom in the structure.
R ¹⁰⁸ and R ¹⁰⁹ are preferably a methyl group from the viewpoint of excellent effects of the present invention.
d is an integer of 1 or more, preferably 1 to 2, and most preferably 1.
n8 and n9 are each independently an integer of 0 or more, and d + n8 + n9 is a value of 4 or less. n8 + n9 is preferably 1 or 2.
n ₁₀ is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, more preferably 0 or 1.

When n ₁₁ is 2, that is, when A is a trivalent linking moiety, specific examples of the linking group include a group represented by general formula (A3-1) shown below.

［式中、Ｗ^１は直鎖状または分岐鎖状のアルキレン基であり、Ｗ^２は３価の直鎖状または分岐鎖状の飽和炭化水素基であり、Ｒ^１１０は芳香族炭化水素基である。］

[Wherein W ¹ is a linear or branched alkylene group, W ² is a trivalent linear or branched saturated hydrocarbon group, and R ¹¹⁰ is an aromatic hydrocarbon group. is there. ]

Wherein (A3-1), as the W ^1, the same as the linear or branched alkylene group mentioned in the like.
Examples of W ² include groups in which one hydrogen atom has been removed from the linear or branched alkylene group mentioned above.
Examples of R ¹¹⁰ include the same aromatic hydrocarbon groups as described above. As the aromatic hydrocarbon group, an arylene group which may have a substituent is particularly preferable, and a phenylene group which may have a substituent is particularly preferable.
As the group represented by the formula (A3-1), a group represented by the following general formula (A3-11) is particularly preferable.

［式中、Ｒ^１１１〜Ｒ^１１３はそれぞれ独立に炭素数１〜５のアルキル基である。］

[Wherein, R ^{111 to} R ¹¹³ each independently represents an alkyl group having 1 to 5 carbon atoms. ]

In formula (A3-11), the alkyl groups represented by R ^{111 to} R ¹¹³ are preferably linear or branched alkyl groups, and more preferably linear alkyl groups. The alkyl group preferably has 1 to 3 carbon atoms, and most preferably a methyl group.

When n ₁₁ is 3, that is, when A is a tetravalent linking moiety, specific examples of the linking group include a group represented by general formula (A4-1) shown below.

［式中、Ｗ^３、Ｗ^４はそれぞれ独立に環状の脂肪族炭化水素基であり、Ｒ^１２０は直鎖状または分岐鎖状のアルキレン基である。］

[Wherein, W ³ and W ⁴ each independently represent a cyclic aliphatic hydrocarbon group, and R ¹²⁰ represents a linear or branched alkylene group. ]

In formula (A4-1), the cyclic aliphatic hydrocarbon group in W ³ and W ⁴ may be a polycyclic group or a monocyclic group. The monocyclic group is preferably a group in which 3 hydrogen atoms are removed from a monocycloalkane having 3 to 6 carbon atoms, and examples of the monocycloalkane include cyclopentane and cyclohexane. As the polycyclic group, a group in which two hydrogen atoms are removed from a polycycloalkane having 7 to 12 carbon atoms is preferable. Specific examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, tetra And cyclododecane. Among these, a group obtained by removing three hydrogen atoms from cyclohexane is preferable.
The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, a carboxy group, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).
^Examples of the linear or branched alkylene group for R ¹²⁰ include the same as those described above.
As the group represented by the formula (A4-1), a group represented by the following general formula (A4-11) is particularly preferable.

［式中、Ｒ^１２１、Ｒ^１２２はそれぞれ独立に炭素数１〜５のアルキル基である。］

[Wherein, R ¹²¹ and R ¹²² each independently represents an alkyl group having 1 to 5 carbon atoms. ]

In formula (A4-11), the alkyl group for R ¹²¹ and R ¹²² is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
The alkyl group preferably has 1 to 3 carbon atoms, and most preferably a methyl group.

In formula (I-31), a and n1 are each independently an integer of 1 or more, n2 and n5 are each independently an integer of 0 or more, and a + n1 + n2 + n5 is 5 or less.
a is preferably 1 or 2, and most preferably 1. n1 is preferably 1 or 2, and most preferably 1. n2 is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 1. n5 is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 0.
b is an integer of 1 or more, n3 and n4 are each independently an integer of 0 or more, and b + n3 + n4 is 4 or less.
b is preferably an integer of 1 to 4, more preferably 1 or 2, and most preferably 1. n3 is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 1. n4 is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 1.
c is an integer of 1 or more, n6 and n7 are each independently an integer of 0 or more, and c + n6 + n7 is 4 or less.
c is preferably an integer of 1 to 4, more preferably 1 or 2, and most preferably 1. n6 is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 1. n7 is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 1.

In the present invention, it is particularly preferable that b and c are 1 and n ₁₁ is an integer of 1 to 3. That is, it is particularly preferable that the compound (I-31) is represented by the following general formula (I-31-1).

［式中、ｎ_１３は、１〜３の整数であり；Ａ、ａ、ｎ１、ｎ２、ｎ５はそれぞれ前記と同じであり；ｎ３’およびｎ４’はそれぞれ独立に０以上の整数であり、かつｎ３’＋ｎ４’が３以下であり；ｎ６’およびｎ７’はそれぞれ独立に０以上の整数であり、かつｎ６’＋ｎ７’が３以下であり；Ｒ^１０１〜Ｒ^１０７、Ｚ^１、Ｚ^２はそれぞれ前記と同じである。］

[Wherein n ₁₃ is an integer of 1 to 3; A, a, n1, n2 and n5 are the same as defined above; n3 ′ and n4 ′ are each independently an integer of 0 or more; n3 ′ + n4 ′ is 3 or less; n6 ′ and n7 ′ are each independently an integer of 0 or more, and n6 ′ + n7 ′ is 3 or less; R ^{101 to} R ¹⁰⁷ , Z ¹ , and Z ² are each Same as above. ]

Wherein _{(I-31-1), n 13} is an integer of 1 to 3, most preferably 1.
A, a, n1, n2, n5, R ^{101 to} R ¹⁰⁷ , Z ¹ and Z ² are the same as n ₁₁ , A, R ^{101 to} R ¹⁰⁷ , Z ¹ and Z ^{2 in the} formula (I-31), respectively. It is.
Of these, Z ¹ and Z ² are each preferably a group represented by the general formula (z1) or a group represented by the general formula (z2).
n3 ′ is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 1.
n4 ′ is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 1.
n6 ′ is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 1.
n7 ′ is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 1.
Wherein ^(I-31-1), if the R 101 ^{to R 107} are present in plural, may be ^R 101 ^{to R 107} of the plurality of the same, respectively, may be different.

In formula (I-31), R ^{101 to} R ¹⁰⁷ are each independently an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group.
The alkyl group may be linear, branched or cyclic, and is a linear or branched alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 5 to 6 carbon atoms. Is preferred. 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. A chain or branched alkyl group is exemplified, and among these, a methyl group is preferable. Examples of the cyclic alkyl group include a cyclohexyl group and a cyclopentyl group, and a cyclohexyl group is preferable.
The aromatic hydrocarbon group preferably has 6 to 15 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a phenethyl group, and a naphthyl group.
These alkyl groups or aromatic hydrocarbon groups may contain a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom in the structure.
In the formula ^{(1-31), if R 101} there are a plurality, it may be ^{R 101} the plurality of respectively the same or different. The same applies to R ¹⁰² to R ^107.

In formula (I-31), the group represented by formula (z1) and the group represented by formula (z2) in Z ¹ and Z ² are the same as defined above.
Z ¹ and Z ² are particularly preferably a group represented by the formula (z1) or a group represented by the formula (z2). When Z ¹ and Z ² are each a group represented by the formula (z1) or a group represented by the formula (z2), the effect of the present invention is high, and an excellent roughness reduction effect is obtained. This is because, for example, when the component (A1) is produced by introducing R ¹ and R ² into the unprotected body, the reactivity of the carboxy group is higher than that of the phenolic hydroxyl group, so that R ¹ and R ² Is selectively introduced at the positions of Z ¹ and Z ² , and it is presumed that the variation in the structure between molecules in the component (A1) is very small.
Further, since R ¹ and R ² are introduced in a regioselective manner, there is an advantage that the properties of the entire component (A1) can be easily adjusted by selecting the types of R ¹ and R ² respectively. For example, in the case where a group having a polycyclic structure such as adamantane is selected as R ¹ , the case where a group having a monocyclic structure such as cyclohexane is selected, and the case where a group having a chain structure is selected, the component (A1) The solubility in an alkaline developer is a group having a polycyclic structure <a group having a monocyclic structure <a group having a chain structure.

The compound (I-31) represented by the above formula (I-31) has 2 to 4 triphenylmethane structures. The number of the triphenylmethane structures is most preferably 2.
1-5 are preferable and, as for the number of the phenolic hydroxyl groups contained in one triphenylmethane structure in a compound (I-31), 2-3 are more preferable.
In the compound (I-31), as described above, Z ¹ and Z ² are each preferably a group represented by the formula (z1) or a group represented by the formula (z2). That is, it is preferable to have at least one carboxy group in one triphenylmethane structure.
The number of carboxy groups in one triphenylmethane structure (that is, the values of b and c in formula (I-31)) is preferably 1 to 4, more preferably 1 or 2, and most preferably 1.

In compound (I-31), among the three benzene rings constituting each triphenylmethane structure, the bonding position of A in the benzene ring to which A is bonded is not particularly limited, but the other two benzene rings are bonded. It is preferable that it is bonded to the meta position with respect to the position to which the carbon atom is bonded. Such a compound has advantages such as being suitable for a resist composition and being easily synthesized.
The bonding position of the hydroxyl group with the subscript a (ie, — (OH) _a ) is not particularly limited, but the obtained component (A1) is suitable for a resist composition, and is easy to synthesize. It is preferable that it is bonded at least to the para position (4 position) of the phenyl group.
The bonding position of R ^{101 to} R ¹⁰⁷ is not particularly limited, but R ¹⁰¹ is at least one of carbon atoms adjacent to the carbon atom to which the hydroxyl group is bonded (ortho-position carbon atom) in terms of ease of synthesis and the like. It is preferable that it is couple | bonded with.
The bonding position of —OZ ¹ and —OZ ² is not particularly limited, but is preferably bonded at least to the para position with respect to the bonding position of A. Such a compound has advantages such as being suitable for a resist composition and being easily synthesized.
As compound (I-31), a compound represented by general formula (1-11) shown below is particularly desirable.

［式中、ｎ_１１、Ａ、ｎ３〜ｎ４、ｎ６〜ｎ７、ｂ、ｃ、Ｒ^１０１〜Ｒ^１０４、Ｒ^１０６〜Ｒ^１０７、Ｚ^１およびＺ^２はそれぞれ前記と同じである。］

[Wherein, n ₁₁ , A, n3 to n4, n6 to n7, b, c, R ^{101 to} R ¹⁰⁴ , R ^{106 to} R ¹⁰⁷ , Z ¹ and Z ² are the same as defined above. ]

In the formula, a plurality of R ¹⁰¹ may each represent the same group, or may represent different groups. The same applies to R ^102.
The bonding position of R ¹⁰² is not particularly limited, but from the viewpoint of ease of synthesis, the position of the hydroxyl group at the ortho position of R ¹⁰¹ and the position of R ¹⁰¹ meta position, or the position of the hydroxyl group meta position and R ¹⁰¹ paraffin. It is preferable that it is bonded to a position that is a position.
The bonding positions of R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁶ , and R ¹⁰⁷ are not particularly limited, but the ortho position or meta position of the hydroxyl group is preferable from the viewpoint of ease of synthesis.
OZ ¹ and OZ ² are each preferably bonded to the para position with respect to the bonding position of A.

Compound (I-31) can be produced by a known method.
For example, when Z ¹ and Z ² are each a hydrogen atom, compound (I-31) can be obtained by, for example, subjecting a salicylaldehyde derivative and a phenol compound which may have a substituent to dehydration condensation under acidic conditions. Can be synthesized.
When Z ¹ and Z ² are each a group represented by the formula (z1) or (z2), a compound in which Z ¹ and Z ² are each a hydrogen atom is obtained as described above. The compound (I-31) can be produced by further introducing a carboxy group-containing group by reacting a precursor compound of a group represented by the formula (z1) or (z2) with a hydroxyl group. Examples of the precursor compound include halogenated acetic acid derivatives such as methyl chloroacetate, and halogenated alkyl benzoic acids such as chloromethyl benzoic acid derivatives and bromomethyl benzoic acid derivatives.

However, the method as described above has a problem that it is difficult to control the position and number of the hydroxyl group into which the group represented by the formula (z1) or (z2) is introduced, and the yield of the obtained compound is low.
Therefore, when Z ¹ and Z ² are groups represented by the formula (z1) or (z2), respectively, as a method for producing the phenol compound (I-31), first, the hydroxyl group of the salicylaldehyde derivative A method in which the group represented by the formula (z1) or (z2) is introduced in the same manner as described above and then dehydrated and condensed under acidic conditions with a phenol compound which may have a substituent is preferable.
Hereinafter, an example of the production method is a case of producing a compound in which a group represented by the formula (z1) is introduced at the positions of Z ¹ and Z ² (hereinafter referred to as compound (I-31-1)). This will be described more specifically with an example.
The production method is carried out by reacting a compound (1-01) represented by the following general formula (1-01) with a compound (1-02) represented by the following general formula (1-02). A step of obtaining a compound (1-03) represented by (1-03) (hereinafter referred to as a compound (1-03) formation step);
A step of obtaining a compound (I-31-1) through a step of reacting the compound (1-03) and a compound (1-04) represented by the following general formula (1-04) under acidic conditions (hereinafter referred to as “the compound (1-03)”) And compound (I-31-1) formation step).

［式中、ｎ_１１、Ａ、ａ、ｂ、ｃ、ｎ１〜ｎ７、Ｒ^１０１〜Ｒ^１０７およびＲ^３はそれぞれ前記と同じであり；Ｘ^ｈはハロゲン原子であり；Ｒ^２０１は保護基である。］

[Wherein, n ₁₁ , A, a, b, c, n1 to n7, R ^{101 to} R ¹⁰⁷ and R ³ are the same as defined above; X ^h is a halogen atom; R ²⁰¹ is a protecting group] . ]

In general formula (1-02), examples of the halogen atom for X ^h include a bromine atom, a chlorine atom, and a fluorine atom. A chlorine atom and a bromine atom are preferable because of excellent reactivity.
The protecting group for R ²⁰¹ is not particularly limited as long as it is a group that does not react when reacting compound (1-01) and compound (1-02) and hydrolyzes under basic conditions. Examples of the group that hydrolyzes under basic conditions include a linear alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group.
A commercially available compound can be used as the compound (1-02).
Compound (1-01) may be commercially available or synthesized. For example, a compound represented by the following general formula (1-01-2) by introducing a hydroxymethyl group into the compound (1-01-1) represented by the following general formula (1-01-1) (1 The compound (1-01) can be obtained by obtaining -01-2) and formylating the alcoholic hydroxyl group.

［式中、ｎ_１１、Ａ、ｎ３〜ｎ４、ｎ６〜ｎ７、ｂ、ｃ、Ｒ^１０３〜Ｒ^１０４およびＲ^１０６〜Ｒ^１０７はそれぞれ前記と同じである。］

[Wherein, n ₁₁ , A, n3 to n4, n6 to n7, b, c, R ^{103 to} R ¹⁰⁴ and R ^{106 to} R ¹⁰⁷ are the same as defined above. ]

(Compound (1-03) formation step)
Compound (1-01) and compound (1-02) can be reacted by a known method. For example, the compound (1-01) is dissolved in an organic solvent such as N-methylpyrrolidone, a base such as potassium carbonate is added to the solution, and the compound (1-02) is added to the solution while stirring. Can be reacted.
As an organic solvent used at this time, any compound can be used as long as it dissolves the compound (1-01), the compound (1-02), and the compound (1-03) to be formed. Should be selected. Examples of common organic solvents include cyclic amides such as N-methylpyrrolidone, ketones such as acetone, methyl ethyl ketone, methyl pentyl ketone, and cyclohexanone; ethers such as tetrahydrofuran (THF), dioxane, glyme, and propylene glycol monomethyl ether. And the like; esters such as ethyl acetate and ethyl lactate; ether esters such as propylene glycol methyl ether acetate; lactones such as γ-butyrolactone, and the like can be used alone or in combination. .
The reaction conditions may be appropriately selected according to the combination of raw materials used, the boiling point of the organic solvent, etc., but the reaction temperature is preferably switched in two stages, for example, compound (1-01) and compound (1-02) The temperature at the time of mixing is preferably 30 to 80 ° C., more preferably 40 to 70 ° C., then the temperature is raised, and the reaction is continued preferably at 60 to 130 ° C., more preferably 60 to 120 ° C. It is good.
The reaction time is, for example, preferably 0.5 to 3.5 hours, more preferably 1.5 to 3.0 hours before the temperature rise, and preferably 1 to 24 hours, more preferably 3 to 3 hours after the temperature rise. 15 hours is recommended.
After completion of the reaction, the reaction solution may be used as it is in the next step, but water and an organic solvent such as methyl isobutyl ketone and ethyl acetate are added, and the organic phase (methyl isobutyl ketone phase, etc.) is concentrated under reduced pressure. Compound (1-03) may be obtained, or acid precipitation may be performed by adding an appropriate amount of acid.

(Compound (I-31-1) formation step)
Next, the compound (1-03) and the compound (1-04) are reacted under acidic conditions. Thereby, the formyl group (—CHO) of the compound (1-03) reacts with the compound (1-04). Then, by carrying out hydrolysis under basic conditions, the protecting group ^R201 is dissociated to form the compound (I-31-1).
A commercially available compound can be used as the compound (1-04).
The compound (1-03) and the compound (1-04) are prepared by, for example, dissolving the compound (1-04) in an organic solvent such as methanol and adding an acid such as hydrochloric acid to the solution. It can be made to react by adding a compound (1-03) in it.
There is no restriction | limiting in particular as an acid used at this time, if the reaction of a compound (1-03) and a compound (1-04) can be advanced. Preferred examples include hydrochloric acid, sulfuric acid, sulfuric anhydride, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, trifluoroacetic acid and the like. Of these, hydrochloric acid is preferred. When hydrochloric acid gas is used, it may be blown into an organic solvent, and is preferably blown before the compound (1-04) is added to the organic solvent. Any one of these acids may be used alone, or two or more of these acids may be mixed and used.
What is necessary is just to adjust the addition amount of an acid suitably with the kind of acid.
The reaction conditions may be appropriately selected according to the combination of raw materials to be used. For example, the reaction temperature is preferably 10 to 80 ° C, more preferably 30 to 60 ° C. The reaction time is preferably 1 to 96 hours, more preferably 3 to 72 hours.
After completion of the reaction, a base such as sodium hydroxide or tetramethylammonium hydroxide is added to the reaction solution to neutralize the acid in the reaction solution. At this time, by adding an excess base, it may be dissociated protecting group R ²⁰¹ with neutralization, after neutralization may further base was to dissociate protecting group R ²⁰¹ with added. The type of the base may be the same as or different from the base used for neutralization.
The reaction solution thus obtained is further concentrated as necessary, and then transferred to a separatory funnel, extracted, concentrated, and dried to obtain the target product.
The structure of the obtained compound is as follows: ¹ H-nuclear magnetic resonance (NMR) spectrum method, ¹³ C-NMR spectrum method, ¹⁹ F-NMR spectrum method, infrared absorption (IR) spectrum method, mass spectrometry (MS) method, element It can be confirmed by a general organic analysis method such as analysis method or X-ray crystal diffraction method.

Compound (I-31 ′) is a compound in which part of the hydrogen atoms of the hydroxyl group of Compound (I-31) is substituted with an alkyl group having 1 to 10 carbon atoms.
Examples of the alkyl group include the same groups as those described above as the alkyl group having 1 to 10 carbon atoms of R ^{101 to} R ¹⁰⁵ .
In the compound (I-31 ′), —OH in which a hydrogen atom is substituted with an alkyl group having 1 to 10 carbon atoms is preferably only a phenolic hydroxyl group. That is, as the compound (I-31 ′), a part of hydrogen atoms of the phenolic hydroxyl group (hydroxyl group directly bonded to the benzene ring) in the general formula (I-31) is substituted with the alkyl group, and Z ¹ and A compound in which the hydrogen atom of the hydroxyl group at the carboxy group terminal in Z ² is not substituted with the alkyl group is preferred.

Component (A1) is one in which one —OH is substituted with —OR ¹ and one to three —OH is substituted with —OR ² in —OH in the unprotected form.
When the unprotected body has both a phenolic hydroxyl group and a carboxylic acid hydroxyl group, among the —OH in the unprotected body, “—OH” substituted with —OR ¹ or —OR ² is a phenolic hydroxyl group. It may be a carboxylic acid hydroxyl group, and a carboxylic acid hydroxyl group is preferred.
When the unprotected body does not have a carboxylic acid hydroxyl group, the phenolic hydroxyl group in the unprotected body is substituted with -OR ¹ or -OR ² .

In the present invention, the component (A1) is such that the unprotected body has (n ₁₂ +1) or more carboxylic acid hydroxyl groups, and one of the carboxylic acid hydroxyl groups of the unprotected body is substituted with —OR ^1. It is preferable that 1 to 3 of the remaining carboxylic acid hydroxyl groups are substituted with —OR ² . That is, the component (A1) has one —C (═O) —O—R ¹ and one to three —C (═O) —O—R ² in the structure. preferable.
When the component (A1) has such a structure, a carboxy group having a stronger acidity than the phenolic hydroxyl group is formed when R ¹ is dissociated in the exposed area when forming a resist pattern. Will improve. In addition, by protecting the carboxy group with R ² , it is possible to control the solubility in an alkali developer after exposure and to control thermophysical properties, and to suppress pattern collapse and improve substrate adhesion. Effects such as can be obtained. Therefore, resolution, pattern shape, etc. are improved. In addition, since the carboxylic acid hydroxyl group is more reactive with the phenolic hydroxyl group and the carboxylic acid hydroxyl group, R ¹ and R ² can be easily selectively introduced only into the carboxylic acid hydroxyl group, and the production thereof is easy. .
The component (A1) may have a carboxylic acid hydroxyl group that is not substituted with —OR ¹ or —OR ² . However, considering the ease of synthesis of the component (A1), the number of carboxylic acid hydroxyl groups in the component (A1) is most preferably 0. That is, the component (A1) preferably has no carboxy group.

  As the component (A1), a compound represented by the following general formula (A1-11) is particularly preferable.

［式中、ｎ_１３は１〜３の整数であり；Ａは（ｎ_１３＋１）価の連結部であり；ａおよびｎ１はそれぞれ独立に１以上の整数であり、ｎ２およびｎ５はそれぞれ独立に０以上の整数であり、かつａ＋ｎ１＋ｎ２＋ｎ５が５以下であり；ｎ３’およびｎ４’はそれぞれ独立に０以上の整数であり、かつｎ３’＋ｎ４’が３以下であり；ｎ６’およびｎ７’はそれぞれ独立に０以上の整数であり、かつｎ６’＋ｎ７’が３以下であり；Ｒ^１０１〜Ｒ^１０７はそれぞれ独立に炭素数１〜１０のアルキル基または芳香族炭化水素基であって、その構造中にヘテロ原子を含んでもよく；Ｒ^３は置換基を有していてもよい２価の炭化水素基であり、式中の複数のＲ^３はそれぞれ同じであっても異なっていてもよく；Ｒ^１は前記と同じであり；Ｌ^１は−Ｒ^４−Ｃ（＝Ｏ）−Ｏ−（Ｒ^４は２価の連結基である。）または単結合であり；Ｚ^１１は、Ｒ^２（Ｒ^２は前記と同じである。）または水素原子であって、ｎ_１３が１の場合はＲ^２であり、ｎ_１３が２または３の場合、式中の２または３個のＺ^１１のうち少なくとも１つはＲ^２である。］

[Wherein n ₁₃ is an integer of 1 to 3; A is a (n ₁₃ +1) -valent linking moiety; a and n 1 are each independently an integer of 1 or more, and n 2 and n 5 are each independently N is an integer of 0 or more, and a + n1 + n2 + n5 is 5 or less; n3 ′ and n4 ′ are each independently an integer of 0 or more, and n3 ′ + n4 ′ is 3 or less; n6 ′ and n7 ′ are each independent And n6 ′ + n7 ′ is 3 or less; R ^{101 to} R ¹⁰⁷ are each independently an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group, May contain a heteroatom; R ³ is a divalent hydrocarbon group which may have a substituent, and a plurality of R ³ in the formula may be the same or different from each other; R ¹ It is the same as above; ^{L 1} is -R ⁴ - (= O) -O- ^{(R 4} represents a divalent linking group.) Or a single ^{bond; Z 11 is,} R 2 (. ^{R 2} is the same as defined above) or a hydrogen atom, When n ₁₃ is 1, it is R ² , and when n ₁₃ is 2 or 3, at least one of 2 or 3 Z ^{11 in} the formula is R ² . ]

Wherein _{(A1-11), n 13, A} , a, n1, n2, n5, n3 ', n4', n6 ', n7', R 101 ~R 107 each Formula (I-31-1) in N ₁₃ , A, a, n 1, n 2, n 5, n 3 ′, n 4 ′, n 6 ′, n 7 ′, and the same as R ^{101 to} R ¹⁰⁷ .
R ³ is the same as ^{R 3} in the general formula (z1).
L ¹ is ^{-R 4 -C (= O) -O-} (R 4 represents a divalent linking group.) Or a single bond, wherein ^{R 4} is a ^{R 4} in the general formula (z2) It is the same.
R ¹ is the same as ^{R 1} in the general formula (A1-1).
In Z ^{11, R 2} is the same as ^{R 2} in the general formula (A1-1).

The component (A1) is a material that can form an amorphous film by spin coating. Here, the amorphous film means an optically transparent film that does not crystallize. The spin coating method is one of generally used thin film forming methods.
Whether or not the compound is a material capable of forming an amorphous film by spin coating can be determined by whether or not the coating film formed by spin coating on an 8-inch silicon wafer is entirely transparent. More specifically, for example, the determination can be made as follows. First, for the compound, a solvent generally used as a resist solvent is used, for example, a mixed solvent of ethyl lactate / propylene glycol monomethyl ether acetate = 40/60 (mass ratio) (hereinafter abbreviated as EM). The solution is dissolved so as to have a concentration of 14% by mass, and is subjected to ultrasonic treatment (dissolution treatment) using an ultrasonic cleaner, and the solution is spin-coated on a wafer at 1500 rpm and optionally dried and baked. (PAB, Post Applied Bake) is applied under conditions of 110 ° C. and 90 seconds, and in this state, it is visually confirmed whether an amorphous film is formed depending on whether it is transparent or not. A cloudy film that is not transparent is not an amorphous film.
In the present invention, the component (A1) preferably has good stability of the amorphous film formed as described above. For example, after the PAB, the amorphous film is amorphous even after being left in a room temperature environment for 2 weeks. It is preferable that the state is maintained.

The manufacturing method of (A1) component is not specifically limited. For example, a part of —OH hydrogen atom in the unprotected or precursor compound thereof is substituted with —R ² (R ² is the same as above), and —OH hydrogen atom in the obtained compound Can be produced by substituting -L ¹ -R ¹ (L ¹ and R ¹ are the same as defined above), respectively.
The introduction of —R ² or —L ¹ —R ¹ (substitution of —OH hydrogen atom) utilizes a well-known method conventionally used for introducing a substituent into a phenolic hydroxyl group or a carboxy group, respectively. Can be implemented. For example, by reacting X—R ² or X—L ¹ —R ¹ (X is a hydroxy group or a halogen atom), the —OH hydrogen atom can be replaced with —R ² or —L ¹ —R ¹ .
When -R ² or -L ¹ -R ¹ is introduced, if -OH having the same reactivity is present in the unprotected form, the number of introduced -R ² or -L ¹ -R ¹ is different. In this case, since the molecular weight, polarity, alkali solubility, etc. are different for each molecule, -R ² or -L ¹ -R ¹ is introduced by performing column chromatography using a silica gel column, for example. Molecules with different numbers can be separated.
The number of —R ² or —L ¹ —R ¹ introduced into the molecule can be confirmed by NMR (nuclear magnetic resonance spectrum) such as proton-NMR and carbon NMR.

In the component (A), the component (A1) may be used alone or in combination of two or more.
In the component (A), the proportion of the component (A1) is preferably more than 40% by mass, more preferably more than 50% by mass, further preferably more than 80% by mass, most preferably 100% by mass. is there. The proportion of the component (A1) in the component (A) can be measured by means such as reverse phase chromatography.

The component (A) is further a “base component whose solubility in an alkali developer is increased by the action of an acid” other than the compound (A1) within the range not impairing the effect of using the component (A1) (hereinafter referred to as “component (A1)”). , (Referred to as component (A2)).
Examples of the component (A2) include those proposed as base resins such as conventional chemically amplified positive resist compositions for chemically amplified KrF and ArF positive resist compositions. It can be appropriately selected according to the type of the above. As the component (A2), a resin whose solubility in an alkaline developer is increased by the action of an acid, or a low molecular compound whose solubility in an alkali developer is increased by the action of an acid may be used. May be used in combination.
The content of the component (A) in the positive resist composition may be adjusted according to the resist film thickness to be formed.

<(B) component>
The component (B) is not particularly limited, and those that have been proposed as acid generators for chemically amplified resists can be used. Examples of such acid generators include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyldiazomethanes, and poly (bissulfonyl) diazomethanes. There are various known diazomethane acid generators, nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, disulfone acid generators, and any of them can be used.

  As the onium salt acid generator, for example, a compound represented by the following general formula (b-1) or (b-2) can be used.

［式中、Ｒ^１”〜Ｒ^３”，Ｒ^５”〜Ｒ^６”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またはアルキル基を表し；式（ｂ−１）におけるＲ^１”〜Ｒ^３”のうち、いずれか２つが相互に結合して式中のイオウ原子と共に環を形成してもよく；Ｒ^４”は、置換基を有していても良いアルキル基、ハロゲン化アルキル基、アリール基、またはアルケニル基を表し；Ｒ^１”〜Ｒ^３”のうち少なくとも１つはアリール基を表し、Ｒ^５”〜Ｒ^６”のうち少なくとも１つはアリール基を表す。］

[Wherein, R ¹ ″ to R ³ ″ and R ⁵ ″ to R ⁶ ″ each independently represents an aryl group or an alkyl group which may have a substituent; R in the formula (b-1) Any one of ¹ ″ to R ³ ″ may be bonded to each other to form a ring together with the sulfur atom in the formula; R ⁴ ″ represents an alkyl group which may have a substituent, a halogen atom; An alkyl group, an aryl group, or an alkenyl group; at least one of R ¹ ″ to R ³ ″ represents an aryl group, and at least one of R ⁵ ″ to R ⁶ ″ represents an aryl group.]

In formula (b-1), R ¹ ″ to R ³ ″ each independently represents an aryl group or an alkyl group which may have a substituent. In addition, any two of R ¹ ″ to R ³ ″ in formula (b-1) may be bonded to each other to form a ring together with the sulfur atom in the formula.
Further, at least one of R ¹ ″ to R ³ ″ represents an aryl group. Of R ¹ ″ to R ³ ″, two or more are preferably aryl groups, and most preferably all of R ¹ ″ to R ³ ″ are aryl groups.

The aryl group for R ¹ ″ to R ³ ″ is not particularly limited, and examples thereof include an aryl group having 6 to 20 carbon atoms. The aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at a low cost. Specific examples include a phenyl group and a naphthyl group.
The aryl group may have a substituent. “Having a substituent” means that part or all of the hydrogen atoms of the aryl group are substituted with a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, An alkoxyalkyloxy group, —O—R ⁵⁰ —CO—O—R ^{51 wherein} R ⁵⁰ is an alkylene group and R ⁵¹ is an acid-dissociable group; ] Etc. are mentioned.
The alkyl group that may be substituted for the hydrogen atom of the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and is a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Is most preferred.
As the alkoxy group that may be substituted for the hydrogen atom of the aryl group, 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, A tert-butoxy group is preferable, and a methoxy group and an ethoxy group are most preferable.
The halogen atom that may be substituted with the hydrogen atom of the aryl group is preferably a fluorine atom.

Examples of the alkoxyalkyloxy group in which the hydrogen atom of the aryl group may be substituted include, for example, —O—C (R ⁴⁷ ) (R ⁴⁸ ) —O—R ^{49 wherein} R ⁴⁷ and R ⁴⁸ are each It is independently a hydrogen atom or a linear or branched alkyl group, R ⁴⁹ is an alkyl group, and R ⁴⁸ and R ⁴⁹ may be bonded to each other to form one ring structure. Provided ^that at least one of ^{R 47} and ^{R 48} are hydrogen atoms. ].
In R ⁴⁷ and R ⁴⁸ , the alkyl group preferably has 1 to 5 carbon atoms, preferably an ethyl group or a methyl group, and most preferably a methyl group.
One of R ⁴⁷ and R ⁴⁸ is preferably a hydrogen atom, the other is preferably a hydrogen atom or a methyl group, and both R ⁴⁷ and R ⁴⁸ are particularly preferably hydrogen atoms.
The alkyl group for R ⁴⁹ preferably has 1 to 15 carbon atoms and may be linear, branched or cyclic.
The linear or branched alkyl group for R ⁴⁹ preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group. Can be mentioned.
The cyclic alkyl group for R ⁴⁹ preferably has 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms.
Specifically, monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane, etc., which may or may not be substituted with an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a fluorinated alkyl group, etc. And a group obtained by removing one or more hydrogen atoms from the polycycloalkane. Examples of the monocycloalkane include cyclopentane and cyclohexane. Examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among them, a group obtained by removing one or more hydrogen atoms from adamantane is preferable.
R ⁴⁸ and R ⁴⁹ may be bonded to each other to form one ring structure. In this case, the R ⁴⁸ and R ^49, the oxygen atom having R ⁴⁹ is bonded, a cyclic group is formed by the carbon atom having the oxygen atom and R ⁴⁸ are bonded. The cyclic group is preferably a 4-7 membered ring, and more preferably a 4-6 membered ring.

In —O—R ⁵⁰ —CO—O—R ⁵¹ in which the hydrogen atom of the aryl group may be substituted, the alkylene group in R ⁵⁰ is preferably a linear or branched alkylene group, and the carbon number thereof Is preferably 1-5. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a 1,1-dimethylethylene group.
The acid dissociable group in R ⁵¹ is not particularly limited as long as it is an organic group that can be dissociated by the action of an acid (acid generated from the component (B) at the time of exposure). Examples include the same acid dissociable, dissolution inhibiting groups. Among them, the tertiary alkyl ester type is preferable.

The alkyl group for R 1 ^{"~R 3",} is not particularly limited, for example, linear C1-10, branched or cyclic alkyl group, and the like. It is preferable that it is C1-C5 from the point which is excellent in resolution. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a nonyl group, and a decanyl group. A methyl group is preferable because it is excellent in resolution and can be synthesized at low cost.
The alkyl group may have a substituent. “Having a substituent” means that part or all of the hydrogen atoms of the alkyl group are substituted with a substituent, and the substituent may be a substituent that the aryl group may have. The thing similar to what was mentioned as a group is mentioned.

When any two of R ¹ ″ to R ³ ″ in formula (b-1) are bonded to each other to form a ring together with the sulfur atom in the formula, a 3 to 10 membered ring including the sulfur atom is formed. It is preferable that a 5- to 7-membered ring is formed.
When any two of R ¹ ″ to R ³ ″ in formula (b-1) are bonded to each other to form a ring together with the sulfur atom in the formula, the remaining one may be an aryl group preferable. Examples of the aryl group are the same as the aryl groups of R ¹ ″ to R ³ ″.

Of the cation moieties of the compound represented by formula (b-1), when R ¹ ″ to R ³ ″ are all phenyl groups that may have a substituent, that is, the cation moiety is triphenylmethane. Specific examples of preferred skeletons include cation moieties represented by the following formulas (I-1-1) to (I-1-8).
Moreover, what substituted a part or all of the phenyl group in these cation parts with the naphthyl group which may have a substituent is mentioned as a preferable thing. Of the three phenyl groups, 1 or 2 is preferably substituted with the naphthyl group.

Moreover, among the cation moieties of the compound represented by the formula (b-1), any two of R ¹ ″ to R ³ ″ are bonded to each other to form a ring together with the sulfur atom in the formula. Preferable specific examples of the case include, for example, cation moieties represented by the following formulas (I-1-10) to (I-1-11).
In the following formula (I-1-10), R ⁹ is a phenyl group, a naphthyl group, or an alkyl group having 1 to 5 carbon atoms which may have a substituent.
In the following formula (I-1-11), R ¹⁰ represents a phenyl group, a naphthyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a hydroxyl group, which may have a substituent.
u is an integer of 1 to 3, and 1 or 2 is most preferable.

［式中、Ｒ^９は、置換基を有していてもよいフェニル基、ナフチル基または炭素数１〜５のアルキル基であり、Ｒ^１０は、置換基を有していてもよいフェニル基、ナフチル基、炭素数１〜５のアルキル基、アルコキシ基または水酸基であり、ｕは１〜３の整数である。］

[Wherein, R ⁹ is a phenyl group optionally having a substituent, a naphthyl group or an alkyl group having 1 to 5 carbon atoms, and R ¹⁰ is a phenyl group optionally having a substituent, A naphthyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group or a hydroxyl group, and u is an integer of 1 to 3; ]

R ⁴ ″ represents an alkyl group, a halogenated alkyl group, an aryl group, or an alkenyl group which may have a substituent.
The alkyl group for R ⁴ ″ may be linear, branched or cyclic.
The linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
The cyclic alkyl group preferably has 4 to 15 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms.
Examples of the halogenated alkyl group for R ⁴ ″ include groups in which part or all of the hydrogen atoms of the linear, branched, or cyclic alkyl group have been substituted with halogen atoms. A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable.
In the halogenated alkyl group, the ratio of the number of halogen atoms to the total number of halogen atoms and hydrogen atoms contained in the halogenated alkyl group (halogenation rate (%)) is preferably 10 to 100%. 50 to 100% is preferable, and 100% is most preferable. The higher the halogenation rate, the better the acid strength.
The aryl group for R ⁴ ″ is preferably an aryl group having 6 to 20 carbon atoms.
The alkenyl group in R ⁴ ″ is preferably an alkenyl group having 2 to 10 carbon atoms.
In the above R ⁴ ″, “optionally substituted” means one of hydrogen atoms in the linear, branched or cyclic alkyl group, halogenated alkyl group, aryl group, or alkenyl group. It means that part or all may be substituted with a substituent (an atom or group other than a hydrogen atom).
The number of substituents in R ⁴ ″ may be one or two or more.

Examples of the substituent include a halogen atom, a hetero atom, an alkyl group, an oxygen atom (═O), a formula: ZQ ¹ — [wherein Q ¹ is a divalent linking group containing an oxygen atom, Z is a hydrocarbon group having 3 to 30 carbon atoms which may have a substituent. ] Etc. which are represented by these.
Examples of the halogen atom include the same halogen atoms as those described above for the halogenated alkyl group mentioned for R ⁴ ″.
Examples of the alkyl group include the same alkyl groups as those described above for R ⁴ ″.
Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.

Z-Q 1 ^- In the group represented by, Q ¹ represents a divalent linking group containing an oxygen atom.
Q ¹ may contain an atom other than an oxygen atom. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, oxygen atoms, sulfur atoms, and nitrogen atoms.
Examples of the divalent linking group containing an oxygen atom include an oxygen atom (ether bond; —O—), an ester bond (—C (═O) —O—), and an amide bond (—C (═O) —NH. -), A carbonyl group (-C (= O)-), a non-hydrocarbon oxygen atom-containing linking group such as a carbonate bond (-O-C (= O) -O-); the non-hydrocarbon oxygen atom Examples include a combination of a containing linking group and an alkylene group.
Examples of the combination include —R ⁹¹ —O—, —R ⁹² —O—C (═O) —, —C (═O) —O—R ⁹³ —O—C (═O) —, —O. —R ⁹³ —O—C (═O) —, —R ⁹² —O—C (═O) —R ⁹³ —O—C (═O) — (wherein R ^{91 to} R ⁹³ are each independently alkylene. Group.) And the like.
The alkylene group for R ^{91 to} R ⁹³ is preferably a linear or branched alkylene group, and the alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms. preferable.
Specific examples of the alkylene group include a methylene group [—CH ₂ —]; —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ) ₂ —, —C ( _{CH 3) (CH 2 CH 3} ) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as ethylene group _[-CH 2 CH _2— ]; —CH (CH ₃ ) CH ₂ —, —CH (CH ₃ ) CH (CH ₃ ) —, —C (CH ₃ ) ₂ CH ₂ —, —CH (CH ₂ CH ₃ ) CH ₂ — and the like. Alkylethylene groups; trimethylene groups (n-propylene groups) [—CH ₂ CH ₂ CH ₂ —]; alkyls such as —CH (CH ₃ ) CH ₂ CH ₂ — and —CH ₂ CH (CH ₃ ) CH ₂ — trimethylene; tetramethylene group _[-CH 2 _CH 2 C _{2 CH 2 -]; - CH} (CH 3) CH 2 CH 2 CH 2 -, - CH 2 CH (CH 3) CH 2 CH 2 - alkyl tetramethylene group and the like; pentamethylene group _[-CH 2 _CH 2 CH ₂ CH ₂ CH ₂ —] and the like.
Q ¹ is preferably a divalent linking group containing an ester bond and / or an ether bond, and in particular, —O—, —R ⁹¹ —O—, —R ⁹² —O—C (═O) —, — C (═O) —O—, —C (═O) —O—R ⁹³ —, —C (═O) —O—R ⁹³ —O—C (═O) —, —O—R ⁹³ —O —C (═O) —, —R ⁹² —O—C (═O) —R ⁹³ —O—C (═O) — are preferred.

In the group represented by ZQ ^1- , the hydrocarbon group of Z may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.
The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, 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 hydrocarbon group include a hydrogen atom from an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. Examples include aryl groups such as aryl group, benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc., from which one is removed. The number of carbon atoms of the alkyl chain in the arylalkyl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
The aromatic hydrocarbon group may have a substituent. For example, a part of carbon atoms constituting the aromatic ring of the aromatic hydrocarbon group may be substituted with a hetero atom, and the hydrogen atom bonded to the aromatic ring of the aromatic hydrocarbon group is substituted with the substituent. May be.
Examples of the former include heteroaryl groups in which some of the carbon atoms constituting the ring of the aryl group are substituted with heteroatoms such as oxygen atoms, sulfur atoms and nitrogen atoms, and aromatic hydrocarbons in the arylalkyl groups Examples include heteroarylalkyl groups in which some of the carbon atoms constituting the ring are substituted with the above heteroatoms.
Examples of the substituent of the aromatic hydrocarbon group in the latter example include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (═O), —COOR ″, and —OC (═O). R ″, a hydroxyalkyl group, a cyano group and the like can be mentioned. R ″ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms.

The alkyl group as a substituent of the aromatic hydrocarbon group is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. preferable.
The alkoxy group as a substituent of the aromatic hydrocarbon group is preferably an alkoxy group having 1 to 5 carbon atoms, and is a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert- A butoxy group is preferable, and a methoxy group and an ethoxy group are most preferable.
Examples of the halogen atom as a substituent for the aromatic hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent of the aromatic hydrocarbon group include groups in which part or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms.
R ″ in —COOR ″ and —OC (═O) R ″ as a substituent of the aromatic hydrocarbon group is the same as R ″ in the structural unit (a2).
Examples of the hydroxyalkyl group as the substituent of the aromatic hydrocarbon group include groups in which at least one hydrogen atom of the alkyl group mentioned as the substituent is substituted with a hydroxyl group.

As the aromatic hydrocarbon group for Z, an aryl group, arylalkyl group or heteroaryl group which may have a substituent is preferable.
The aryl group is preferably an unsubstituted aryl group or an aryl group having a halogen atom as a substituent (halogenated aryl group), particularly preferably a phenyl group, a naphthyl group, or a fluorinated phenyl group.
As the arylalkyl group, an alkyl group is preferably a methyl group, and a naphthylmethyl group or a benzyl group is preferable.
As the heteroaryl group, those containing a nitrogen atom as a hetero atom are preferred, and a group obtained by removing one hydrogen atom from pyridine is particularly preferred.

The aliphatic hydrocarbon group in Z may be a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, or a combination thereof. The aliphatic hydrocarbon group may be linear, branched or cyclic.
In Z, the aliphatic hydrocarbon group may have a part of the carbon atoms constituting the aliphatic hydrocarbon group substituted with a substituent containing a hetero atom, and the hydrogen atom constituting the aliphatic hydrocarbon group May be substituted with a substituent containing a hetero atom.
The “heteroatom” in Z is not particularly limited as long as it is an atom other than a carbon atom and a hydrogen atom, and examples thereof include a halogen atom, an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom.
The substituent containing a hetero atom may be composed only of the hetero atom, or may be a group containing a group or atom other than the hetero atom.
Specific examples of the substituent for substituting a part of carbon atoms include, for example, —O—, —C (═O) —O—, —C (═O) —, —O—C (═O) —O. -, - C (= O) -NH -, - NH- (H is an alkyl group, may be substituted with a substituent such as an acyl group), - S -, - S (= O) 2 -, - S (= O) ₂ —O— and the like can be mentioned. When the aliphatic hydrocarbon group is cyclic, these substituents may be included in the ring structure.
Specific examples of the substituent that substitutes part or all of the hydrogen atoms include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (═O), and a cyano group.
The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and a methoxy group or an ethoxy group. Is most preferred.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable.
As the halogenated alkyl group, a part or all of hydrogen atoms of an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, etc. And a group substituted with a halogen atom.

Examples of the aliphatic hydrocarbon group include a linear or branched saturated hydrocarbon group, a linear or branched monovalent unsaturated hydrocarbon group, and a cyclic aliphatic hydrocarbon group (aliphatic cyclic group). Group) or a combination thereof.
The linear saturated hydrocarbon group (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, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group Group, pentadecyl group, hexadecyl group, isohexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group and the like.
The branched saturated hydrocarbon group (alkyl group) preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, for example, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, Examples include 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group and the like.

As an unsaturated hydrocarbon group, it is preferable that carbon number is 2-10, 2-5 are preferable, 2-4 are preferable, and 3 is especially preferable. Examples of the linear monovalent unsaturated hydrocarbon group include a vinyl group, a propenyl group (allyl group), and a butynyl group. Examples of the branched monovalent unsaturated hydrocarbon group include a 1-methylpropenyl group and a 2-methylpropenyl group.
Among the above, the unsaturated hydrocarbon group is particularly preferably a propenyl group.

The aliphatic cyclic group may be a monocyclic group or a polycyclic group. The number of carbon atoms is preferably 3 to 30, more preferably 5 to 30, further preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12.
Specifically, for example, a group in which one or more hydrogen atoms have been removed from a monocycloalkane; a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as bicycloalkane, tricycloalkane, tetracycloalkane, etc. Can be mentioned. More specifically, a group in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane; one or more polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. Examples include a group excluding a hydrogen atom.
When the aliphatic cyclic group does not contain a substituent containing a hetero atom in the ring structure, the aliphatic cyclic group is preferably a polycyclic group, and one or more hydrogen atoms from the polycycloalkane are substituted. Excluded groups are preferred, and groups obtained by removing one or more hydrogen atoms from adamantane are most preferred.
When the aliphatic cyclic group includes a substituent containing a hetero atom in the ring structure, examples of the substituent containing a hetero atom include —O—, —C (═O) —O—, —S—. , —S (═O) ₂ — and —S (═O) ₂ —O— are preferable. Specific examples of the aliphatic cyclic group include the following formulas (L1) to (L5), (S1) to (S4), and the like.

［式中、Ｑ”は炭素数１〜５のアルキレン基、−Ｏ−、−Ｓ−、−Ｏ−Ｒ^９４−または−Ｓ−Ｒ^９５−であり、Ｒ^９４およびＲ^９５はそれぞれ独立に炭素数１〜５のアルキレン基であり、ｍは０または１の整数である。］

[Wherein, Q ″ is an alkylene group having 1 to 5 carbon atoms, —O—, —S—, —O—R ⁹⁴ — or —S—R ⁹⁵ —, wherein R ⁹⁴ and R ⁹⁵ are each independently carbon. An alkylene group of 1 to 5 and m is an integer of 0 or 1.]

In the formula, examples of the alkylene group for Q ″, R ⁹⁴ and R ⁹⁵ include the same alkylene groups as those described above for R ^{91 to} R ⁹³ .
In these aliphatic cyclic groups, a part of hydrogen atoms bonded to carbon atoms constituting the ring structure may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and an oxygen atom (═O).
The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, particularly preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
Examples of the alkoxy group and the halogen atom are the same as those exemplified as the substituent for substituting part or all of the hydrogen atoms.

In the present invention, Z preferably has a cyclic group which may have a substituent. The cyclic group may be an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a substituent. It is preferably an aliphatic cyclic group that may be used.
The aromatic hydrocarbon group is preferably a naphthyl group which may have a substituent or a phenyl group which may have a substituent.
As the aliphatic cyclic group which may have a substituent, a polycyclic aliphatic cyclic group which may have a substituent is preferable. The polycyclic aliphatic cyclic group is preferably a group obtained by removing one or more hydrogen atoms from the polycycloalkane, the above (L2) to (L5), (S3) to (S4), and the like.

In the present invention, ^{R 4} ", ^{Z-Q 1} - as a substituent preferably has the case, ^{R 4."} The, ^{Z-Q 1} -Y 1 - in the Formula, ^{Q 1} and Z is the And Y ¹ is an optionally substituted alkylene group having 1 to 4 carbon atoms or an optionally substituted fluorinated alkylene group having 1 to 4 carbon atoms. ] Is preferable.
That is, R ⁴ ″ —SO ₃ ^— is preferably an anion represented by the following general formula (x-11).

［式中、Ｑ^１は酸素原子を含む２価の連結基であり、Ｚは置換基を有していてもよい炭素数３〜３０の炭化水素基であり、Ｙ^１は置換基を有していてもよい炭素数１〜４のアルキレン基または置換基を有していてもよい炭素数１〜４のフッ素化アルキレン基である。］

[Wherein, Q ¹ is a divalent linking group containing an oxygen atom, Z is an optionally substituted hydrocarbon group having 3 to 30 carbon atoms, and Y ¹ has a substituent. Or an optionally substituted alkylene group having 1 to 4 carbon atoms or an optionally substituted fluorinated alkylene group having 1 to 4 carbon atoms. ]

In formula (x-11), Z and Q ¹ are the same as defined above.
Examples of the alkylene group for Y ¹ include the same alkylene groups as those described above for Q ¹ having 1 to 4 carbon atoms.
Examples of the fluorinated alkylene group include groups in which part or all of the hydrogen atoms of the alkylene group have been substituted with fluorine atoms.
As Y ^1, _{specifically, -CF 2 -, - CF 2} CF 2 -, - CF 2 CF 2 CF 2 -, - CF (CF 3) CF 2 -, - CF (CF 2 CF 3) -, _{-C (CF 3) 2 -,} - CF 2 CF 2 CF 2 CF 2 -, - CF (CF 3) CF 2 CF 2 -, - CF 2 CF (CF 3) CF 2 -, - CF (CF 3) CF (CF ₃ ) —, —C (CF ₃ ) ₂ CF ₂ —, —CF (CF ₂ CF ₃ ) CF ₂ —, —CF (CF ₂ CF ₂ CF ₃ ) —, —C (CF ₃ ) (CF _{2 CF 3) -; - CHF} -, - CH 2 CF 2 -, - CH 2 CH 2 CF 2 -, - CH 2 CF 2 CF 2 -, - CH (CF 3) CH 2 -, - CH (CF 2 _{CF 3) -, - C (} CH 3) (CF 3) -, - CH 2 CH 2 CH 2 CF 2 -, - C H ₂ CH ₂ CF ₂ CF ₂ —, —CH (CF ₃ ) CH ₂ CH ₂ —, —CH ₂ CH (CF ₃ ) CH ₂ —, —CH (CF ₃ ) CH (CF ₃ ) —, —C ( _{CF 3) 2 CH 2 -;} - CH 2 -, - CH 2 CH 2 -, - CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 -, - CH (CH 2 CH 3) -, - _{C (CH 3) 2 -,} - CH 2 CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 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) CH 2 -, - CH (CH 2 CH 2 CH 3) -, - C (CH 3) (CH 2 CH ₃ ) — and the like.

Y ¹ is preferably a fluorinated alkylene group, and particularly preferably a fluorinated alkylene group in which the carbon atom bonded to the adjacent sulfur atom is fluorinated. Examples of such fluorinated alkylene _{group, -CF 2 -, - CF 2} CF 2 -, - CF 2 CF 2 CF 2 -, - CF (CF 3) CF 2 -, - CF 2 CF 2 CF 2 CF 2 _{-, - CF (CF 3)} CF 2 CF 2 -, - CF 2 CF (CF 3) CF 2 -, - CF (CF 3) CF (CF 3) -, - C (CF 3) 2 CF 2 -, _{-CF (CF 2 CF 3) CF} 2 -; - CH 2 CF 2 -, - CH 2 CH 2 CF 2 -, - CH 2 CF 2 CF 2 -; - CH 2 CH 2 CH 2 CF 2 -, - CH ₂ CH ₂ CF ₂ CF ₂ —, —CH ₂ CF ₂ CF ₂ CF ₂ — and the like can be mentioned.
Of _{these, -CF 2 -, - CF 2} CF 2 -, - CF 2 CF 2 CF 2 -, or _CH 2 _CF 2 CF ₂ - is _{preferable, -CF 2 -, - CF 2} CF 2 - or -CF ₂ CF ₂ CF ₂ - is more preferable, -CF ₂ - is particularly preferred.

The alkylene group or fluorinated alkylene group may have a substituent. An alkylene group or a fluorinated alkylene group has a “substituent” means that part or all of the hydrogen atom or fluorine atom in the alkylene group or fluorinated alkylene group is substituted with an atom or group other than a hydrogen atom and a fluorine atom. Means that
Examples of the substituent that the alkylene group or fluorinated alkylene group may have include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyl group.

  Preferable examples of the anion represented by the formula (x-11) include anions represented by the following general formula (x-11-1).

［式中、Ｚは前記と同じであり、Ｑ^２は単結合またはアルキレン基であり、ｐは１〜３の整数であり、ｍ１〜ｍ４はそれぞれ独立に０または１である。ただし、ｍ２＋ｍ３は１または２である。］

[In the formula, Z is the same as defined above, Q ² is a single bond or an alkylene group, p is an integer of 1 to 3, and m1 to m4 are each independently 0 or 1. However, m2 + m3 is 1 or 2. ]

In the formula (x-11-1), p is an integer of 1 to 3, and 1 or 2 is preferable.
Examples of the alkylene group for Q ² include the same alkylene groups as R ^{91 to} R ⁹³ in the description of Q ¹ .
m1 to m4 are each 0 or 1. However, m2 + m3 is 1 or 2.

  More specifically, as an anion represented by the formula (x-11-1), an anion represented by the following general formula (x-11-10), represented by the general formula (x-11-20) And an anion represented by the general formula (x-11-40), an anion represented by the general formula (x-11-40), and the like.

..Anions represented by general formula (x-11-10)

［式（ｘ−１１−１０）中、Ｚ、Ｑ^２、ｍ３およびｐはそれぞれ前記と同じである。］

[In the formula (x-11-10), Z, Q ² , m3 and p are the same as defined above. ]

In formula (x-11-10), as Z, an aliphatic cyclic group which may have a substituent, a linear aliphatic hydrocarbon group which may have a substituent, or a substituent An aromatic hydrocarbon group which may have a group is preferred. Among these, an aliphatic cyclic group containing a substituent containing a hetero atom in the ring structure is preferable.
Q ² is particularly preferably a single bond or a methylene group. Among them, when Z is an aliphatic cyclic group which may have a substituent, Q ² is preferably a single bond. Further, Z is, if substituted also aromatic hydrocarbon group is preferably Q ² is a methylene group.
Specific examples of suitable anions represented by general formula (x-11-10) are shown below.

［式中、Ｑ”、ｍ３およびｐはそれぞれ前記と同じであり、Ｒ^７およびＲ^７’はそれぞれ独立に置換基であり、ｗ１〜ｗ６はそれぞれ独立に０〜３の整数であり、ｖ１〜ｖ２はそれぞれ独立に０〜５の整数である。］

Wherein, Q ", m3 and p are the same as defined above, a substituent, each ^{R 7} and ^{R 7} 'are independently, W1 to W6 are each independently an integer of 0 to 3, V1 to v2 is each independently an integer of 0 to 5.]

In the formula, examples of the substituent for R ⁷ include the same substituents as those described above as the substituent that the aliphatic hydrocarbon group may have in Z.
In the formula, examples of the substituent for R ⁷ ′ include the same groups as those described above for Z as the substituent that the aromatic hydrocarbon group may have.
^'If the sign attached to (W1 to W6) is an integer of 2 or more, a plurality of R ⁷ or R ⁷ in the ^compound' R ⁷ or R ⁷ may be the same, respectively, be different Good.
w1 to w6 are each independently preferably 0 to 2, and most preferably 0.
v1 to v2 are each independently preferably 0 to 3, and most preferably 0.

..Anions represented by general formula (x-11-20)

［式（ｘ−１１−２０）中、Ｚおよびｐはそれぞれ前記と同じであり、Ｑ^３はアルキレン基である。］

[In formula (x-11-20), Z and p are the same as defined above, and Q ³ represents an alkylene group. ]

In formula (x-11-20), as Z, an aliphatic cyclic group which may have a substituent, a linear aliphatic hydrocarbon group which may have a substituent, or a substituent An aromatic hydrocarbon group which may have a group is preferred.
As the alkylene group for Q ^3, the same alkylene groups as those described above for R ^{91 to} R ⁹³ in the description of Q ¹ can be given.
Specific examples of preferable anions represented by general formula (x-11-20) are shown below.

［式中、ｐ、Ｒ^７およびＲ^７’はそれぞれ前記と同じであり、ｖ０は０〜３の整数であり、ｗ７〜ｗ９はそれぞれ独立に０〜３の整数であり、ｑ１は１〜１２の整数であり、ｇは１〜２０の整数である。］

[Wherein, p, R ⁷ and R ⁷ ′ are the same as defined above, v0 is an integer of 0 to 3, w7 to w9 are each independently an integer of 0 to 3, and q1 is 1 to 12] G is an integer of 1-20. ]

^'If the sign attached to (w7~w9) is an integer of 2 or more, a plurality of R ⁷ or R ⁷ in the ^compound' R ⁷ or R ⁷ may be the same, respectively, be different Good.
w7 to w9 are each independently preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
q1 is preferably 1 to 8, more preferably 1 to 5, and still more preferably 1 to 3.
g is preferably from 1 to 15, and more preferably from 1 to 10.
p is preferably 1 or 2, and most preferably 1.

..Anions represented by general formula (x-11-30)

［式（ｘ−１１−３０）中、ｐは前記と同じであり、ｑ２は０〜５の整数であり；Ｒ^７０”はアルキル基、アルコキシ基、ハロゲン原子（ただし、フッ素原子を除く。）、ハロゲン化アルキル基、水酸基、酸素原子（＝Ｏ）、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基又はシアノ基であり；ｒ１は０〜２の整数であり、ｒ２は１〜５の整数であり、１≦ｒ１＋ｒ２≦５である。］

[In formula (x-11-30), p is the same as defined above, q2 is an integer of 0 to 5; R ⁷⁰ ″ represents an alkyl group, an alkoxy group, or a halogen atom (excluding a fluorine atom). , A halogenated alkyl group, a hydroxyl group, an oxygen atom (═O), —COOR ″, —OC (═O) R ″, a hydroxyalkyl group or a cyano group; r1 is an integer of 0 to 2, and r2 is 1. Is an integer of ˜5, and 1 ≦ r1 + r2 ≦ 5.]

In formula (x-11-30), q2 is preferably 1 to 4, more preferably 1 or 2, and most preferably 2.
R ^70, "alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, -COOR (excluding a fluorine atom.)" - OC (= O ) R ", hydroxyalkyl group, respectively, at the Z The thing similar to what was illustrated in description about the substituent which an aromatic hydrocarbon group may have is mentioned.
r1 is most preferably 0.
r2 is preferably 2 to 5, and most preferably 5.

..Anions represented by general formula (x-11-40)

［式（ｘ−１１−４０）中、ｐおよびＲ^７はそれぞれ前記と同じであり、ｑ３は１〜１２の整数であり、ｒ３は０〜３の整数である。］

[In Formula (x-11-40), p and R ⁷ are the same as defined above, q3 is an integer of 1 to 12, and r3 is an integer of 0 to 3, respectively. ]

In formula (x-11-40), R ⁷ is preferably an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (═O), or a cyano group.
The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, particularly preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and a methoxy group or an ethoxy group. Is most preferred.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable.
As the halogenated alkyl group, a part or all of hydrogen atoms of an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, etc. And a group substituted with a halogen atom.
If signs placed R ⁷ (r3) is an integer of 2 or more, a plurality of R ⁷ in the compounds may be each the same or different.
p is preferably 1 or 2, and most preferably 1.
q3 is preferably 1 to 5, more preferably 1 to 3, and most preferably 1.
r3 is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.

R ⁴ ″ is preferably one having an oxygen atom (═O) as a substituent. In this case, R ⁴ ″ is R ¹⁰ ″ — (CH ₂ ) _{n ″} — [wherein as a substituent A cyclic alkyl group having 4 to 20 carbon atoms having an oxygen atom (═O); n ″ is 0 or 1.] is preferred.
“Having an oxygen atom (═O) as a substituent” means that two hydrogen atoms bonded to one carbon atom constituting a cyclic alkyl group having 4 to 20 carbon atoms are replaced with an oxygen atom (═O). Means the group being
The cyclic alkyl group for R ¹⁰ ″ is not particularly limited as long as it has 4 to 20 carbon atoms, and may be either a polycyclic group or a monocyclic group. For example, monocycloalkane, bicycloalkane, tricyclo Examples include groups in which one hydrogen atom is removed from polycycloalkanes such as alkanes, tetracycloalkanes, etc. Monocyclic groups are those in which one hydrogen atom is removed from monocycloalkanes having 3 to 8 carbon atoms. Specific examples include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc. The polycyclic group preferably has 7 to 12 carbon atoms, specifically an adamantyl group. , Norbornyl group, isobornyl group, tricyclodecanyl group, tetracyclododecanyl group and the like.
R ¹⁰ ″ is preferably a polycyclic alkyl group having 4 to 20 carbon atoms having an oxygen atom (═O) as a substituent, and industrially constitutes an adamantyl group, norbornyl group, or tetracyclododecanyl group. A group in which two hydrogen atoms bonded to one carbon atom are substituted with an oxygen atom (═O) is preferable, and a norbornyl group having an oxygen atom (═O) as a substituent is particularly preferable.
The alkyl group for R ¹⁰ ″ may have a substituent other than the oxygen atom. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms.
In the formula: R ¹⁰ ″ — (CH ₂ ) _{n ″} —, n ″ is 0 or 1, and preferably 1.
_"- if it is a group represented ^by, R 4" -SO ₃ ^- - R ⁴ 'is ^R 10 _{"(CH 2) n,} one of the camphor sulfonate ion (hydrogen atoms of camphor -SO ₃ ^- in A substituted ion), and in particular, an ion represented by the following chemical formula (x-12-1) (a sulfonate ion (—SO ₃ ^— ) on the carbon atom of the methyl group bonded to the 1-position of the norbornane ring. ) Is preferably bonded).

Further, onium salt-based acid generator, the anion moiety in the general formula (b-1) or ^{(b-2) (R 4} "-SO 3 -) of the following general formula (b-3) or (b-4 An onium salt-based acid generator (the cation portion is the same as (b-1) or (b-2)) replaced with an anion portion represented by) can also be used.

［式中、Ｘ”は、少なくとも１つの水素原子がフッ素原子で置換された炭素数２〜６のアルキレン基を表し；Ｙ”、Ｚ”は、それぞれ独立に、置換基を有していてもよいアルキル基またはハロゲン化アルキル基を表す。Ｚ”に結合した−ＳＯ_２−は、−Ｃ（＝Ｏ）−に置換されていてもよい。］

[Wherein X ″ represents an alkylene group having 2 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; Y ″ and Z ″ each independently have a substituent. -SO 2 bound to .Z "representing an alkyl group or halogenated alkyl group _- is, -C (= O) - may be substituted with. ]

X ″ is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, Most preferably, it has 3 carbon atoms.
The number of carbon atoms of the alkylene group of X ″ is preferably as small as possible because, for example, the solubility in a resist solvent is good within the range of the carbon number.
In the alkylene group of X ″, the larger the number of hydrogen atoms substituted by fluorine atoms, the stronger the acid and the better the transparency to high energy light of 200 nm or less and electron beam. The proportion of fluorine atoms in the group or alkyl group, that is, the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably, a hydrogen atom in which all hydrogen atoms are substituted with fluorine atoms. A fluoroalkylene group or a perfluoroalkyl group;

The alkyl group in Y ″ and Z ″ may be linear, branched or cyclic, and examples thereof include the same alkyl groups as those described above for R ⁴ ″.
The halogenated alkyl group in Y ″ and Z ″ is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms, and examples thereof include the same as the halogenated alkyl group in R ⁴ ″. .
In the halogenated alkyl group, the ratio of the number of halogen atoms to the total number of halogen atoms and hydrogen atoms contained in the halogenated alkyl group (halogenation rate (%)) is preferably 10 to 100%. 50 to 100% is preferable, and 100% is most preferable. The higher the halogenation rate, the better the acid strength.
As the halogenated alkyl group, a fluorinated alkyl group is particularly preferred.

The alkyl group or halogenated alkyl group in Y ″ and Z ″ may have a substituent.
The phrase “may be substituted” in the alkyl group in Y ″ and Z ″ means that part or all of the hydrogen atoms in the alkyl group may be substituted with a substituent. The halogenated alkyl group in Y ″ and Z ″ “may have a substituent” means that some or all of the halogen atoms and hydrogen atoms in the halogenated alkyl group are substituted with substituents. Also means good. The number of substituents in Y ″ and Z ″ may be one or two or more.
The substituent which the alkyl group or halogenated alkyl group in Y ″ and Z ″ may have may be any atom or group other than a carbon atom, a hydrogen atom and a halogen atom. group, ^wherein: Z 5 -Q ⁴ - [wherein, ^{Q 4} represents a divalent linking group containing an oxygen atom, ^{Z 5} is a hydrocarbon group of 3 to 30 carbon atoms which may have a substituent It is. ] Etc. which are represented by these.
Among these substituents, examples of the hetero atom and the alkyl group include the same hetero atoms and alkyl groups as those described above as the substituent for R ⁴ ″.

Z ⁵ -Q ⁴ - In the group represented by, ^{Q 4} represents a divalent linking group containing an oxygen atom.
The Q ^4, the ^{Z-Q 1} - are the same as those for ^{Q 1} in a group represented.
Q ⁴ is preferably a divalent linking group containing an ester bond and / or an ether bond, and in particular, —O—, —R ⁹¹ —O—, —R ⁹² —O—C (═O) —, — C (═O) —O—, —C (═O) —O—R ⁹³ — or —C (═O) —O—R ⁹³ —O—C (═O) — are preferred. R ^{91 to} R ⁹³ are the same as described above.
Z ⁵ -Q ⁴ - In the group represented by, ^{Z 5} represents a hydrocarbon group which may 3-30 carbon atoms which may have a substituent.
Examples of Z ⁵ include the same as Z in the group represented by ZQ ¹ —.
Z ⁵ is preferably an aliphatic hydrocarbon group, more preferably a linear or cyclic aliphatic hydrocarbon group, and still more preferably a cyclic aliphatic hydrocarbon group.

In formula (b-4), —SO ₂ — bonded to Z ″ may be substituted with —C (═O) —. That is, the anion moiety represented by formula (b-4) is: It may be represented by the following general formula (b-4 ′).

［式中、Ｙ”、Ｚ”は、上記と同様である。］

[Wherein Y ″ and Z ″ are the same as above. ]

In the present invention, in formula (b-4) and formula (b-4 ′), at least one of Y ″ and Z ″ is a fluorinated alkyl group which may have a substituent. preferable.
In particular, in formula (b-4), it is preferable that one of Y ″ and Z ″ is a perfluoroalkyl group, and the other is an optionally substituted alkyl group or fluorinated alkyl group. . In formula (b-4 ′), one of Y ″ and Z ″ is preferably a perfluoroalkyl group, and the other is preferably an alkyl group which may have a substituent. It is preferably a perfluoroalkyl group, and Z ″ is an alkyl group which may have a substituent.
Examples of the anion represented by the formula (b-4) or the formula (b-4 ′) in such a case include anions represented by the following formulas (b4-1) to (b4-8). .

［式中、Ｒ^７は置換基であり、ｓ１〜ｓ４はそれぞれ独立に０〜３の整数であり、ｚ１〜ｚ６はそれぞれ独立に０〜３の整数であり、ｐ’は０〜４の整数であり、ｍ_１１〜ｍ_１３は０又は１であり、ｒは１〜４の整数であり、ｉは１〜２０の整数である。］

[Wherein, R ⁷ is a substituent, s1 to s4 are each independently an integer of 0 to 3, z1 to z6 are each independently an integer of 0 to 3, and p ′ is an integer of 0 to 4. M _{11 to} m ₁₃ are 0 or 1, r is an integer of 1 to 4, and i is an integer of 1 to 20. ]

In the above formula, as the substituent for R ^7, the substituent that the aliphatic hydrocarbon group may have in the Z of the group represented by ZQ ¹ — may have. The thing similar to what was mentioned as is mentioned.
If signs placed R ⁷ (s1 to s4) is an integer of 2 or more, a plurality of the R ⁷ groups may be the same, respectively, it may be different.
s1 to s4 are preferably 0 or 1, and most preferably 0.
z1 to z6 are preferably 0 or 1.
p ′ is preferably 0 to 2.
m ₁₂ is preferably 0.
r is preferably 1 or 2, and most preferably 1.
i is more preferably 1 to 15, and further preferably 3 to 12.
In the present invention, anions represented by formulas (b4-1) to (b4-4) are particularly preferable.

Further, as an onium salt acid generator, an onium salt acid generator (cation moiety) in which the anion moiety (R ⁴ ″ -SO ₃ ⁻ ) in the general formula (b-1) or (b-2) is replaced with a methide anion. (B-1) or (b-2) can also be used. Examples of the methide anion include anions represented by the following general formula (b-c1).

［式中、Ｒ^１８”は、少なくとも１の水素原子がフッ素置換されている炭素数１〜１０のアルキル基であり；Ｒ^１９”は、置換基を有していてもよい炭化水素基、または−ＳＯ_２−Ｒ^１８”である。］

[Wherein R ¹⁸ ″ is an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with fluorine; R ¹⁹ ″ is a hydrocarbon group which may have a substituent, or —SO ₂ —R ¹⁸ ″.]

In formula (b-c1), R ¹⁸ ″ is an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with fluorine. Examples of the alkyl group include linear, branched, and cyclic. In the present invention, R ¹⁸ ″ is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
In the formula (b-c1), when R ¹⁹ ″ is a hydrocarbon group which may have a substituent (the “hydrocarbon group which may have a substituent” refers to the hydrocarbon group This means that a part or all of the hydrogen atoms constituting may be substituted with a substituent group.), The hydrocarbon group of R ¹⁹ ″ may be an aliphatic hydrocarbon group or an aromatic carbon group. A hydrogen group may be used, and specific examples include the same as Z in the above formula: ZQ ^1- .
R ¹⁹ ″ is preferably an aryl group having a halogen atom as a substituent (halogenated aryl group) or —SO ₂ —R ¹⁸ ″. Examples of the aryl group in the halogenated aryl group include groups in which some or all of the hydrogen atoms of an aryl group having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group are substituted with a halogen atom. The halogen atom in the halogenated aryl group is preferably a fluorine atom.

  Moreover, the sulfonium salt which has a cation part represented by the following general formula (b-5) or (b-6) can also be used as an onium salt type | system | group acid generator.

［式中、Ｒ^４１〜Ｒ^４６はそれぞれ独立してアルキル基、アセチル基、アルコキシ基、カルボキシ基、水酸基またはヒドロキシアルキル基であり；ｎ_１〜ｎ_５はそれぞれ独立して０〜３の整数であり、ｎ_６は０〜２の整数である。］

[Wherein R ^{41 to} R ⁴⁶ are each independently an alkyl group, acetyl group, alkoxy group, carboxy group, hydroxyl group or hydroxyalkyl group; n _{1 to} n ₅ are each independently an integer of 0 to 3; There, _{n 6} is an integer of 0-2. ]

In R ^{41 to} R ⁴⁶ , the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group, and a methyl group, an ethyl group, a propyl group, an isopropyl group, n A butyl group or a tert-butyl group is particularly preferable.
The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a linear or branched alkoxy group, and particularly preferably a methoxy group or an ethoxy group.
The hydroxyalkyl group is preferably a group in which one or more hydrogen atoms in the alkyl group are substituted with a hydroxy group, and examples thereof include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
When the symbols n _{1 to} n ₆ attached to R ^{41 to} R ⁴⁶ are integers of 2 or more, the plurality of R ^{41 to} R ⁴⁶ may be the same or different.
n ₁ is preferably 0 to 2, more preferably 0 or 1, and still more preferably 0.
n ₂ and n ₃ are preferably each independently 0 or 1, more preferably 0.
n ₄ is preferably 0 to 2, more preferably 0 or 1.
n ₅ is preferably 0 or 1, more preferably 0.
n ₆ is preferably 0 or 1, more preferably 1.

The anion part of the sulfonium salt having a cation part represented by the formula (b-5) or (b-6) is not particularly limited, and is the same as the anion part of the onium salt acid generators proposed so far. It may be a thing. Examples of the anion moiety include fluorinated alkyl sulfonate ions such as the anion moiety (R ⁴ ″ SO ₃ ⁻ ) of the onium salt acid generator represented by the general formula (b-1) or (b-2). An anion moiety represented by the general formula (b-3) or (b-4); a metide anion, and the like.

  In this specification, the oxime sulfonate acid generator is a compound having at least one group represented by the following general formula (B-1), and has a property of generating an acid upon irradiation with radiation. is there. Such oxime sulfonate-based acid generators are frequently used for chemically amplified resist compositions, and can be arbitrarily selected and used.

（式（Ｂ−１）中、Ｒ^３１、Ｒ^３２はそれぞれ独立に有機基を表す。）

(In formula (B-1), R ³¹ and R ³² each independently represents an organic group.)

The organic groups of R ³¹ and R ³² are groups containing carbon atoms, and atoms other than carbon atoms (for example, hydrogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms (fluorine atoms, chlorine atoms, etc.), etc.) You may have.
As the organic group for R ^31, a linear, branched, or cyclic alkyl group or aryl group is preferable. These alkyl groups and aryl groups may have a substituent. There is no restriction | limiting in particular as this substituent, For example, a fluorine atom, a C1-C6 linear, branched or cyclic alkyl group etc. are mentioned. Here, “having a substituent” means that part or all of the hydrogen atoms of the alkyl group or aryl group are substituted with a substituent.
As an alkyl group, C1-C20 is preferable, C1-C10 is more preferable, C1-C8 is more preferable, C1-C6 is especially preferable, and C1-C4 is the most preferable. As the alkyl group, a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is particularly preferable. The partially halogenated alkyl group means an alkyl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated alkyl group means that all of the hydrogen atoms are halogen atoms. Means an alkyl group substituted with Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.
The aryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms. As the aryl group, a partially or completely halogenated aryl group is particularly preferable. The partially halogenated aryl group means an aryl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated aryl group means that all of the hydrogen atoms are halogen atoms. Means an aryl group substituted with.
R ³¹ is particularly preferably an alkyl group having 1 to 4 carbon atoms having no substituent or a fluorinated alkyl group having 1 to 4 carbon atoms.
As the organic group for R ^32, a linear, branched, or cyclic alkyl group, aryl group, or cyano group is preferable. As the alkyl group and aryl group for R ^32, the same alkyl groups and aryl groups as those described above for R ³¹ can be used.
R ³² is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms.

  More preferable examples of the oxime sulfonate-based acid generator include compounds represented by the following general formula (B-2) or (B-3).

［式（Ｂ−２）中、Ｒ^３３は、シアノ基、置換基を有さないアルキル基またはハロゲン化アルキル基である。Ｒ^３４はアリール基である。Ｒ^３５は置換基を有さないアルキル基またはハロゲン化アルキル基である。］

[In Formula (B-2), R ³³ represents a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁴ is an aryl group. R ³⁵ represents an alkyl group having no substituent or a halogenated alkyl group. ]

［式（Ｂ−３）中、Ｒ^３６はシアノ基、置換基を有さないアルキル基またはハロゲン化アルキル基である。Ｒ^３７は２または３価の芳香族炭化水素基である。Ｒ^３８は置換基を有さないアルキル基またはハロゲン化アルキル基である。ｐ”は２または３である。］

[In Formula (B-3), R ³⁶ represents a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁷ is a divalent or trivalent aromatic hydrocarbon group. ^R38 is an alkyl group having no substituent or a halogenated alkyl group. p ″ is 2 or 3.]

In the general formula (B-2), alkyl or halogenated alkyl group having no substituent group for R ³³ preferably has 1 to 10 carbon atoms, 1 to 8 carbon atoms, more preferably, carbon Numbers 1 to 6 are most preferable.
R ³³ is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group.
The fluorinated alkyl group for R ³³ is preferably such that the hydrogen atom of the alkyl group is 50% or more fluorinated, more preferably 70% or more fluorinated, and 90% or more fluorinated. Particularly preferred.
As the aryl group of R ³⁴ , one hydrogen atom is removed from an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, or a phenanthryl group. And a heteroaryl group in which a part of carbon atoms constituting the ring of these groups is substituted with a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom. Among these, a fluorenyl group is preferable.
The aryl group of R ³⁴ may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or an alkoxy group. The alkyl group or halogenated alkyl group in the substituent preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. The halogenated alkyl group is preferably a fluorinated alkyl group.
The alkyl group or halogenated alkyl group having no substituent for R ³⁵ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms.
R ³⁵ is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group.
The fluorinated alkyl group for R ³⁵ is preferably such that the hydrogen atom of the alkyl group is 50% or more fluorinated, more preferably 70% or more fluorinated, and 90% or more fluorinated. Particularly preferred is the strength of the acid generated. Most preferably, it is a fully fluorinated alkyl group in which a hydrogen atom is 100% fluorine-substituted.

In the general formula (B-3), the alkyl group or halogenated alkyl group having no substituent for R ³⁶ is the same as the alkyl group or halogenated alkyl group having no substituent for R ^33. Is mentioned.
Examples of the divalent or trivalent aromatic hydrocarbon group for R ³⁷ include groups obtained by further removing one or two hydrogen atoms from the aryl group for R ³⁴ .
Examples of the alkyl group or halogenated alkyl group having no substituent of R ³⁸ include the same alkyl groups or halogenated alkyl groups having no substituent as R ³⁵ described above.
p ″ is preferably 2.

Specific examples of the oxime sulfonate acid generator include α- (p-toluenesulfonyloxyimino) -benzyl cyanide, α- (p-chlorobenzenesulfonyloxyimino) -benzyl cyanide, α- (4-nitrobenzenesulfonyloxy). Imino) -benzylcyanide, α- (4-nitro-2-trifluoromethylbenzenesulfonyloxyimino) -benzylcyanide, α- (benzenesulfonyloxyimino) -4-chlorobenzylcyanide, α- (benzenesulfonyl) Oxyimino) -2,4-dichlorobenzyl cyanide, α- (benzenesulfonyloxyimino) -2,6-dichlorobenzyl cyanide, α- (benzenesulfonyloxyimino) -4-methoxybenzyl cyanide, α- ( 2-Chlorobenzenesulfonyloxyimino) 4-methoxybenzylcyanide, α- (benzenesulfonyloxyimino) -thien-2-ylacetonitrile, α- (4-dodecylbenzenesulfonyloxyimino) -benzylcyanide, α-[(p-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(dodecylbenzenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α- (tosyloxyimino) -4-thienyl cyanide, α- (methylsulfonyloxyimino) -1-cyclo Pentenyl acetonitrile, α- (methylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (methylsulfonyloxyimino) -1-cycloheptenylacetonitrile, α- (methylsulfonyloxyimino) -1-cyclooctene Acetonitrile, α- (trifluoromethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -cyclohexylacetonitrile, α- (ethylsulfonyloxyimino) -ethylacetonitrile, α- (propyl Sulfonyloxyimino) -propylacetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclopentylacetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclohexylacetonitrile, α- (cyclohexylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- ( Ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclope N-tenyl acetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclohexenylacetonitrile , Α- (n-butylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (trifluoro Methylsulfonyloxyimino) -phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -p- Butoxy phenylacetonitrile, alpha-(propylsulfonyl oxyimino)-p-methylphenyl acetonitrile, alpha-like (methylsulfonyloxyimino)-p-bromophenyl acetonitrile.
Also, an oxime sulfonate-based acid generator disclosed in JP-A-9-208554 (paragraphs [0012] to [0014] [chemical formula 18] to [chemical formula 19]), WO 2004 / 074242A2 (pages 65 to 85). The oxime sulfonate acid generators disclosed in Examples 1 to 40) of No. 1 can also be suitably used.
Moreover, the following can be illustrated as a suitable thing.

Among diazomethane acid generators, specific examples of bisalkyl or bisarylsulfonyldiazomethanes include bis (isopropylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, Examples include bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, and the like.
Further, diazomethane acid generators disclosed in JP-A-11-035551, JP-A-11-035552, and JP-A-11-035573 can also be suitably used.
Examples of poly (bissulfonyl) diazomethanes include 1,3-bis (phenylsulfonyldiazomethylsulfonyl) propane and 1,4-bis (phenylsulfonyldiazo) disclosed in JP-A-11-322707. Methylsulfonyl) butane, 1,6-bis (phenylsulfonyldiazomethylsulfonyl) hexane, 1,10-bis (phenylsulfonyldiazomethylsulfonyl) decane, 1,2-bis (cyclohexylsulfonyldiazomethylsulfonyl) ethane, 1,3 -Bis (cyclohexylsulfonyldiazomethylsulfonyl) propane, 1,6-bis (cyclohexylsulfonyldiazomethylsulfonyl) hexane, 1,10-bis (cyclohexylsulfonyldiazomethylsulfonyl) decane, etc. Door can be.

(B) As a component, these acid generators may be used individually by 1 type, and may be used in combination of 2 or more type.
In the present invention, it is preferable to use, as the component (B), an onium salt having a fluorinated alkyl sulfonate ion which may have a substituent as an anion.
In the resist composition, the content of the component (B) is preferably 0.5 to 50 parts by mass and more preferably 1 to 40 parts by mass with respect to 100 parts by mass of the component (A). By setting it within the above range, pattern formation is sufficiently performed. Moreover, since a uniform solution is obtained and storage stability becomes favorable, it is preferable.

<Optional component>
The positive resist composition of the present invention may contain a nitrogen-containing organic compound (D) (hereinafter referred to as “component (D)”) as an optional component.
The component (D) is not particularly limited as long as it acts as an acid diffusion controller, that is, a quencher that traps the acid generated from the component (B) by exposure, and a wide variety of components have already been proposed. Therefore, any known one may be used, and aliphatic amines, particularly secondary aliphatic amines and tertiary aliphatic amines are particularly preferable. Here, the aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic groups preferably have 1 to 20 carbon atoms.
Examples of the aliphatic amine include an amine (alkylamine or alkyl alcohol amine) or a cyclic amine in which at least one hydrogen atom of ammonia NH ₃ is substituted with an alkyl group or hydroxyalkyl group having 20 or less carbon atoms. .
Specific examples of alkylamines and alkyl alcohol amines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; diethylamine, di-n-propylamine, di- -Dialkylamines such as n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine , Tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decanylamine, tri-n-dodecylamine, and the like; diethanolamine, triethanolamine, diisopropanolamine Triisopropanolamine, di -n- octanol amine, tri -n- octanol amine, stearyl diethanolamine, alkyl alcohol amines such as lauryl diethanolamine. Among these, trialkylamine and / or alkyl alcohol amine are preferable.
Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a hetero atom. The heterocyclic compound may be monocyclic (aliphatic monocyclic amine) or polycyclic (aliphatic polycyclic amine).
Specific examples of the aliphatic monocyclic amine include piperidine and piperazine.
As the aliphatic polycyclic amine, those having 6 to 10 carbon atoms are preferable. Specifically, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5. 4.0] -7-undecene, hexamethylenetetramine, 1,4-diazabicyclo [2.2.2] octane, and the like.
Other aliphatic amines include tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2 -(1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2- {2- (2-hydroxy Ethoxy) ethoxy} ethylamine and the like.
Moreover, you may use an aromatic amine as (D) component.
Examples of the aromatic amine include aniline, pyridine, 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, diphenylamine, triphenylamine, and tribenzylamine.
These may be used alone or in combination of two or more.
(D) component is normally used in 0.01-5.0 mass parts with respect to 100 mass parts of (A) component. By setting the content in the above range, the resist pattern shape, the stability over time, and the like are improved.

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

  If desired, the positive resist composition of the present invention may further contain miscible additives such as an additional resin for improving the performance of the resist film, a surfactant for improving the coating property, and a dissolution inhibitor. , Plasticizers, stabilizers, colorants, antihalation agents, dyes, and the like can be added as appropriate.

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

The positive resist composition of the present invention and the component (A1) blended in the positive resist composition are novel ones not conventionally known.
The component (A1) is useful as a base material component of a positive resist composition. That is, the component (A1) has a film-forming ability by having the specific unprotected body in the skeleton, and can form a film made of only the component (A1), for example. Further, by having R ¹ (acid dissociable, dissolution inhibiting group), when acid is generated from the component (B), the acid has the property of increasing solubility in an alkali developer due to the action of the acid. Therefore, when selective exposure is performed on the film containing the component (A1) and the component (B), R ¹ (acid dissociable, dissolution inhibiting group) is dissociated by the action of the acid generated from the component (B). And the solubility with respect to the alkali developing solution of the exposed part of this film | membrane increases. Therefore, when the film is alkali-developed, the exposed portion is removed and a resist pattern is formed.
In addition, according to the positive resist composition of the present invention, a high-resolution resist pattern, for example, a pattern size of 200 nm or less, and an ultrafine resist pattern of several tens of nm level can be formed, and the sensitivity is also good. In addition, a resist pattern having a small roughness such as a line edge roughness (LER) or a line width roughness (LWR) can be formed. “LWR” refers to a phenomenon in which the line width of a line pattern becomes non-uniform when a resist pattern is formed using a resist composition.
The reason why the above effect is obtained is not clear, but as one of the reasons, the compound (A1) has the above-described structure, so that the resist pattern can be exposed to an alkaline developer in an unexposed area and an exposed area when forming a resist pattern. It is considered that the difference in solubility (dissolution contrast) is improved. That is, conventionally used base material components usually have a plurality of acid-dissociable, dissolution-inhibiting groups introduced in one molecule for reasons such as increasing the difference in solubility in an alkaline developer before and after exposure. . However, molecules that differ in the number of dissociated acid dissociable, dissolution-inhibiting groups that remain partially undissociated in the exposed area due to differences in structure, bonding position, and other lithography conditions. That is, a plurality of types of molecules having different solubility in an alkali developer are present. In particular, when a high molecular weight polymer (resin) is used as the base material component, there is a large variation in alkali solubility due to variations in molecular weight and structure. Therefore, it is presumed that in the exposure area, the dispersion of the solubility in the alkali developer occurs, which lowers the dissolution contrast and causes the roughness and resolution to deteriorate.
On the other hand, in the present invention, only one acid dissociable, dissolution inhibiting group introduced into compound (A1) functions as a switch for switching the solubility to the alkaline developer of compound (A1). In other words, the behavior that the compound (A1) can take is only two, ie, the acid dissociable, dissolution inhibiting group remains not dissociated at all, or the acid dissociable, dissolution inhibiting group all dissociates. It is considered that there is little variation in solubility in an alkali developer, and the above effect is achieved.
In the present invention, having to select the type of R ^1, the difference in solubility in an alkali developing solution before and after dissociation of R ^1, an advantage that can be adjusted and thus dissolution contrast.

≪Resist pattern formation method≫
The resist pattern forming method of the present invention includes a step of forming a resist film on a support using the positive resist composition of the present invention, a step of exposing the resist film, and developing the resist film to form a resist. Forming a pattern.
Each step in the method for forming a resist pattern of the present invention can be performed using a known technique except that the positive resist composition of the present invention is used.
The resist pattern forming method of the present invention can be performed, for example, as follows. That is, first, the positive resist composition is applied onto a support with a spinner or the like, and pre-baked (post-applied baking) at a temperature of about 80 to 150 ° C. for 40 to 120 seconds, preferably 60 to 90 seconds. (PAB)) to form a resist film. The formed resist film is exposed by exposure through a mask pattern using an exposure apparatus such as an ArF exposure apparatus, an electron beam drawing apparatus, or an EUV exposure apparatus, or by drawing by direct irradiation of an electron beam without using a mask pattern. After the selective exposure, PEB (post-exposure heating) is performed at a temperature of about 80 to 150 ° C. for 40 to 120 seconds, preferably 60 to 90 seconds. Subsequently, after alkali development using an alkali developer, for example, an aqueous solution of 0.1 to 10% by mass tetramethylammonium hydroxide (TMAH), a water rinse treatment is preferably performed using pure water, followed by drying. In some cases, a baking process (post-bake) may be performed after the development process. In this way, a resist pattern faithful to the mask pattern can be obtained.

The support is not particularly limited, and a conventionally known one can be used, and examples thereof include a substrate for electronic components and a substrate on which a predetermined wiring pattern is formed. More specifically, a silicon substrate, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. As a material for the wiring pattern, for example, copper, aluminum, nickel, gold or the like can be used.
Further, the support may be a substrate in which an inorganic and / or organic film is provided on the above-described substrate. An inorganic antireflection film (inorganic BARC) is an example of the inorganic film. Examples of the organic film include an organic antireflection film (organic BARC).

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

The resist film may be exposed by normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or by immersion exposure.
Immersion exposure is a lithography method in which exposure (immersion exposure) is performed by interposing a liquid (immersion medium) having a higher refractive index than air between an objective lens of an exposure machine and a sample, so-called immersion lithography ( (Liquid Immersion Lithography), which is known as one of methods for further improving the resolution (for example, Proceedings of SPIE, Vol. 5754, pp. 119-128 ( 2005)). According to immersion exposure, even when a light source having the same exposure wavelength is used, the same high resolution as when using a light source with a shorter wavelength or a high NA lens can be achieved, and the depth of focus can be reduced. It is said that there is no decline. In addition, immersion exposure can be performed by applying an existing exposure apparatus. For this reason, immersion exposure is expected to be able to form resist patterns with low cost, high resolution, and excellent depth of focus. In particular, in terms of lithography characteristics such as resolution, the semiconductor industry has been attracting attention as a great effect.

In immersion exposure, as described above, the portion between the lens, which has been filled with an inert gas such as air or nitrogen, and the resist film on the wafer at the time of exposure is refracted larger than the refractive index of air. The exposure is performed in a state filled with a solvent having a high rate (immersion medium). More specifically, the immersion exposure is a solvent (immersion medium) having a refractive index larger than the refractive index of air between the resist film obtained as described above and the lowermost lens of the exposure apparatus. And in that state, exposure can be performed through a desired photomask (immersion exposure).
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 exposed by the immersion exposure 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 fluorinated compounds such as C ₃ HCl ₂ F ₅ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , and C ₅ H ₃ F ₇ as main components. Examples thereof include liquids, and those having a boiling point of 70 to 180 ° C are preferable, and those having a boiling point of 80 to 160 ° C are more preferable. It is preferable that the fluorine-based inert liquid has a boiling point in the above range since the medium used for immersion can be removed by a simple method after the exposure is completed.
As the fluorine-based inert liquid, a perfluoroalkyl compound in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms is particularly preferable. Specific examples of the perfluoroalkyl compound include a perfluoroalkyl ether compound and a perfluoroalkylamine compound.
More specifically, examples of the perfluoroalkyl ether compound include perfluoro (2-butyl-tetrahydrofuran) (boiling point: 102 ° C.). Examples of the perfluoroalkylamine compound include perfluorotributylamine ( Boiling point of 174 ° C.).
Among the above, water is preferably used as the immersion medium from the viewpoints of cost, safety, environmental problems, and versatility.

≪Compound≫
The compound of the third aspect of the present invention is the same as the component (A1) in the resist composition of the first aspect of the present invention.
The compound is a novel compound that has not been conventionally known. In addition, the compound exhibits the effects as described above when used as a resist composition, and is useful as a component for a resist composition, particularly as a substrate component.

≪Dissolution inhibitor≫
The compound of the third aspect of the present invention can also be suitably used as a dissolution inhibitor for positive resist compositions. By using the dissolution inhibitor composed of the compound, the alkali solubility of the resist film (before exposure) obtained using the positive resist composition containing the dissolution inhibitor is suppressed. Therefore, when the resist film is selectively exposed, the difference in alkali solubility (dissolution contrast) between the exposed portion and the unexposed portion is increased, and a resist pattern with good resolution and shape can be formed. .
Such a dissolution inhibitor can be used by being added to a two-component chemically amplified resist composition containing a resin component having an acid dissociable dissolution inhibiting group and an acid generator component, and can also be used to inhibit acid dissociable dissolution. It can also be used as a so-called three-component chemically amplified resist composition using a resin component having no group, an acid generator component, and a dissolution inhibitor.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.
In this example, the unit represented by the chemical formula (1) is referred to as “compound (1)”, and the same applies to compounds represented by other formulas.
[Synthesis Example 1 (Synthesis of Compound (2))]
Compound (1) was synthesized in the same manner as in Synthesis Example 1 of JP2008-19235A.
27.6 g of compound (1) and 5.0 g of 1-hydroxymethyladamantane were dissolved in 300 ml of tetrahydrofuran (THF). Next, 7 g of ethyldiisopropylaminocarbodiimide hydrochloride (EDCl · HCl) was added, and the mixture was cooled to 0 ° C., dimethylaminopyridine (DMAP) was added, and the mixture was allowed to react for 10 minutes. Then, it was made to react at room temperature for 12 hours.
After completion of the reaction, 100 ml of water was added and concentrated under reduced pressure.
Thereafter, the organic layer obtained by extraction with ethyl acetate was washed with water. Next, the operation of washing the organic layer obtained by extraction with ethyl acetate with a 0.3N aqueous hydrochloric acid solution was repeated twice. Next, the operation of washing the organic layer obtained by extraction with ethyl acetate with water was repeated three times.
Thereafter, the mixture was concentrated under reduced pressure and washed twice with heptane. The resulting liquid was purified by column chromatography (using SiO ₂ as a filler and a mixed solvent of heptane: ethyl acetate = 6: 4 (mass ratio) as a developing solvent), and fractions containing the desired compound were reduced in pressure. By concentrating, 2.5 g of the target compound (2) was obtained.

Compound (2) was analyzed by NMR and IR to confirm the structure of compound (2).
¹ H-NMR (solvent: deuterated dimethyl sulfoxide (DMSO), 400 MHz, internal standard: tetramethylsilane): δ (ppm) = 12.83 (brs, 1H, Ha), 8.85 (s, 4H, Hb), 6.32-6.78 (m, 14H, Hc), 5.82 (d, 2H, Hd), 4.62 (s, 4H, He), 4. 46 (s, 2H, H-f), 3.71 (s, 2H, H-g), 3.57 (s, 2H, H-h), 1.96 (s, 12H, Hi), 1.89 (s, 3H, Hj), 1.85 (s, 12H, Hk), 1.43-1.66 (m, 12H, H-1).
IR: 3386cm < ^-1 >, 2905cm < ^-1 >, 2850cm < ^-1 >, 1737cm < ^-1 >, 1495cm < ^-1 >, 1285cm < ^-1 >.

[Synthesis Example 2 (Synthesis of Compound (3))]
Compound (2) (2.2 g, 2.26 mmol) and 20 mL of tetrahydrofuran (THF) were placed in a 100 mL two-necked flask and stirred at room temperature with 2-methyl-2-adamantyl bromoacetate (0.72 g, 2. 5 mmol) was added, and triethylamine (0.40 g, 4 mmol) was further added dropwise, and the mixture was allowed to react at room temperature for 10 hours.
After completion of the reaction, filtration was performed, and the filtrate was concentrated under reduced pressure to remove THF. Thereafter, 50 mL of pure water was added, the mixture was extracted into 50 mL of ethyl acetate, and washing operation with 50 mL of pure water was performed three times. Thereafter, the ethyl acetate solution was concentrated under reduced pressure, and the resulting solid was purified by column chromatography (using SiO ₂ as a filler and a mixed solvent of heptane: ethyl acetate = 6: 4 (mass ratio) as a developing solvent), The fraction containing the target compound was concentrated under reduced pressure to obtain 1.5 g of compound (3).

Compound (3) was analyzed by NMR and IR to confirm the structure of compound (3).
¹ H-NMR (solvent: DMSO, 400 MHz, internal standard: tetramethylsilane): δ (ppm) = 8.85 (s, 4H, Ha), 6.85-6.30 (m, 14H, H -B), 5.84 (s, 2H, Hc), 4.69 (s, 2H, Hd), 4.68 (s, 2H, He), 4.63 (s, 2H) Hf), 3.73 (s, 2H, Hg), 3.59 (s, 2H, Hh), 1.98 (s, 12H, Hi), 1.88 (s) 12H, Hj), 2.23-1.38 (m, 32H, Hk).
IR: 3361 cm ⁻¹ , 2907 cm ⁻¹ , 2851 cm ⁻¹ , 1743 cm ⁻¹ , 1495 cm ⁻¹ , 1286 cm ⁻¹ .

[Synthesis Example 3 (Synthesis of Compound (4))]
104.3 g of the compound (1) and 20.0 g of 2-naphthalenemethanol were dissolved in 300 ml of tetrahydrofuran (THF), and 31.5 g of ethyldiisopropylaminocarbodiimide hydrochloride (EDCl.HCl) and 0. 8 g of dimethylaminopyridine (DMAP) was added and stirred at room temperature for 10 hours. After completion of the reaction, the reaction mixture was concentrated, extracted with water / ethyl acetate, 1N aqueous hydrochloric acid / ethyl acetate, and water / ethyl acetate. The resulting ethyl acetate solution was concentrated under reduced pressure. Thereafter, the obtained liquid was purified by column chromatography (using a mixed solvent of SiO ₂ as a filler and heptane: ethyl acetate = 6: 4 (mass ratio) as a developing solvent) to obtain the target compound (4). Of 48.8 g was obtained.

The compound (4) was analyzed by NMR and IR to confirm the structure of the compound (4).
¹ H-NMR (solvent: deuterated dimethyl sulfoxide (DMSO), 400 MHz, internal standard: tetramethylsilane): δ (ppm) = 12.85 (brs, 1H, Ha), 8.85 (s, 4H, Hb), 7.41-7.98 (m, 7H, Hc), 6.30-6.86 (m, 14H, Hd), 5.84 (s, 1H, He ), 5.85 (s, 1H, Hf), 5.33 (s, 2H, H-g), 4.74 (s, 2H, Hh), 4.48 (s, 2H, H) -I), 3.58 (s, 2H, Hj), 1.93-2.00 (m, 24H, Hk).
^{IR: 3396cm -1, 2921cm -1,} 1740cm -1, 1496cm -1, 1284cm -1, 1193cm -1.

[Synthesis Example 4 (Synthesis of Compound (5))]
Compound (4) (16.0 g, 16.6 mmol) and 100 mL of tetrahydrofuran (THF) were placed in a 500 mL two-necked flask and stirred at room temperature with 2-methyl-2-adamantyl bromoacetate (5.16 g, 18 .6 mmol) was added, and triethylamine (2.64 g 26.1 mmol) was further added dropwise, and the mixture was allowed to react at room temperature for 10 hours.
After completion of the reaction, filtration was performed, and the filtrate was concentrated under reduced pressure to remove THF. Thereafter, 100 mL of pure water was added, extracted into 100 mL of ethyl acetate, and washing operation with 100 mL of pure water was performed three times. Thereafter, the ethyl acetate solution was concentrated under reduced pressure, and the resulting solid was purified by column chromatography (using SiO ₂ as a filler and a mixed solvent of heptane: ethyl acetate = 6: 4 (mass ratio) as a developing solvent), The fraction containing the target compound was concentrated under reduced pressure to obtain 13.8 g of compound (5).

The compound (5) was analyzed by NMR and IR to confirm the structure of the compound (5).
¹ H-NMR (solvent: DMSO, 400 MHz, internal standard: tetramethylsilane): δ (ppm) = 8.88 (s, 4H, Ha), 7.42-7.98 (m, 7H, H -B), 6.30-6.87 (m, 14H, H-c), 5.83 (s, 2H, Hd), 5.33 (s, 2H, He), 4.74 (S, 2H, H-f), 4.68 (s, 2H, H-g), 4.67 (s, 2H, H-h), 3.60 (s, 2H, H-i), 1 .41-2.22 (m, 41H, Hj).
^{IR: 3390cm -1, 2921cm -1,} 2863cm -1, 1745cm -1, 1495cm -1, 1284cm -1, 1182cm -1.

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

The numerical value shown in [] in Table 1 is the blending amount (part by mass). Moreover, the symbol in Table 1 shows the following.
(A) -1: the compound (3).
(A) -1: the compound (5).
(A ′)-1: A compound represented by the following chemical formula (A ′)-1, which was synthesized in the same manner as in Synthesis Example 3 of JP-A-2008-19235.
(B) -1: Triphenylsulfonium nonafluoro-n-butanesulfonate.
(D) -1: tri-n-octylamine.
(E) -1: salicylic acid.
(S) -1: PGMEA.
(S) -2: PGME.

The following evaluation was performed using the obtained resist composition.
[Formation of resist pattern (1)]
The resist compositions of Example 1 and Comparative Example 1 were each uniformly applied to an 8-inch silicon substrate subjected to hexamethyldisilazane (HMDS) treatment (90 ° C., 36 seconds) using a spinner, and 110 ° C. Then, a baking process (PAB) for 60 seconds was performed to form a resist film (film thickness 60 nm).
Using the electron beam drawing machine HL-800D (VSB) (manufactured by Hitachi), the resist film is drawn (exposed) at an acceleration voltage of 70 kV, and a baking process (PEB) is performed at 100 ° C. for 60 seconds. After developing for 60 seconds using a 2.38 mass% aqueous solution (23 ° C.) of tetramethylammonium hydroxide (TMAH), the film was rinsed with pure water for 30 seconds.
As a result, in each example, a line-and-space resist pattern (hereinafter referred to as a 100 nm LS pattern) having a line width of 100 nm and a line width: space width = 1: 1 was formed.

[Formation of resist pattern (2)]
In the formation of the resist pattern (1), the resist composition of Example 2 was used in place of the resist composition of Example 1, except that PAB was performed at 110 ° C. for 90 seconds and PEB was performed at 100 ° C. for 90 seconds. The same operation as the formation of the resist pattern (1) was performed.
As a result, as in Example 1, a 100 nm LS pattern was formed.

[Sensitivity and resolution]
In the formation of the resist pattern (1) to (2), the optimum exposure dose EOP (μC / cm ² ) for forming the 100 nm LS pattern was determined. The results are shown in Table 2 as “sensitivity”.
Further, as the “resolution”, the limit resolution (nm) in the Eop was determined using a length measurement SEM (scanning electron microscope) S-9220 (manufactured by Hitachi). The results are shown in Table 2.

[Line edge roughness (LER)]
Regarding the 100 nm LS pattern formed in the above-mentioned resist pattern formation (1) to (2), the width of the resist pattern of the sample was measured at 32 locations by a length measurement SEM (manufactured by Hitachi, Ltd., trade name “S-9220”). The triple value (3σ, unit: nm) of the standard deviation (σ) calculated from the result was obtained. The results are shown in Table 2. This 3σ is a scale indicating LER, and the smaller the value, the smaller the LER, which means that a resist pattern with a uniform width was obtained.

  As shown in the above results, according to the resist compositions of Examples 1 and 2 using the compounds (3) and (5) as the base component, respectively, a high-resolution resist pattern can be formed with good sensitivity. The roughness of the resist pattern was also small.

Claims (8)

A positive resist composition comprising a base component (A) whose solubility in an alkaline developer is increased by the action of an acid and an acid generator component (B) that generates an acid upon exposure,
The positive resist composition, wherein the substrate component (A) contains a compound (A1) represented by the following general formula (A1-1).

[Wherein, P is a group obtained by removing (n ₁₂ +1) -OH from a polyhydric phenol compound having a molecular weight of 500 to 2500, R ¹ is an acid dissociable, dissolution inhibiting group, and R ² is an acid non-acid group. a dissociative _{group, n 12} is an integer of 1-3. ]   The positive resist composition according to claim 1, wherein the polyhydric phenol compound has 2 to 6 triphenylmethane structures. The positive resist composition according to claim 1, wherein the compound (A1) is represented by the following general formula (A1-11).

[Wherein n ₁₃ is an integer of 1 to 3; A is a (n ₁₃ +1) -valent linking moiety; a and n 1 are each independently an integer of 1 or more, and n 2 and n 5 are each independently N is an integer of 0 or more, and a + n1 + n2 + n5 is 5 or less; n3 ′ and n4 ′ are each independently an integer of 0 or more, and n3 ′ + n4 ′ is 3 or less; n6 ′ and n7 ′ are each independent And n6 ′ + n7 ′ is 3 or less; R ^{101 to} R ¹⁰⁷ are each independently an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group, May contain a heteroatom; R ³ is a divalent hydrocarbon group which may have a substituent, and a plurality of R ³ in the formula may be the same or different from each other; R ¹ It is the same as above; ^{L 1} is -R ⁴ - (= O) -O- ^{(R 4} represents a divalent linking group.) Or a single ^{bond; Z 11 is,} R 2 (. ^{R 2} is the same as defined above) or a hydrogen atom, When n ₁₃ is 1, it is R ² , and when n ₁₃ is 2 or 3, at least one of 2 or 3 Z ^{11 in} the formula is R ² . ]   Furthermore, the positive resist composition as described in any one of Claims 1-3 containing a nitrogen-containing organic compound (D).   A step of forming a resist film on the support using the positive resist composition according to any one of claims 1 to 4, a step of exposing the resist film, and an alkali development of the resist film A resist pattern forming method including a step of forming a resist pattern. The compound represented by the following general formula (A1-1).

[Wherein, P is a group obtained by removing (n ₁₂ +1) -OH from a polyhydric phenol compound having a molecular weight of 500 to 2500, R ¹ is an acid dissociable, dissolution inhibiting group, and R ² is an acid non-acid group. a dissociative _{group, n 12} is an integer of 1-3. ]   The compound according to claim 6, wherein the polyhydric phenol compound has 2 to 6 triphenylmethane structures. The compound of Claim 6 or 7 represented by the following general formula (A1-11).

[Wherein n ₁₃ is an integer of 1 to 3; A is a (n ₁₃ +1) -valent linking moiety; a and n 1 are each independently an integer of 1 or more, and n 2 and n 5 are each independently N is an integer of 0 or more, and a + n1 + n2 + n5 is 5 or less; n3 ′ and n4 ′ are each independently an integer of 0 or more, and n3 ′ + n4 ′ is 3 or less; n6 ′ and n7 ′ are each independent And n6 ′ + n7 ′ is 3 or less; R ^{101 to} R ¹⁰⁷ are each independently an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group, May contain a heteroatom; R ³ is a divalent hydrocarbon group which may have a substituent, and a plurality of R ³ in the formula may be the same or different from each other; R ¹ It is the same as above; ^{L 1} is -R ⁴ - (= O) -O- ^{(R 4} represents a divalent linking group.) Or a single ^{bond; Z 11 is,} R 2 (. ^{R 2} is the same as defined above) or a hydrogen atom, When n ₁₃ is 1, it is R ² , and when n ₁₃ is 2 or 3, at least one of 2 or 3 Z ^{11 in} the formula is R ² . ]