JP2008001906A - Acid generator, sulfonic acid, sulfonic acid derivative and radiation-sensitive resin composition - Google Patents

Abstract

〔但し、Ｒはフッ素含有率が５０重量％以下である１価の有機基で、置換されてもよい直鎖状もしくは分岐状の１価の炭化水素基、または該置換されてもよい１価の炭化水素基が−ＣＯ−、−ＣＯＯ−、−Ｓ−、−ＳＯ−、−ＳＯ₂ −等に結合した基を示し、Ｚ¹ およびＺ² はフッ素原子またはパーフルオロアルキル基を示す。〕
感放射線性樹脂組成物は、該酸発生剤以外に、ポジ型では酸解離性基含有樹脂を含有し、ネガ型ではアルカリ可溶性樹脂と架橋剤を含有する。
【選択図】なしPROBLEM TO BE SOLVED: To provide a novel flammability, no problem in human accumulation, sufficiently high acidity and boiling point of the acid generated, moderately short diffusion length in a resist film, and small mask pattern dependency A radiation-sensitive acid generator, a sulfonic acid (derivative) related to the acid generator, and a radiation-sensitive resin composition containing the acid generator are provided.
A radiation sensitive acid generator has a structure represented by the following general formula (I).
[Chemical 1]

[However, R is a monovalent organic group having a fluorine content of 50% by weight or less, a linear or branched monovalent hydrocarbon group which may be substituted, or the monovalent which may be substituted. Represents a group bonded to —CO—, —COO—, —S—, —SO—, —SO ₂ — and the like, and Z ¹ and Z ^{2 each} represents a fluorine atom or a perfluoroalkyl group. ]
In addition to the acid generator, the radiation-sensitive resin composition contains an acid-dissociable group-containing resin in the positive type and an alkali-soluble resin and a crosslinking agent in the negative type.
[Selection figure] None

Description

The present invention relates to an acid generator, a sulfonic acid and its derivatives, and a radiation-sensitive resin composition. More specifically, the present invention particularly relates to a KrF excimer laser, ArF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet) or the like. Radiation sensitive acid generation of radiation sensitive resin composition used as a chemically amplified resist useful for microfabrication using various types of radiation such as ultraviolet rays, synchrotron radiation, etc. Acid generators suitable as agents, sulfonic acids generated from the acid generators, sulfonic acid derivatives useful as raw materials or intermediates for synthesizing the acid generators, and positive and negative types containing the acid generator The present invention relates to a radiation sensitive resin composition.

In the field of microfabrication represented by the manufacture of integrated circuit elements, a lithography process capable of microfabrication at a level of 0.20 μm or less is recently required to obtain a higher degree of integration.
However, in the conventional lithography process, near ultraviolet rays such as i rays are generally used as radiation, and it is said that fine processing at the subquarter micron level is extremely difficult with this near ultraviolet rays.
Therefore, in order to enable microfabrication at a level of 0.20 μm or less, use of radiation having a shorter wavelength is being studied. Examples of such short-wavelength radiation include an emission line spectrum of a mercury lamp, deep ultraviolet rays typified by an excimer laser, X-rays, and electron beams. Among these, a KrF excimer laser (wavelength 248 nm) is particularly preferable. ), ArF excimer laser (wavelength 193 nm),
A technique using an F ₂ excimer laser (wavelength 157 nm), EUV (wavelength 13 nm, etc.), an electron beam or the like has attracted attention.

As a radiation-sensitive resin composition suitable for short-wave radiation, a component having an acid-dissociable functional group and a radiation-sensitive acid generator that generates an acid upon irradiation with radiation (hereinafter referred to as “exposure”) Many compositions utilizing the chemical amplification effect between them (hereinafter referred to as “chemically amplified radiation-sensitive composition”) have been proposed.
Examples of the chemically amplified radiation-sensitive composition include, for example, JP-B-2-27660, a polymer having a t-butyl ester group of carboxylic acid or a t-butyl carbonate group of phenol and generation of a radiation-sensitive acid. A composition containing an agent has been proposed. In this composition, the t-butyl ester group or t-butyl carbonate group present in the polymer is dissociated by the action of an acid generated by exposure, and the polymer is an acidic compound comprising a carboxyl group or a phenolic hydroxyl group. A group is formed, and as a result, a phenomenon that the exposed region of the resist film becomes readily soluble in an alkali developer is utilized.

By the way, properties required for a radiation-sensitive acid generator in a chemically amplified radiation-sensitive composition are excellent in transparency to radiation, have a high quantum yield in acid generation, and have a sufficiently strong acid to be generated. For example, the boiling point of the acid is sufficiently high and the diffusion distance of the generated acid in the resist film (hereinafter referred to as “diffusion length”) is appropriate.
Among these, regarding the strength, boiling point, and diffusion length of the acid, the structure of the anion moiety is important in the ionic radiation-sensitive acid generator, and the nonionic property having a normal sulfonyl structure or sulfonate structure is used. In the radiation-sensitive acid generator, the structure of the sulfonyl moiety is important. For example, in the case of a radiation sensitive acid generator having a trifluoromethanesulfonyl structure, the acid generated is sufficiently strong and the resolution performance as a photoresist is sufficiently high, but the acid boiling point is low, and the acid diffusion length is also low. However, there is a drawback that the mask dependency as a photoresist is increased. Further, in the case of a radiation sensitive acid generator having a sulfonyl structure bonded to a large organic group such as 10-camphorsulfonyl structure, the boiling point of the generated acid is sufficiently high and the diffusion length of the acid is sufficiently short. Although the dependence becomes small, the strength of acid is not sufficient, so that the resolution performance as a photoresist is not sufficient.

On the other hand, a radiation-sensitive acid generator having a perfluoroalkylsulfonyl structure such as perfluoro-n-octanesulfonic acid (PFOS) has sufficient acidity, and the boiling point and diffusion length of the acid are generally appropriate. In recent years, it has attracted particular attention.
However, radiation sensitive acid generators having a perfluoroalkylsulfonyl structure such as PFOS are generally low in flammability and suspected to accumulate in the human body when considering environmental issues. Report by ENVIRONMENTAL PROTECTION AGENCY in the US (See Non-Patent Document 1), a proposal for restricting use is made. Therefore, in the field of microfabrication, there is an urgent need to develop an alternative component that does not have such drawbacks and has an excellent function as a radiation-sensitive acid generator.
“Perfluorooctyl Sulfonates; Proposed Significant New Use Rule”

The subject of the present invention is excellent in transparency to actinic radiation, particularly KrF excimer laser, ArF excimer laser, F ₂ excimer laser, EUV, and the like, and sensitive radiation sensitive to these actinic radiations. As an acid generator or as a thermal acid generator, it has a relatively high flammability, has no problem with human accumulation, and has a sufficiently high acidity and boiling point, and diffusion in a resist film. A novel acid generator having a moderately short length and low dependence on the sparse density of the mask pattern, a sulfonic acid generated from the acid generator, a sulfonic acid useful as a raw material or an intermediate for synthesizing the acid generator It is an object to provide a positive-type and negative-type radiation-sensitive resin composition containing a derivative and the acid generator.

The present invention, first,
It consists of an acid generator (hereinafter referred to as “acid generator (I)”) comprising a compound having a structure represented by the following general formula (I) (hereinafter referred to as “structure (I)”).

〔一般式（Ｉ）において、Ｒはフッ素含有率が５０重量％以下である１価の有機基、ニトロ基、シアノ基または水素原子を示し、Ｚ¹ およびＺ² は相互に独立にフッ素原子または炭素数１〜１０の直鎖状もしくは分岐状のパーフルオロアルキル基を示す。〕

[In the general formula (I), R represents a monovalent organic group, nitro group, cyano group or hydrogen atom having a fluorine content of 50% by weight or less, and Z ¹ and Z ² are each independently a fluorine atom or A linear or branched perfluoroalkyl group having 1 to 10 carbon atoms is shown. ]

The present invention secondly,
It consists of a sulfonic acid represented by the following general formula (Ia) (hereinafter referred to as “sulfonic acid (Ia)”).

〔一般式（Ｉ−ａ）において、Ｒはフッ素含有率が５０重量％以下である１価の有機基、ニトロ基、シアノ基または水素原子を示し、Ｚ¹ およびＺ² は相互に独立にフッ素原子または炭素数１〜１０の直鎖状もしくは分岐状のパーフルオロアルキル基を示す。〕

[In the general formula (Ia), R represents a monovalent organic group, a nitro group, a cyano group, or a hydrogen atom having a fluorine content of 50% by weight or less, and Z ¹ and Z ² are each independently fluorine. An atom or a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms is shown. ]

Third, the present invention
It consists of a sulfonate represented by the following general formula (1C) (hereinafter referred to as “sulfonate (1C)”).

〔一般式（１Ｃ）において、Ｒはフッ素含有率が５０重量％以下である１価の有機基、ニトロ基、シアノ基または水素原子を示し、Ｚ¹ およびＺ² は相互に独立にフッ素原子または炭素数１〜１０の直鎖状もしくは分岐状のパーフルオロアルキル基を示し、ＭはＮａ、ＫまたはＬｉを示す。〕

[In the general formula (1C), R represents a monovalent organic group, nitro group, cyano group or hydrogen atom having a fluorine content of 50% by weight or less, and Z ¹ and Z ² are each independently a fluorine atom or A linear or branched perfluoroalkyl group having 1 to 10 carbon atoms is shown, and M is Na, K or Li. ]

〔一般式（４Ａ）において、Ｒはフッ素含有率が５０重量％以下である１価の有機基、ニトロ基、シアノ基または水素原子を示し、Ｚ¹ およびＺ² は相互に独立にフッ素原子または炭素数１〜１０の直鎖状もしくは分岐状のパーフルオロアルキル基を示し、Ａはハロゲン原子を示す。〕 The present invention fourthly,
It consists of a sulfonyl halide compound represented by the following general formula (4A) (hereinafter referred to as “sulfonyl halide compound (4A)”).

[In the general formula (4A), R represents a monovalent organic group, nitro group, cyano group or hydrogen atom having a fluorine content of 50% by weight or less, and Z ¹ and Z ² are each independently a fluorine atom or A linear or branched perfluoroalkyl group having 1 to 10 carbon atoms is shown, and A represents a halogen atom. ]

The present invention fifthly,
(I) An acid generator (I) and (b) an alkali-insoluble or alkali-insoluble resin having an acid-dissociable group, which contains a resin that becomes alkali-soluble when the acid-dissociable group is dissociated. It consists of positive type radiation sensitive resin composition characterized by these.

Sixth, the present invention
It comprises a positive radiation sensitive resin composition comprising (i) an acid generator (I), (b) an alkali-soluble resin, and (c) an alkali solubility control agent.

Seventh, the present invention
(A) It comprises a negative radiation sensitive resin composition comprising an acid generator (I), (b) an alkali-soluble resin, and (c) a compound that crosslinks the alkali-soluble resin in the presence of an acid. .

Hereinafter, embodiments of the present invention will be described in detail.
Acid generator (I)
The acid generator (I) is a component that generates sulfonic acid (Ia) by exposure or heating.
Since the acid generator (I) has a strong fluorine-containing electron withdrawing group at the α-position of the sulfonyl group in the structure (I), the acidity of the acid such as sulfonic acid generated is high, and the boiling point is sufficient. Since it is high, it is difficult to volatilize during the photolithography process, and the acid diffusion length in the resist film is also reasonably short. Furthermore, since the fluorine content in the generated acid is lower than that of perfluoroalkylsulfonic acid, the combustibility is relatively high and the human body accumulation property is also low.

In the general formula (I), examples of the monovalent organic group having a fluorine content of R of 50% by weight or less include -R ¹¹ , -CO-R ¹¹ , -COO-R ¹¹ , -CON (R ¹¹ ) (R ¹² ), —S—R ¹¹ , —SO—R ¹¹ , —SO ₂ —R ¹¹ (where R ¹¹ and R ¹² are each independently a substituted or unsubstituted straight chain having 1 to 30 carbon atoms) And a substituted, unsubstituted or monovalent hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted monovalent heterocyclic organic group having 4 to 30 carbon atoms.) Etc.

Examples of the unsubstituted linear, branched or cyclic monovalent hydrocarbon group having 1 to 30 carbon atoms represented by R ¹¹ and R ¹² include, for example, methyl group, ethyl group, n-propyl group, i-propyl Group, n-butyl group, t-butyl group, n-pentyl group, i-pentyl group, n-hexyl group, i-hexyl group, n-octyl group, i-octyl group, 2-ethylhexyl group, n-dodecyl group And groups such as a group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a group having a norbornene skeleton, a group having a norbornane skeleton, a group having a tricyclodecane skeleton, and a group having a tetracyclododecane skeleton.
Examples of the substituent of the hydrocarbon group include an aryl group, an alkenyl group, and an organic group containing a hetero atom such as a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Can do.
Examples of the linear, branched or cyclic monovalent hydrocarbon group having 1 to 30 carbon atoms substituted with the substituent include benzyl, methoxymethyl, methylthiomethyl, ethoxymethyl, and phenoxy. Methyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, acetylmethyl group, fluoromethyl group, trifluoromethyl group, chloromethyl group, trichloromethyl group, 2-fluoropropyl group, trifluoroacetylmethyl group, trichloroacetylmethyl group , Pentafluorobenzoylmethyl group, aminomethyl group, cyclohexylaminomethyl group, diphenylphosphinomethyl group, trimethylsilylmethyl group, 2-phenylethyl group, 3-phenylpropyl group, 2-aminoethyl group and the like.

Examples of the unsubstituted aryl group having 6 to 30 carbon atoms of R ¹¹ and R ¹² include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, and a 1-phenanthryl group. .
Examples of the unsubstituted monovalent heterocyclic organic group having 4 to 30 carbon atoms of R ¹¹ and R ¹² include a furyl group, a thienyl group, a pyranyl group, a pyrrolyl group, a thiantenyl group, a pyrazolyl group, an isothiazolyl group, and an isoxazolyl group. , A pyrazinyl group, a pyrimidinyl group, and a pyridazinyl group.
Examples of the substituent for the aryl group and the monovalent heterocyclic organic group include an alkyl group and an organic group containing a hetero atom such as a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Can be mentioned.

Examples of the substituted aryl group having 6 to 30 carbon atoms include, for example, o-tolyl group, m-tolyl group, p-tolyl group, p-methoxyphenyl group, mesityl group, o-cumenyl group, and 2,3-xylyl. Group, p-fluorophenyl group, p-trifluoromethylphenyl group, p-bromophenyl group, p-chlorophenyl group, p-iodophenyl group and the like.
Examples of the substituted monovalent heterocyclic organic group having 4 to 30 carbon atoms include a 2-bromofuryl group and a 3-methoxythienyl group.

R in the general formula (I) has a methyl group, an ethyl group, an n-butyl group, a cyclohexyl group, a phenyl group, a 1-naphthyl group, a group having a norbornene skeleton, a group having a norbornane skeleton, or a tricyclodecane skeleton. R ¹¹ is a methyl group or an ethyl group among hydrocarbon groups such as a group, a group having a tetracyclododecane skeleton, or a group represented by —S—R ¹¹ , —SO—R ¹¹ or —SO ₂ —R ¹¹ , N-butyl group, cyclohexyl group, phenyl group and other hydrocarbon groups are preferable, and a group having a norbornene skeleton, a group having a norbornane skeleton, a group having a tetracyclododecane skeleton, and the like are particularly preferable.

In the general formula (I), examples of the perfluoroalkyl group having 1 to 10 carbon atoms of Z ¹ and Z ² include trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, and nonafluoro-n-butyl. Groups and the like.

  Preferable structure (I) includes, for example, structures represented by the following general formula (I-1), general formula (I-2), or general formula (I-3), and more preferably It is a structure represented by Formula (I-1) or General Formula (I-3).

  Moreover, as another preferable structure (I), the structure etc. which are represented by the following general formula (IA) or general formula (IB) can be mentioned, for example.

〔一般式（Ｉ−１）、一般式（Ｉ−２）および一般式（Ｉ−３）において、各Ｒは相互に独立に一般式（Ｉ）におけるＲと同義である。〕

[In General Formula (I-1), General Formula (I-2), and General Formula (I-3), each R is independently the same as R in General Formula (I). ]

〔一般式（Ｉ−Ａ）および一般式（Ｉ−Ｂ）において、Ｚ¹ およびＺ² は相互に独立に一般式（Ｉ）におけるそれぞれＺ¹ およびＺ² と同義であり、Ｙ¹ は単結合または２価の基を示し、Ｒ’は１価の置換基を示し、ｋは０以上の整数であり、ｎは０〜５の整数である。〕

[In formula (I-A) and the general formula (I-B), Z ¹ and Z ² have the same meanings as Z ¹ and Z ^2, respectively, in the general formula (I) independently from each other, Y ¹ is a single bond Or it shows a bivalent group, R 'shows a monovalent substituent, k is an integer greater than or equal to 0, and n is an integer of 0-5. ]

Examples of the divalent group represented by Y ¹ include —O—, —S—, carbonyl group, sulfinyl group, sulfonyl group, methylene group, 1,1-ethylene group, 1,2-ethylene group, propylene group, 1 -Methylpropylene group, 1-ethylpropylene group, trimethylene group, difluoromethylene group, tetrafluoro-1,2-ethylene group, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, etc. Can be mentioned.

  Of these divalent groups, a carbonyl group, a methylene group, a difluoromethylene group, a tetrafluoro-1,2-ethylene group and the like are preferable.

  Examples of the monovalent or divalent substituent for R ′ include an oxo group (═O), a hydroxyl group, a carboxyl group, a formyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, C1-C10 linear or branched vinylidene group, C1-C12 monovalent cyclic organic group, C6-C20 aryl group, C1-C10 linear or branched An alkoxyl group, an aryloxy group having 6 to 20 carbon atoms, a linear or branched alkylcarbonyl group having 2 to 10 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, a straight chain having 1 to 10 carbon atoms or Examples thereof include a branched alkoxycarbonyl group and an aryloxycarbonyl group having 7 to 20 carbon atoms.

Examples of the linear or branched alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, and n-pentyl. Group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.
Examples of the linear or branched vinylidene group having 1 to 10 carbon atoms include carbenyl group, 1,1-ethylidenyl group, propylidenyl group, 1-methylpropylidenyl group, 1-ethylpropylidene group. A denyl group etc. can be mentioned.
Examples of the monovalent cyclic organic group having 1 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, and a camphoroyl group.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, p-hydroxyphenyl group, 1-naphthyl group, 1-anthracenyl group, A benzyl group etc. can be mentioned.
Examples of the linear or branched alkoxyl group having 1 to 10 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, and t-butoxy group. Can be mentioned.
Moreover, as said C6-C20 aryloxy group, a phenoxy group, p-hydroxyphenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group etc. can be mentioned, for example.

Examples of the linear or branched alkylcarbonyl group having 2 to 10 carbon atoms include a methylcarbonyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an i-propylcarbonyl group, an n-butylcarbonyl group, Examples thereof include a t-butylcarbonyl group.
Examples of the arylcarbonyl group having 7 to 20 carbon atoms include a phenylcarbonyl group and a benzylcarbonyl group.
Examples of the linear or branched alkoxycarbonyl group having 2 to 10 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, Examples thereof include a t-butoxycarbonyl group.

Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms include a phenoxycarbonyl group and a benzyloxycarbonyl group. In addition, these substituents can further have an arbitrary substituent, for example, one or more of the above-described substituents.
In general formula (IA) and general formula (IB), R ′ can be bonded to any of the carbon atoms constituting the norbornene ring or norbornane ring in each formula, and a plurality of R ′ are present. They may be the same or different from each other.

In general formula (IA) and general formula (IB), Y ¹ is preferably a single bond, a methylene group, a carbonyl group, k is preferably 0, and n is preferably 0 or 1.

  Preferred examples of the structure (IA) and the structure (IB) include, for example, the following formulas (A-1) to (A-12) and the following formulas (B-1) to (B-12). And the like.

  Among the acid generators (I), examples of the ionic compound include a sulfonic acid onium salt compound represented by the following general formula (1) (hereinafter referred to as “sulfonic acid onium salt compound (1)”). be able to. The sulfonic acid onium salt compound (1) is a compound in which a sulfonyl group in the structure (I) is bonded to an oxygen anion to form a sulfonic acid anion.

〔一般式（１）において、Ｒ、Ｚ¹ およびＺ² は一般式（Ｉ）におけるそれぞれＲ、Ｚ¹ およびＺ² と同義であり、Ｍ⁺ は１価のオニウムカチオンを示す。〕

In [Formula (1), R, Z ¹ and Z ² are each in the general formula (I) has the same meaning R, a Z ¹ and Z ^2, M ⁺ represents a monovalent onium cation. ]

In the general formula (1), examples of the monovalent onium cation of M ⁺ include onium cations such as O, S, Se, N, P, As, Sb, Cl, Br, and I. Of these onium cations, S and I onium cations are preferred.
In the general formula (1), examples of the M ⁺ monovalent onium cation include those represented by the following general formula (i) or general formula (ii).

〔一般式（ｉ）において、Ｒ¹ 、Ｒ² およびＲ³ は相互に独立に置換もしくは非置換の炭素数１〜２０の直鎖状もしくは分岐状のアルキル基または置換もしくは非置換の炭素数６〜２０のアリール基を示すか、あるいはＲ¹ 、Ｒ² およびＲ³ のうちの何れか２つ以上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いる。〕

[In General Formula (i), R ¹ , R ² and R ³ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted carbon number of 6 Or an aryl group of ˜20, or any two or more of R ¹ , R ² and R ³ are bonded to each other to form a ring together with the sulfur atom in the formula. ]

〔一般式（ii）において、Ｒ⁴ およびＲ⁵ は相互に独立に置換もしくは非置換の炭素数１〜２０の直鎖状もしくは分岐状のアルキル基または置換もしくは非置換の炭素数６〜２０のアリール基を示すか、あるいはＲ⁴ およびＲ⁵ が相互に結合して式中のヨウ素原子と共に環を形成している。〕

[In General Formula (ii), R ⁴ and R ⁵ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted 6 to 20 carbon atoms. It represents an aryl group, or R ⁴ and R ⁵ are bonded to each other to form a ring together with the iodine atom in the formula. ]

The monovalent onium cation moiety of M ⁺ can be produced according to the general method described in “JV Crivello, Advances in Polymer Science 62, 49, 1984”, for example.

  Preferred monovalent onium cations include, for example, sulfonium cations represented by the following formulas (i-1) to (i-64) and iodonium cations represented by the following formulas (ii-1) to (ii-39). Etc.

  Among these monovalent onium cations, for example, the formula (i-1), formula (i-2), formula (i-6), formula (i-8), formula (i-13), formula ( i-19), a sulfonium cation represented by formula (i-25), formula (i-27), formula (i-29), formula (i-51) or formula (i-54); -1) or an iodonium cation represented by the formula (ii-11) is preferable.

  Preferred examples of the sulfonic acid onium salt compound (1) include compounds represented by the following general formula (1-A) or general formula (1-B).

〔一般式（１−Ａ）および一般式（１−Ｂ）において、Ｚ¹ およびＺ² は一般式（Ｉ）におけるそれぞれＺ¹ およびＺ² と同義であり、Ｙ¹ 、Ｒ’、ｋおよびｎは一般式（Ｉ−Ａ）および一般式（Ｉ−Ｂ）におけるそれぞれＹ¹ 、Ｒ’、ｋおよびｎと同義であり、Ｍ⁺ は一般式（１）におけるＭ⁺ と同義である。〕

[Formula (1-A) and general formula ^(1-B), Z 1 and Z ² have the same meanings as Z ¹ and Z ^2, respectively, in the general formula ^{(I), Y 1, R} ', k and n the formula (I-a) and the general formula each Y ¹ in (I-B), R ' , has the same meaning as k and n, M ⁺ is synonymous with M ⁺ in the general formula (1). ]

  Moreover, as a nonionic compound among acid generators (I), for example, an N-sulfonyloxyimide compound represented by the following general formula (2) (hereinafter, “N-sulfonyloxyimide compound (2)”) Can be mentioned).

〔一般式（２）において、Ｒ、Ｚ¹ およびＺ² は一般式（Ｉ）におけるそれぞれＲ、Ｚ¹ およびＺ² と同義であり、Ｒ⁶ およびＲ⁷ は相互に独立に水素原子または置換もしくは非置換の１価の有機基を示すか、あるいはＲ⁶ およびＲ⁷ が相互に結合してそれらが結合している炭素原子と共に環を形成しており、Ｙ² は単結合、二重結合または２価の有機基を示す。〕

In [Formula (2), R, Z ¹ and Z ² have the same meanings R, and Z ¹ and Z ^2, respectively, in the general formula (I), R ⁶ and R ⁷ are hydrogen atoms or substituted or independently from each other Represents an unsubstituted monovalent organic group, or R ⁶ and R ⁷ are bonded to each other to form a ring together with the carbon atom to which they are bonded, and Y ² is a single bond, a double bond or A divalent organic group is shown. ]

  Preferable examples of the N-sulfonyloxyimide compound (2) include compounds represented by the following general formula (2-A) or general formula (2-B).

〔一般式（２−Ａ）および一般式（２−Ｂ）において、Ｚ¹ およびＺ² は一般式（Ｉ）におけるそれぞれＺ¹ およびＺ² と同義であり、Ｙ¹ 、Ｒ’、ｋおよびｎは一般式（Ｉ−Ａ）および一般式（Ｉ−Ｂ）におけるそれぞれＹ¹ 、Ｒ’、ｋおよびｎと同義であり、Ｒ⁶ 、Ｒ⁷ およびＹ² は一般式（２）におけるそれぞれ
Ｒ⁶ 、Ｒ⁷ およびＹ² と同義である。〕

[Formula (2-A) and general formula (2-B), Z ¹ and Z ² have the same meanings as Z ¹ and Z ^2, respectively, in the general formula ^{(I), Y 1, R} ', k and n Is synonymous with Y ¹ , R ′, k and n in general formula (IA) and general formula (IB), respectively, and R ⁶ , R ⁷ and Y ² are R ⁶ in general formula (2), respectively. , R ⁷ and Y ² . ]

In the general formula (2), general formula (2-A) and general formula (2-B), examples of preferable imide groups bonded to the sulfonyloxy group (SO ₂ —O—) in each formula include the following formulas Examples include groups (2-1) to (2-9).

  Of these imide groups, for example, a group represented by the formula (2-1), formula (2-4), formula (2-8) or formula (2-9) is preferred.

Here, the production method of the sulfonic acid onium salt compound (1) will be described in detail.
The sulfonic acid onium salt compound (1) can be produced, for example, according to the general methods described in Non-Patent Document 2 and Non-Patent Document 3.
That is, as shown in the following reaction formula [1], the corresponding precursor compound [1a] is converted to a sulfinate [1b] by reacting with sodium dithionite in the presence of an inorganic base, This is oxidized with an oxidizing agent such as hydrogen peroxide to convert it to a sulfonate (1C) such as sulfonate [1c], and then subjected to an ion exchange reaction with a counter ion exchange precursor M ⁺ X ^−. It can manufacture by doing.
DD DesMarteau, Inorganic Chemistry, Vol.32, 5007, 1993 JV Crivello, Advances in Polymer Science 62, 49, 1984

〔反応式 [１] において、Ｘは脱離性の１価の基を示し、Ｘ^- は１価のアニオンを示す。〕

[In Reaction Formula [1], X represents a leaving monovalent group, and X ⁻ represents a monovalent anion. ]

  Examples of the detachable monovalent group of X in the precursor compound [1a] include halogen atoms such as chlorine atom, bromine atom and iodine atom, methanesulfonate group, p-toluenesulfonate group and the like. Preferably, they are a bromine atom and an iodine atom.

In the reaction of the precursor compound [1a] with sodium dithionite, the molar ratio of sodium dithionite to the precursor compound [1a] is usually 0.01 to 100, preferably 1.0 to 10.
Examples of the inorganic base used in the reaction include lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like, preferably sodium hydrogen carbonate, potassium hydrogen carbonate and the like. .
The molar ratio of the inorganic base to sodium dithionite is usually 1.0 to 10.0, preferably 2.0 to 4.0.
This reaction is preferably performed in a mixed solvent of an organic solvent and water. As the organic solvent, for example, a solvent having good compatibility with water, such as lower alcohols, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethylsulfoxide, and the like are more preferable. N-dimethylacetamide, acetonitrile, dimethyl sulfoxide and the like are preferable, and acetonitrile is particularly preferable.
The use ratio of the organic solvent is usually 5 to 100 parts by weight, preferably 10 to 100 parts by weight, and more preferably 20 to 90 parts by weight with respect to 100 parts by weight of the total of the organic solvent and water. The reaction temperature is usually 40 to 200 ° C., preferably 60 to 120 ° C., and the reaction time is usually 0.5 to 72 hours, preferably 2 to 24 hours. When the reaction temperature is higher than the boiling point of the organic solvent or water, a pressure vessel such as an autoclave is used.

In the oxidation reaction of the sulfinate [1b], as an oxidizing agent, in addition to hydrogen peroxide, metachloroperbenzoic acid, t-butyl hydroperoxide, potassium peroxysulfate, potassium permanganate, sodium perborate, metaiodine Sodium oxalate, chromic acid, sodium dichromate, halogen, iodobenzene dichloride, iodobenzene diacetate, osmium oxide (VII), ruthenium oxide (VII), sodium hypochlorite, sodium chlorite, oxygen gas, ozone gas Among them, hydrogen peroxide, metachloroperbenzoic acid, t-butyl hydroperoxide and the like are preferable.
The molar ratio of the oxidizing agent to the sulfinate [1b] is usually 1.0 to 10.0, preferably 1.5 to 4.0.
In addition, a transition metal catalyst can be used in combination with the oxidizing agent.
Examples of the transition metal catalyst include disodium tungstate, iron (III) chloride, ruthenium (III) chloride, selenium oxide (IV) and the like, preferably disodium tungstate.
The molar ratio of the transition metal catalyst to the sulfinate [1b] is usually 0.001 to 2.0, preferably 0.01 to 1.0, and more preferably 0.03 to 0.5.

Furthermore, in addition to the oxidizing agent and the transition metal catalyst, a buffering agent may be used in combination for the purpose of adjusting the pH of the reaction solution.
Examples of the buffer include disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, and potassium dihydrogen phosphate. The molar ratio of the buffering agent to the sulfinate [1b] is usually 0.01 to 2.0, preferably 0.03 to 1.0, and more preferably 0.05 to 0.5.
This reaction is usually performed in a reaction solvent. The reaction solvent is preferably water or an organic solvent such as lower alcohols, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, acetic acid, trifluoroacetic acid, and more preferably. Methanol, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide and the like are preferable, and methanol is particularly preferable.
The amount of the reaction solvent used per 100 parts by weight of the sulfinate [1b] is usually 5 to 100 parts by weight, preferably 10 to 100 parts by weight, and more preferably 20 to 50 parts by weight. Moreover, the said organic solvent and water can also be used together as needed, and the usage-amount of the organic solvent in that case is 5-100 weight part normally with respect to a total of 100 weight part of an organic solvent and water. The amount is preferably 10 to 100 parts by weight, more preferably 20 to 90 parts by weight.
The reaction temperature is usually 0 to 100 ° C., preferably 5 to 60 ° C., more preferably 5 to 40 ° C., and the reaction time is usually 0.5 to 72 hours, preferably 2 to 24 hours.

Further, the ion exchange reaction of the sulfonate [1c] can be performed, for example, according to the general method described in Non-Patent Document 3.
In the ion exchange reaction, for example, a method such as ion exchange chromatography can be employed.
Examples of the monovalent anion of X ⁻ in the reaction formula [1] include F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , perchlorate ion, hydrogen sulfate ion, dihydrogen phosphate ion, and tetrafluoroboric acid. Ion, aliphatic sulfonate ion, aromatic sulfonate ion, trifluoromethanesulfonate ion, fluorosulfonate ion, hexafluorophosphate ion, hexachloroantimonate ion, etc., preferably Cl ⁻ ,
Br ⁻ , hydrogen sulfate ion, tetrafluoroborate ion, aliphatic sulfonate ion and the like, more preferably chloride ion, bromide ion and hydrogen sulfate ion. The molar ratio of the counter ion precursor to the sulfonate [1c] is usually 0.1 to 10.0, preferably 0.3 to 4.0, more preferably 0.7 to 2.0. is there.

This reaction is usually performed in a reaction solvent. The reaction solvent is preferably water or an organic solvent such as lower alcohols, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, more preferably water, methanol, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide and the like, particularly preferably water.
The use amount of the reaction solvent is usually 5 to 100, preferably 10 to 100 parts by weight, and more preferably 20 to 50 parts by weight with respect to 100 parts by weight of the counter ion exchange precursor. Moreover, if necessary, water and an organic solvent can be used in combination, and the use ratio of the organic solvent in this case is usually 5 to 100 parts by weight with respect to a total of 100 parts by weight of water and the organic solvent. Preferably it is 10-100 weight part, More preferably, it is 20-90 weight part.
The reaction temperature is usually 0 to 80 ° C., preferably 5 to 30 ° C., and the reaction time is usually 10 minutes to 6 hours, preferably 30 minutes to 2 hours.

The sulfonic acid onium salt compound (1) thus obtained can be purified by extraction with an organic solvent.
Examples of organic solvents used for purification include organic solvents that are not miscible with water, such as esters such as ethyl acetate and n-butyl acetate; ethers such as diethyl ether; alkyl halides such as methylene chloride and chloroform. Is preferred.

  In addition, the sulfonic acid onium salt compound (1) represented by the general formula (1-A) includes, for example, a corresponding ethylene derivative [2a] and a corresponding cyclopentadiene compound as shown in the following reaction formula [2] A norbornene derivative [2b] is synthesized by a Diels-Alder reaction with, or as shown in the following reaction formula [3], a norbornene derivative [2b] obtained by the procedure of the corresponding cyclopentadiene compound and the reaction formula [2] The norbornene derivatives [3b] are synthesized by a Diels-Alder reaction with the compound, and can be produced by reacting these norbornene derivatives with the procedure shown in the above reaction formula [1]. The sulfonic acid onium salt compound (1) having a total of three or more norbornene or norbornane rings is produced in the same manner as described above after synthesizing a polycyclic norbornene derivative by repeating the procedure shown in the reaction formula [3]. be able to.

〔反応式 [２] において、Ｚ¹ およびＺ² は一般式（Ｉ）におけるそれぞれＺ¹ およびＺ² と同義であり、Ｙ¹ は一般式（Ｉ−Ａ）および一般式（Ｉ−Ｂ）におけるＹ¹ と同義であり、Ｘは反応式 [１] におけるＸと同義である。〕

In [reaction formula [2], Z ¹ and Z ² have the same meanings as Z ¹ and Z ^2, respectively, in the general formula (I), Y ¹ is in the formula (I-A) and formula (I-B) It is synonymous with Y ¹ , and X is synonymous with X in the reaction formula [1]. ]

〔反応式 [３] において、Ｚ¹ およびＺ² は一般式（Ｉ）におけるそれぞれＺ¹ およびＺ² と同義であり、Ｙ¹ は一般式（Ｉ−Ａ）および一般式（Ｉ−Ｂ）におけるＹ¹ と同義であり、Ｘは反応式 [１] におけるＸと同義である。〕

In [reaction formula [3], Z ¹ and Z ² have the same meanings as Z ¹ and Z ^2, respectively, in the general formula (I), Y ¹ is in the formula (I-A) and formula (I-B) It is synonymous with Y ¹ , and X is synonymous with X in the reaction formula [1]. ]

Here, the reaction formula [2] and the reaction formula [3] will be described more specifically.
Each Diels-Alder reaction in Reaction Formula [2] and Reaction Formula [3] can be performed, for example, according to a general method described in Non-Patent Document 4.
Comprehensive Organic Synthesis, BM Trost & I. Fleming, Pergamon Press, New York, 1991, Vol. The molar ratio of the system compound to the norbornene derivative [2b] is usually 0.01 to 100, preferably 0.1 to 10, respectively. These reactions are performed in the absence of a solvent or in a reaction solvent such as toluene, xylene, N, N-dimethylformamide, tetrahydrofuran, 1,2-dichloroethane. The reaction temperature is usually 20 to 250 ° C., preferably 80 to 180 ° C., and the reaction time is usually 0.5 to 24 hours, preferably 4 to 12 hours. When the reaction temperature is higher than the boiling point of the reaction raw material or reaction solvent, a pressure vessel such as an autoclave is used.

In addition, the sulfonic acid onium salt compound (1) represented by the general formula (1-B) includes, for example, a norbornene derivative [2b] synthesized by the procedure shown in the reaction formula [2], the reaction formula [3], and the like. Norbornene derivatives such as norbornene derivative [3b] can be carried out by contacting with hydrogen gas in the reaction solvent in the presence of a hydrogenation catalyst.
Examples of the hydrogenation catalyst include transition metal catalysts such as Raney nickel, palladium-carbon, platinum (IV) oxide, rhodium-carbon, rhodium-alumina, ruthenium-carbon, and tris (triphenylphosphine) chlororhodium (I). Can be mentioned.
The weight ratio of the transition metal catalyst to each norbornene derivative is usually 0.001-1, preferably 0.01-0.2.
Moreover, the pressure of the hydrogen gas during the hydrogenation reaction is usually 1 to 120 atmospheres, preferably 1 to 100 atmospheres, and more preferably 1 to 50 atmospheres.
This reaction is usually performed in a reaction solvent. As the reaction solvent, for example, organic solvents such as methanol, ethanol, ethyl acetate, toluene, xylene, tetrahydrofuran, 1,2-dichloroethane are preferable.
The weight ratio of the reaction solvent to each norbornene derivative is usually 1 to 100, preferably 5 to 100, more preferably 10 to 80.
The reaction temperature is usually 20 to 200 ° C., preferably 20 to 150 ° C., more preferably 20 to 100 ° C., and the reaction time is usually 0.5 to 24 hours, preferably 4 to 12 hours. When the reaction temperature is higher than the boiling point of the reaction raw material or reaction solvent, or when the pressure of the hydrogen gas used exceeds 1 atm, a pressure vessel such as an autoclave is used.

Next, the production method of the N-sulfonyloxyimide compound (2) will be described in detail.
The N-sulfonyloxyimide compound (2) can be produced, for example, using the sulfinate [1b] or the sulfonate [1c] shown in the reaction formula [1].
That is, as shown in the following reaction formula [4], the sulfinate [1b] is converted into a sulfonyl halide compound (4A) such as sulfonyl chloride [4a] using a halogenating agent such as chlorine gas. And the corresponding N-hydroxyimide compound in the presence of a base catalyst in a reaction solvent.

The reaction of the sulfinate [1b] and the chlorinating agent can be carried out, for example, according to the general method described in Non-Patent Document 5 or the method described in Synthesis Example * described later.
DD DesMarteau, Inorganic Chemistry, Vol. 32, 5007, 1993 For the reaction, for example, a method of blowing chlorine gas into the reaction solution can be employed. The amount of the chlorinating agent used for the sulfinate [1b] during the reaction is usually a large excess. This reaction is usually performed in a reaction solvent. The reaction solvent is preferably, for example, water or an organic solvent such as tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, and more preferably water, methanol, N, N— Organic solvents such as dimethylacetamide, acetonitrile, dimethylsulfoxide and the like are preferable, and water is particularly preferable. The amount of the reaction solvent used per 100 parts by weight of the sulfinate [1b] is usually 5 to 100 parts by weight, preferably 10 to 100 parts by weight, and more preferably 20 to 50 parts by weight. Further, if necessary, water and the organic solvent can be used in combination, and the use ratio of the organic solvent in that case is usually 5 to 100 parts by weight with respect to 100 parts by weight of the total of water and the organic solvent. The amount is preferably 10 to 100 parts by weight, more preferably 20 to 90 parts by weight. The reaction temperature is usually 0 to 100 ° C., preferably 5 to 60 ° C., more preferably 5 to 40 ° C., and the reaction time is usually 5 minutes to 12 hours, preferably 10 minutes to 5 hours.

In the reaction of the sulfonyl chloride [4a] with the N-hydroxyimide compound, the molar ratio of the N-hydroxyimide compound to the sulfonyl chloride [4a] is usually 0.1 to 10.0, preferably 0.3 to 5. 0.0, more preferably 0.5 to 2.0.
This reaction is usually performed in a reaction solvent. As the reaction solvent, for example, organic solvents such as acetonitrile, dimethylformamide, tetrahydrofuran, dimethyl sulfoxide, methylene chloride, methylene bromide and chloroform are preferable, and acetonitrile, tetrahydrofuran, methylene chloride and the like are more preferable.
The usage-amount with respect to 100 weight part of sulfonyl chloride [4a] of a reaction solvent is 5-100 weight part normally, Preferably it is 10-100 weight part, More preferably, it is 20-50 weight part.
Examples of the base catalyst include triethylamine, pyridine, N, N-di-i-propyl ethylamine, 2,6-lutidine, N, N-diethylaniline, 4-dimethylaminopyridine, diazabicycloundecene, and the like. More preferred are triethylamine, 4-dimethylaminopyridine and the like.
The molar ratio of the base catalyst to the sulfonyl chloride [4a] is usually 1.0 to 10.0, preferably 1.5 to 5.0, and more preferably 1.5 to 3.0.
The reaction temperature is usually 0 to 80 ° C., preferably 5 to 30 ° C., and the reaction time is usually 5 minutes to 6 hours, preferably 10 minutes to 2 hours.

  Further, the N-sulfonyloxyimide compound (2) represented by the general formula (2-A) or the general formula (2-B) is, for example, the general formula (1-A) or the general formula (1-B). Using the norbornene derivative such as norbornene derivative [2b] and norbornene derivative [3b] described in the production method of the sulfonic acid onium salt compound (1) represented by formula (1), or a hydrogenated product thereof, the reaction formula [1] After the sulfinate [1b] is obtained by the procedure, it can be produced in the same manner as the procedure shown in the reaction formula [4].

Furthermore, examples of the acid generator (I) other than the sulfonic acid onium salt compound (1) and the N-sulfonyloxyimide compound (2) include a sulfone compound, a sulfonic acid ester compound, a disulfonyldiazomethane compound, and a disulfonylmethane compound. Oxime sulfonate compounds, hydrazine sulfonate compounds, and the like.
Hereinafter, these compounds will be described.

Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof.
Specific examples of the sulfone compound include compounds represented by the following general formula (3-1) and general formula (3-2).

〔一般式（３−１）および一般式（３−２）において、Ｒ、Ｚ¹ およびＺ² は一般式（Ｉ）におけるそれぞれＲ、Ｚ¹ およびＺ² と同義であり、一般式（３−２）における２個のＲ、Ｚ¹ およびＺ² はそれぞれ相互に同一でも異なってもよい。〕

[In the general formula (3-1) and the general formula (3-2), R, Z ¹ and Z ² are, respectively, in the general formula (I) as defined R, and Z ¹ and Z ^2, the general formula (3 Two R, Z ¹ and Z ² in 2) may be the same or different from each other. ]

Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.
Specific examples of the sulfonic acid ester include compounds represented by the following general formula (4).

〔一般式（４）において、Ｒ、Ｚ¹ およびＺ² は一般式（Ｉ）におけるそれぞれＲ、Ｚ¹ およびＺ² と同義であり、複数存在するＲ、Ｚ¹ およびＺ² はそれぞれ相互に同一でも異なってもよく、Ａはピロガロール、α−メチロールベンゾイン等に由来するｊ価の有機残基を示し、ｊは１〜３の整数である。〕

In [Formula (4), the same R, respectively Z ¹ and Z ² in the general formula (I) R, has the same meaning as Z ¹ and Z ^2, the R, Z ¹ and Z ² are each mutually presence of a plurality of However, A represents a j-valent organic residue derived from pyrogallol, α-methylolbenzoin and the like, and j is an integer of 1 to 3. ]

  As said disulfonyl diazomethane compound, the compound represented by following General formula (5) can be mentioned, for example.

〔一般式（５）において、Ｒ、Ｚ¹ およびＺ² は一般式（Ｉ）におけるそれぞれＲ、Ｚ¹ およびＺ² と同義であり、２個のＲ、Ｚ¹ およびＺ² はそれぞれ相互に同一でも異なってもよい。〕

In [Formula (5), R, Z ¹ and Z ² have the same meanings R, and Z ¹ and Z ^2, respectively, in the general formula (I), 2 pieces of the same R, are each Z ¹ and Z ² each other But it may be different. ]

  Examples of the disulfonylmethane compound include compounds represented by the following general formula (6).

In [Formula (6), R, Z ¹ and Z ² have the same meanings R, and Z ¹ and Z ^2, respectively, in the general formula (I), 2 pieces of the same R, are each Z ¹ and Z ² each other V and W may each independently represent an aryl group, a hydrogen atom, a linear or branched monovalent aliphatic hydrocarbon group, or other monovalent organic group having a hetero atom. And at least one of V and W is an aryl group, or V and W are connected to each other to form a monocyclic or polycyclic ring having at least one unsaturated bond, or V and W are A group represented by the following formula (7) connected to each other

(In the formula, V ′ and W ′ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, or V ′ bonded to the same or different carbon atoms. W ′ is connected to each other to form a carbon monocyclic structure, and a plurality of V ′ and W ′ may be the same or different, and a is an integer of 2 to 10.)
Is forming. ]

  Examples of the oxime sulfonate compound include compounds represented by general formula (8-1) or general formula (8-2).

〔一般式（８−１）および一般式（８−２）において、Ｒ、Ｚ¹ およびＺ² は一般式（Ｉ）におけるそれぞれＲ、Ｚ¹ およびＺ² と同義であり、一般式（８−２）における２個のＲ、Ｚ¹ およびＺ² はそれぞれ相互に同一でも異なってもよく、Ｒ⁸ および各Ｒ⁹ は相互に独立に１価の有機基を示す。〕

[Formula (8-1) and the general formula (8-2), R, Z ¹ and Z ² are each in the general formula (I) has the same meaning R, a Z ¹ and Z ^2, the general formula (8 Two R, Z ¹ and Z ² in 2) may be the same or different from each other, and R ⁸ and each R ⁹ each independently represent a monovalent organic group. ]

  Examples of the hydrazine sulfonate compound include compounds represented by general formula (9-1) or general formula (9-2).

〔一般式（９−１）および一般式（９−２）において、Ｒ、Ｚ¹ およびＺ² は一般式（Ｉ）におけるそれぞれＲ、Ｚ¹ およびＺ² と同義であり、一般式（９−２）における２個のＲ、Ｚ¹ およびＺ² はそれぞれ相互に同一でも異なってもよい。〕

[Formula (9-1) and the general formula (9-2), R, Z ¹ and Z ² are each in the general formula (I) has the same meaning R, a Z ¹ and Z ^2, the general formula (9 Two R, Z ¹ and Z ² in 2) may be the same or different from each other. ]

Positive type radiation sensitive resin composition The positive type radiation sensitive resin composition of the present invention comprises:
(A) (A) Acid generator (I) and (B) Alkali-insoluble or alkali-insoluble resin having an acid-dissociable group, which becomes alkali-soluble when the acid-dissociable group is dissociated (hereinafter referred to as “resin”) Or a composition containing “acid-dissociable group-containing resin” (hereinafter referred to as “positive-type radiation-sensitive resin composition (A)”), or (B) (A) Acid generator (I) And (C) a composition containing an alkali-soluble resin and (D) an alkali-solubility control agent (hereinafter referred to as “positive type radiation-sensitive resin composition (b)”).
The acid generator (I) in these positive radiation sensitive resin compositions is preferably thermally and chemically stable.
Hereinafter, the positive radiation sensitive resin composition (A) and the positive radiation sensitive resin composition (B) will be described.

In the positive radiation sensitive resin composition (A) and the positive radiation sensitive resin composition (B), the acid generator (I) can be used alone or in admixture of two or more.
In the positive-type radiation-sensitive resin composition (a) and the positive-type radiation-sensitive resin composition (b), the amount of the acid generator (I) used is the acid generator (I) or other acid used in some cases. Although it depends on the type of the generator, it is usually 0.1 to 20 parts by weight, preferably 0.1 to 15 parts by weight, more preferably 0.2 per 100 parts by weight of the acid-dissociable group-containing resin or alkali-soluble resin. ~ 12 parts by weight. In this case, if the amount of the acid generator (I) used is less than 0.1 parts by weight, the desired effect of the present invention may not be sufficiently exhibited, whereas if it exceeds 20 parts by weight, the transparency to radiation is likely to be present. In addition, the pattern shape, heat resistance, etc. may be reduced.

<Acid-dissociable group-containing resin>
The acid-dissociable group-containing resin in the positive-type radiation-sensitive resin composition (a) is an oxygen-containing functional group in the resin having one or more oxygen-containing functional groups such as a phenolic hydroxyl group, an alcoholic hydroxyl group, and a carboxyl group. A hydrogen atom is substituted with one or more acid-dissociable groups capable of dissociating in the presence of an acid, which is itself an alkali-insoluble or hardly alkali-soluble resin, and the acid-dissociable group is dissociated. Sometimes it becomes alkali-soluble resin.
The term “alkali insoluble or hardly alkali-soluble” as used herein is employed when a resist pattern is formed from a resist film formed using a positive radiation-sensitive resin composition containing an acid-dissociable group-containing resin. When a film using only an acid-dissociable group-containing resin instead of the resist film is developed under alkaline development conditions, it means the property that 50% or more of the initial film thickness of the film remains after development.

Examples of the acid dissociable group in the acid dissociable group-containing resin include a substituted methyl group, 1-substituted ethyl group, 1-substituted n-propyl group, 1-branched alkyl group, silyl group, germyl group, and alkoxycarbonyl. Group, acyl group, cyclic acid dissociable group and the like.
Examples of the substituted methyl group include methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, methoxyethoxymethyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, 4-bromophenacyl group, 4 -Methoxyphenacyl group, 4-methylthiophenacyl group, α-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, adamantylmethyl group, 4-bromobenzyl group, 4-nitro Benzyl group, 4-methoxybenzyl group, 4-methylthiobenzyl group, 4-ethoxybenzyl group, 4-ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i- Propoxycarbo Rumechiru group, n- butoxycarbonyl methyl group, and a t- butoxycarbonyl methyl group.
Examples of the 1-substituted ethyl group include 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1- Diethoxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropyloxyethyl group, 1 -Cyclohexyloxyethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group, 1-i-propoxycarbonylethyl Group, 1-n-butoxycarbonylethyl group, 1-t-butoxycarbonylethyl group, 1-cyclo It can be mentioned hexyl butyloxycarbonylethyl group.

Examples of the 1-substituted-n-propyl group include a 1-methoxy-n-propyl group and a 1-ethoxy-n-propyl group.
Examples of the 1-branched alkyl group include i-propyl group, sec-butyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, and the like. Can be mentioned.
Examples of the silyl group include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, i-propyldimethylsilyl group, methyldi-i-propylsilyl group, tri-i-propylsilyl group, Examples thereof include a t-butyldimethylsilyl group, a methyldi-t-butylsilyl group, a tri-t-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group.
Examples of the germyl group include a trimethylgermyl group, an ethyldimethylgermyl group, a methyldiethylgermyl group, a triethylgermyl group, an i-propyldimethylgermyl group, a methyldi-i-propylgermyl group, and a trimethylgermyl group. -I-propylgermyl group, t-butyldimethylgermyl group, methyldi-t-butylgermyl group, tri-t-butylgermyl group, phenyldimethylgermyl group, methyldiphenylgermyl group, triphenylgermyl group, etc. be able to.
Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, i-propoxycarbonyl group, t-butoxycarbonyl group and the like.

Examples of the acyl group include acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, laurylyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl Group, succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, canphoroyl group Benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group Isonicotinoyl group, p- toluenesulfonyl group, and mesyl group.
Furthermore, examples of the cyclic acid dissociable group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 4-t-butylcyclohexyl group, a 4-methoxycyclohexyl group, a cyclohexenyl group, a norbornyl group, an isobornyl group, and a tricyclo group. Decanyl group, adamantyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 3-bromotetrahydropyranyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyrani Group, 3-tetrahydrothiophene-1,1-dioxide group, methyladamantyl group, ethyladamantyl group, methyltricyclodecanyl group, ethyltricyclodecanyl group, methylcyclopentyl group, ethylcyclopentyl group, Le cyclohexyl group, an ethyl cyclohexyl group,
A group —C (R ¹⁰ ) ₃ (wherein each R ¹⁰ is independently a linear or branched alkyl group having 1 to 4 carbon atoms or a monovalent monovalent group having 4 to 20 carbon atoms which may be substituted) An alicyclic hydrocarbon group and at least one R ¹⁰ is a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms which may be substituted, or any two R ¹⁰ are mutually To form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms which may be substituted together with the carbon atom to which each is bonded, and the remaining R ¹⁰ is a straight chain having 1 to 4 carbon atoms. A chain or branched alkyl group or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms which may be substituted.)
Etc.

Among these acid dissociable groups, benzyl group, t-butoxycarbonylmethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-cyclohexyloxyethyl group, 1-ethoxy-n-propyl group, t-butyl Group, 1,1-dimethylpropyl group, trimethylsilyl group, t-butoxycarbonyl group, 4-t-butylcyclohexyl group, isobornyl group, tricyclodecanyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group Tetrahydrothiofuranyl group, methyladamantyl group, ethyladamantyl group, methyltricyclodecanyl group, ethyltricyclodecanyl group, methylcyclopentyl group, ethylcyclopentyl group, methylcyclohexyl group, ethylcyclohexyl group,
The group —C (R ¹⁰ ) ₃ etc. is preferred.

Specific examples of the preferred group —C (R ¹⁰ ) ₃ include 1- (2-norbornyl) -1-methylethyl group, 1- (5-hydroxy-2-norbornyl) -1-methylethyl group, 1- ( 3-tetracyclodecanyl) -1-methylethyl group, 1- (8-hydroxy-3-tetracyclodecanyl) -1-methylethyl group, 1- (1-adamantyl) -1-methylethyl group, 1 -(3-hydroxy-1-adamantyl) -1-methylethyl group, 2-methyl-2-norbornyl group, 2-methyl-5-hydroxy-2-norbornyl group, 3-methyl-3-tetracyclodecanyl group 3-methyl-8-hydroxy-3-tetracyclodecanyl group, 2-methyl-2-adamantyl group, 2-methyl-7-hydroxy-2-adamantyl group and the like.

  The rate of introduction of acid dissociable groups in the acid dissociable group-containing resin (ratio of the number of acid dissociable groups to the total number of oxygen-containing functional groups and acid dissociable groups in the acid dissociable group-containing resin) Although it cannot be generally defined by the type of the dissociable group or the alkali-soluble resin into which the group is introduced, it is preferably 10 to 100%, more preferably 15 to 100%.

The polystyrene-reduced weight molecular weight (hereinafter referred to as “Mw”) of the acid-dissociable group-containing resin measured by gel permeation chromatography is preferably 1,000 to 500,000, more preferably 1,000 to 300,000. Particularly preferred is 3,000 to 300,000.
Further, the ratio (Mw / Mn) of Mw of the acid-dissociable group-containing resin to polystyrene-reduced number molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC) is usually 1 to 10 , Preferably 1-5.
The acid dissociable group-containing resins can be used alone or in admixture of two or more.

The acid-dissociable group-containing resin particularly preferably used for the positive radiation-sensitive resin composition (a) using a KrF excimer laser includes one or more repeating units represented by the following general formula (10) and the acid. An alkali-insoluble or hardly alkali-soluble resin (hereinafter referred to as “resin (B1)”) having at least one repeating unit having a dissociable group is preferred. The resin (B1) can also be suitably used for a positive radiation sensitive resin composition (A) using an ArF excimer laser, an F ₂ excimer laser, an electron beam or the like.

〔一般式（１０）において、Ｒ¹¹は水素原子または１価の有機基を示し、ｅおよびｆはそれぞれ１〜３の整数で、（ｅ＋ｆ）≦５である。〕

[In General Formula (10), R ¹¹ represents a hydrogen atom or a monovalent organic group, e and f are each an integer of 1 to 3, and (e + f) ≦ 5. ]

As the repeating unit represented by the general formula (10), 4-hydroxystyrene, 3-hydroxystyrene, 2-hydroxystyrene, 4-hydroxy-α-methylstyrene, 3-methyl-4-hydroxystyrene, 2-methyl -4-hydroxystyrene, 2-methyl-3-hydroxystyrene, 4-methyl-3-hydroxystyrene, 5-methyl-3-hydroxystyrene, 3,4-dihydroxystyrene, 2,4,6-trihydroxystyrene, etc. And a unit in which the polymerizable unsaturated bond is cleaved.
Among these repeating units, a unit in which a polymerizable unsaturated bond is cleaved such as 4-hydroxystyrene, 3-hydroxystyrene, 2-hydroxystyrene, 4-hydroxy-α-methylstyrene is preferable.

  The repeating unit having an acid dissociable group is a repeating unit containing one or more acidic functional groups such as a phenolic hydroxyl group and a carboxyl group, preferably a repeating unit represented by the general formula (10) or A unit in which a hydrogen atom of a phenolic hydroxyl group or a carboxyl group in a repeating unit in which a polymerizable unsaturated bond of (meth) acrylic acid is cleaved is substituted with the acid dissociable group, more preferably 4-t-butoxystyrene, 4- t-butoxycarbonyloxystyrene, 4-t-butoxycarbonylmethyloxystyrene, 4-tetrahydrofuranyloxystyrene, 4-tetrahydropyranyloxystyrene, 2-ethoxyethoxystyrene, t-butyl (meth) acrylate, methyladamantyl (meta ) Acrylate, ethyl adamantyl Meth) acrylate, methylcyclopentyl (meth) acrylate, ethyl cyclopentyl (meth) acrylate, methylcyclohexyl (meth) acrylate, units polymerizable unsaturated bond is cleaved, such as ethyl cyclohexyl (meth) acrylate.

Further, the resin (B1) can have one or more kinds of repeating units other than those described above (hereinafter referred to as “other repeating units (b1)”).
As other repeating unit (b1), for example,
Styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4- (2-t-butoxycarbonylethyloxy) styrene Vinyl aromatic compounds such as;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, n-pentyl (meth) acrylate, N-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meta ) (Meth) acrylic acid esters such as phenyl acrylate, phenethyl (meth) acrylate, and monomers represented by the following formulas (11) to (13);

〔式（１１）〜（１３）において、ｇは１〜６の整数である。〕

[In Formula (11)-(13), g is an integer of 1-6. ]

Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid;
Carboxyalkyl esters of unsaturated carboxylic acids such as 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate;
Unsaturated nitrile compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinnitrile, fumaronitrile;
Unsaturated amide compounds such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleinamide, fumaramide;
Unsaturated imide compounds such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
N-vinyl-ε-caprolactam, N-vinyl pyrrolidone, 2-vinyl pyridine, 3-vinyl pyridine, 4-vinyl pyridine, 2-vinyl imidazole, other nitrogen-containing vinyl compounds such as 4-vinyl imidazole, etc. Examples include units in which a saturated bond is cleaved.

Among these other repeating units (b1), styrene, α-methylstyrene, 4- (2-t-butoxycarbonylethyloxy) styrene, a monomer represented by formula (11), and formula (12) A unit in which a polymerizable unsaturated bond such as a monomer represented is cleaved is preferable.
In addition, the positive radiation sensitive resin composition (a) using a KrF excimer laser includes a resin in which the hydrogen atom of the phenolic hydroxyl group of the cresol novolak resin is substituted with the acid dissociable group as another acid dissociable group-containing resin. It can be preferably used. Preferred acid dissociable groups in this resin include, for example, ethoxyethyl group, t-butyl group, t-butoxycarbonyl group, t-butoxycarbonylmethyl group and the like.

In addition, as the acid-dissociable group-containing resin particularly preferably used for the positive radiation-sensitive resin composition (A) using an ArF excimer laser, one or more repeating units represented by the following general formula (14) and An alkali-insoluble or hardly-alkali-soluble resin (hereinafter referred to as “resin (B2)”) having at least one repeating unit represented by the following general formula (15) is preferable. The resin (B2) can also be suitably used for a positive radiation sensitive resin composition (A) using a KrF excimer laser, an F ₂ excimer laser, an electron beam or the like.

〔一般式（１４）において、各Ｂは互いに独立に水素原子または酸解離性基を示し、かつ少なくとも１つのＢが酸解離性基であり、各Ｄは互いに独立に水素原子または炭素数１〜４の直鎖状もしくは分岐状の１価のアルキル基を示し、ｘは０〜２の整数である。〕

[In General Formula (14), each B independently represents a hydrogen atom or an acid dissociable group, and at least one B is an acid dissociable group, and each D independently represents a hydrogen atom or a carbon number of 1 to 4 represents a linear or branched monovalent alkyl group, and x is an integer of 0-2. ]

〔一般式（１５）において、Ｒ¹²は水素原子またはメチル基を示し、各Ｒ¹⁰は相互に独立に炭素数１〜４の直鎖状もしくは分岐状のアルキル基または置換されてもよい炭素数４〜２０の１価の脂環式炭化水素基を示すか、あるいは何れか２つのＲ¹⁰が相互に結合して、それぞれが結合している炭素原子と共に、置換されてもよい炭素数４〜２０の２価の脂環式炭化水素基を形成し、残りのＲ¹⁰が炭素数１〜４の直鎖状もしくは分岐状のアルキル基または置換されてもよい炭素数４〜２０の１価の脂環式炭化水素基である。〕

[In General Formula (15), R ¹² represents a hydrogen atom or a methyl group, and each R ¹⁰ is independently a linear or branched alkyl group having 1 to 4 carbon atoms or an optionally substituted carbon number. 4-20 monovalent alicyclic hydrocarbon groups, or any two R ¹⁰ 's bonded to each other, and together with the carbon atoms to which each is bonded, 4 to 4 carbon atoms that may be substituted 20 divalent alicyclic hydrocarbon groups are formed, and the remaining R ¹⁰ is a linear or branched alkyl group having 1 to 4 carbon atoms or an optionally substituted monovalent group having 4 to 20 carbon atoms. An alicyclic hydrocarbon group. ]

As a preferable repeating unit represented by the general formula (14), for example,
5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5- (4-t-butylcyclohexyloxy) carbonylbicyclo [2.2.1] hept-2-ene, 5- (1 -Ethoxyethoxy) carbonylbicyclo [2.2.1] hept-2-ene, 5- (1-cyclohexyloxyethoxy) carbonylbicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylmethoxy Carbonylbicyclo [2.2.1] hept-2-ene, 5-tetrahydrofuranyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-tetrahydropyranyloxycarbonylbicyclo [2.2.1] Hept-2-ene,
8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (4-t-butylcyclohexyloxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (1-ethoxyethoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (1-cyclohexyloxyethoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-t-butoxycarbonylmethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-tetrahydrofuranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-tetrahydropyranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . And a unit in which a polymerizable unsaturated bond of a monomer having a norbornene skeleton such as 1 ^7,10 ] dodec-3-ene is cleaved.

  Moreover, as a preferable repeating unit represented by the said General formula (15), the unit which the polymerizable unsaturated bond of (meth) acrylate t-butyl was cleaved, and following formula (15-1)-(15-12) ) And the like.

Resin (B2) can have 1 or more types of repeating units other than the above (henceforth "other repeating unit (b2)").
As another repeating unit (b2), for example,
Norbornene (bicyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene , 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-fluorobicyclo [2.2.1] hept-2-ene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-hydroxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] a monomer having a norbornene skeleton such as dodec-3-ene;
Unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride;
Units in which polymerizable unsaturated bonds such as (meth) acrylates exemplified as other repeating units (b1) in resin (B1) and (meth) acrylate esters represented by the following formula (16) are cleaved Can be mentioned.

〔式（１６）において、Ｒ¹³は水素原子またはメチル基を示す。）

[In Formula (16), R < ¹³ > shows a hydrogen atom or a methyl group. )

  When the resin (B2) has a repeating unit represented by the general formula (14), it is preferable to have a repeating unit derived from maleic anhydride as the other repeating unit (b2).

Furthermore, the acid-dissociable group-containing resin particularly preferably used for the positive radiation-sensitive resin composition (a) using an F ₂ excimer laser includes one or more structural units represented by the following general formula (17). And / or one or more structural units represented by the following general formula (18), preferably an alkali-insoluble or poorly alkali-soluble polysiloxane having a structural unit represented by the general formula (17) (hereinafter referred to as “resin ( B3) ")) is preferred. The resin (B3) can also be suitably used for a positive radiation sensitive resin composition (A) using a KrF excimer laser, an ArF excimer laser, an electron beam or the like.

〔一般式（１７）および一般式（１８）において、Ｅは相互に独立に酸解離性基を有する１価の有機基を示し、Ｒ¹⁴は置換されてもよい炭素数１〜２０の直鎖状、分岐状もしくは環状の１価の炭化水素基を示す。）

In [Formula (17) and the general formula (18), E is a monovalent represents an organic group, R ¹⁴ is linear carbon atoms which may be 20 substituted with an acid dissociable group independently of one another , Branched or cyclic monovalent hydrocarbon group. )

  E in the general formula (17) and the general formula (18) is an acid dissociable group in an alicyclic hydrocarbon group such as a cycloalkyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclododecanyl group, an adamantyl group or the like. And a group having an acid-dissociable group in the halogenated aromatic hydrocarbon group are preferred.

  Examples of the particularly preferred structural unit represented by the general formula (17) in the resin (B3) include structural units represented by the following formulas (17-1) to (17-4).

The resin (B3) can have one or more structural units other than those described above (hereinafter referred to as “other structural units (b3)”).
As another preferred structural unit (b3), for example,
Structural units obtained by hydrolysis and condensation of alkyl alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane; represented by the following formulas (18-1) to (18-4) The structural unit etc. which can be mentioned.

Resin (B3) is obtained by (co) polycondensing a silane compound containing a monovalent organic group having an acid dissociable group, or by adding an acid dissociable group and / or an acid dissociable group to a previously synthesized organic polysiloxane. It can manufacture by introduce | transducing the monovalent organic group which has.
When (co) polycondensation of a silane compound containing a monovalent organic group having an acid dissociable group, it is preferable to use an acidic catalyst as the catalyst, and in particular, polycondensation of the silane compound in the presence of an acidic catalyst. Then, it is preferable to further react by adding a basic catalyst.

Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, titanium tetrachloride, zinc chloride, and aluminum chloride; formic acid, acetic acid, n-propionic acid, butyric acid, valeric acid, and oxalic acid. Organic acids such as malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, acetic anhydride, maleic anhydride, citric acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, etc. Can be mentioned.
Of these acidic catalysts, hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, acetic anhydride, maleic anhydride and the like are preferable.

  Examples of the basic catalyst include inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, and potassium carbonate; Examples thereof include organic bases such as triethylamine, tri-n-propylamine, tri-n-butylamine, and pyridine.

<Alkali-soluble resin>
The alkali-soluble resin in the positive radiation-sensitive resin composition (b) has at least one functional group having affinity with an alkali developer, for example, one or more oxygen-containing functional groups such as a phenolic hydroxyl group, an alcoholic hydroxyl group, and a carboxyl group. It is a resin that is soluble in an alkaline developer.
Examples of such an alkali-soluble resin include addition polymerization resins having one or more repeating units represented by the following general formulas (19) to (21), and 1 repeating unit represented by the following formula (22). Examples thereof include polycondensation resins having at least species.

〔一般式（１９）および一般式（２０）において、Ｒ¹⁵およびＲ¹⁷は相互に独立に水素原子またはメチル基を示し、Ｒ¹⁶は水酸基、カルボキシル基、
−Ｒ¹⁸ＣＯＯＨ、−ＯＲ¹⁸ＣＯＯＨ、−ＯＣＯＲ¹⁸ＣＯＯＨまたは
−ＣＯＯＲ¹⁸ＣＯＯＨ（但し、各Ｒ¹⁸は相互に独立に−（ＣＨ₂)_h −を示し、ｈは１〜４の整数である。〕

[In General Formula (19) and General Formula (20), R ¹⁵ and R ¹⁷ each independently represent a hydrogen atom or a methyl group, R ¹⁶ represents a hydroxyl group, a carboxyl group,
—R ¹⁸ COOH, —OR ¹⁸ COOH, —OCOR ¹⁸ COOH, or —COOR ¹⁸ COOH (where each R ¹⁸ independently represents — (CH ₂ ) _h —, and h is an integer of 1 to 4). ]

〔一般式（２２）において、各Ｒ¹⁹は相互に独立に水素原子または炭素数１〜４の直鎖状もしくは分岐状のアルキル基を示す。〕

[In General Formula (22), each R ¹⁹ independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. ]

When the alkali-soluble resin is an addition polymerization resin, it may be composed only of the repeating units represented by the general formulas (19) to (21), as long as the generated resin is soluble in an alkali developer. Then, one or more other repeating units (hereinafter referred to as “other repeating units (c1)”) may be further included.
Examples of the other repeating unit (c1) include the same units as the other repeating unit (b1) in the resin (B1) described above.

  Further, when the alkali-soluble resin is a polycondensation resin, it may be composed only of the repeating unit represented by the general formula (22), but as long as the generated resin is soluble in an alkali developer, One or more other repeating units (hereinafter referred to as “other repeating units (c2)”) may be further included.

The content of the repeating unit represented by the general formulas (19) to (22) in the alkali-soluble resin is generally determined depending on the types of other repeating units (c1) and other repeating units (c2) that are optionally contained. Although it cannot be specified, it is preferably 10 to 100 mol%, more preferably 20 to 100 mol%.
When the alkali-soluble resin has a repeating unit containing a carbon-carbon unsaturated bond as represented by the general formula (19), the general formula (22) or the like, it can also be used as a hydrogenated product. The hydrogenation rate in this case is usually 70% or less, preferably 50% or less, of the carbon-carbon unsaturated bond contained in the repeating unit represented by the general formula (19), the general formula (22), etc. More preferably, it is 40% or less. In this case, if the hydrogenation rate exceeds 70%, the developability of the alkali-soluble resin with an alkali developer may be lowered.

Examples of the alkali-soluble resin in the positive radiation sensitive resin composition (b) include poly (4-hydroxystyrene), 4-hydroxystyrene / 4-hydroxy-α-methylstyrene copolymer, 4-hydroxystyrene / A resin mainly composed of a styrene copolymer or the like is preferable.
The Mw of the alkali-soluble resin varies depending on the desired properties of the positive radiation-sensitive resin composition (b), but is preferably 1,000 to 150,000, more preferably 3,000 to 100,000. .
The alkali-soluble resins can be used alone or in admixture of two or more.

<Alkali solubility control agent>
Examples of the alkali solubility control agent in the positive radiation sensitive resin composition (b) include, for example, substitution of a hydrogen atom of an acidic functional group such as a phenolic hydroxyl group or a carboxyl group with an acid dissociable group or a t-butoxycarbonylmethyl group. And the like.
Examples of the acid dissociable group include a substituted methyl group, a 1-substituted ethyl group, a 1-substituted-n-propyl group, a 1-branched alkyl group exemplified for the acid dissociable group in the acid dissociable group-containing resin, Examples thereof include the same groups as silyl group, germyl group, alkoxycarbonyl group, acyl group, cyclic acid dissociable group and the like.
The alkali solubility controller may be a low molecular compound or a high molecular compound. Examples of the low molecular compound include compounds represented by the following general formulas (23) to (27),

[In the general formulas (23) to (27), each R ²⁰ independently represents an acid dissociable group or t-butoxycarbonylmethyl group, and each R ²¹ represents a linear chain having 1 to 4 carbon atoms independently of each other. Jo or branched alkyl group, a phenyl group or a 1-naphthyl group, each R ²² individually represent a hydrogen atom, a linear or branched alkyl group or a phenyl group having 1 to 4 carbon atoms, Q is a single bond, —O—, —S—, —CO—, —COO—, —SO—, —SO ₂ —, —C (R ²³ ) (R ²⁴ ) — (where R ²³ and R ²⁴ are And independently of one another, a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched acyl group having 2 to 11 carbon atoms, a phenyl group or a 1-naphthyl group. Or a phenylene group which may be substituted; p, q, r, s, t, u, v, w are Each is an integer of 0 or more, 5 ≧ p ≧ 1 in the general formula (23), 10 ≧ (p + r) ≧ 1 in the general formula (24), 15 ≧ (p + r + t) ≧ 1 in the general formula (25), 26) satisfies 20 ≧ (p + r + t + v) ≧ 1, and the general formula (27) satisfies 19 ≧ (p + r + t + v) ≧ 1. ];
The hydrogen atom of the carboxyl group in a carboxylic acid compound having an alicyclic ring or an aromatic ring such as steroids (bile acids) such as cholic acid, deoxycholic acid, lithocholic acid, adamantanecarboxylic acid, adamantanedicarboxylic acid, etc. Examples include compounds substituted with an acid dissociable group or a t-butoxycarbonylmethyl group.

In addition, as the polymer alkali solubility control agent, for example, the acid-dissociable group-containing resin described above can be used.
Examples of the alkali dissolution inhibitor in the positive radiation sensitive resin composition (b) include steroids (bile acids) such as cholic acid, deoxycholic acid, and lithocholic acid, and fats such as adamantane carboxylic acid and adamantane dicarboxylic acid. A compound in which a hydrogen atom of a carboxyl group in a carboxylic acid compound having a cyclic ring or an aromatic ring is substituted with the acid dissociable group or the t-butoxycarbonylmethyl group is preferable.
The alkali solubility control agents can be used alone or in admixture of two or more.

Negative-type radiation-sensitive resin composition The negative-type radiation-sensitive resin composition of the present invention is
(C) (A) Acid generator (I), (C) Alkali-soluble resin and (E) A compound capable of crosslinking the alkali-soluble resin in the presence of an acid (hereinafter referred to as “crosslinking agent (E)”). And a composition containing the composition (hereinafter referred to as “negative-type radiation-sensitive resin composition (C)”).
As the acid generator (I) in the negative radiation sensitive resin composition (c), those which are thermally and chemically stable are preferable.
Hereinafter, the negative radiation sensitive resin composition (C) will be described.

<Alkali-soluble resin>
Examples of the alkali-soluble resin in the negative radiation-sensitive resin composition (c) include the same resins as the alkali-soluble resin in the positive radiation-sensitive resin composition (b) described above.
As the alkali-soluble resin in the negative radiation sensitive resin composition (c), in particular, poly (4-hydroxystyrene), 4-hydroxystyrene / 4-hydroxy-α-methylstyrene copolymer, 4-hydroxystyrene / A resin mainly composed of a styrene copolymer or the like is preferable.
The Mw of the alkali-soluble resin varies depending on the desired properties of the negative radiation-sensitive resin composition (c), but is preferably 1,000 to 150,000, more preferably 3,000 to 100,000. .
The alkali-soluble resins can be used alone or in admixture of two or more.

<Crosslinking agent (E)>
As a crosslinking agent (E) in a negative radiation sensitive resin composition (c), it has 1 or more types of functional groups (henceforth a "crosslinkable functional group") which has crosslinking reactivity with alkali-soluble resin, for example. A compound can be mentioned.

  Examples of the crosslinkable functional group include a glycidyl ether group, a glycidyl ester group, a glycidylamino group, a methoxymethyl group, an ethoxymethyl group, a benzyloxymethyl group, an acetoxymethyl group, a benzoyloxymethyl group, a formyl group, and an acetyl group. , Vinyl group, isopropenyl group, (dimethylamino) methyl group, (diethylamino) methyl group, (dimethylolamino) methyl group, (diethylolamino) methyl group, morpholinomethyl group, and the like.

  Examples of the crosslinking agent (E) include bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, novolac resin epoxy compounds, resole resin epoxy compounds, poly (hydroxystyrene) epoxy compounds, and methylol. Group-containing melamine compound, methylol group-containing benzoguanamine compound, methylol group-containing urea compound, methylol group-containing phenol compound, alkoxyalkyl group-containing melamine compound, alkoxyalkyl group-containing benzoguanamine compound, alkoxyalkyl group-containing urea compound, alkoxyalkyl group-containing phenol compound Carboxymethyl group-containing melamine resin, carboxymethyl group-containing benzoguanamine resin, carboxymethyl group-containing urea resin, carboxymethyl Containing phenol resin, carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds, mention may be made of carboxymethyl group-containing phenol compounds and the like.

  Among these crosslinking agents (E), a methylol group-containing phenol compound, a methoxymethyl group-containing melamine compound, a methoxymethyl group-containing phenol compound, a methoxymethyl group-containing glycoluril compound, a methoxymethyl group-containing urea compound, and an acetoxymethyl group-containing phenol Compounds are preferred, and methoxymethyl group-containing melamine compounds (such as hexamethoxymethylmelamine), methoxymethyl group-containing glycoluril compounds, methoxymethyl group-containing urea compounds, and the like are more preferred. The methoxymethyl group-containing melamine compound is a trade name such as CYMEL300, 301, 303, 305 (manufactured by Mitsui Cyanamid Co., Ltd.), and the methoxymethyl group-containing glycoluril compound is CYMEL1174 (Mitsui Cyanamid Co., Ltd.). ) And methoxymethyl group-containing urea compounds are commercially available under trade names such as MX290 (manufactured by Sanwa Chemical Co., Ltd.).

  In addition, as the crosslinking agent (E), a resin imparted with a property as a crosslinking agent by substituting a hydrogen atom of an oxygen-containing functional group in the alkali-soluble resin with the crosslinking functional group can be suitably used. . The introduction rate of the crosslinkable functional group in that case cannot be unconditionally defined by the type of the crosslinkable functional group or the alkali-soluble resin into which the group is introduced, but with respect to the total oxygen-containing functional group in the alkali-soluble resin, Usually, it is 5 to 60 mol%, preferably 10 to 50 mol%, more preferably 15 to 40 mol%. In this case, if the introduction ratio of the crosslinkable functional group is less than 5 mol%, the remaining film ratio tends to decrease, the pattern meanders or swells easily, and if it exceeds 60 mol%, the exposed area is developed. Tend to decrease.

As the crosslinking agent (E) in the negative radiation-sensitive resin composition (c), a methoxymethyl group-containing compound, more specifically dimethoxymethylurea, tetramethoxymethylglycoluril and the like are particularly preferable.
The said crosslinking agent (E) can be used individually or in mixture of 2 or more types.
<Other acid generators>
In some cases, the positive-type radiation-sensitive resin composition (a), the positive-type radiation-sensitive resin composition (b) and the negative-type radiation-sensitive resin composition (c) may generate an acid other than the acid generator (I). An agent (hereinafter referred to as “other acid generator”) can also be contained.

  Examples of other acid generators include sulfonimide compounds, onium salt compounds, sulfone compounds, sulfonic acid ester compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, and the like.

Examples of these other acid generators are shown below.
Sulfonimide compounds;
Examples of the sulfonimide compound include compounds represented by the following general formula (28).

〔一般式（２８）において、Ｒ²⁵は１価の有機基を示し、Ｒ²⁶は２価の有機基を示す。〕 スルホンイミド化合物の具体例としては、
Ｎ−（トリフルオロメタンスルホニルオキシ）スクシンイミド、Ｎ−（トリフルオロメチルスルホニルオキシ）フタルイミド、Ｎ−（トリフルオロメチルスルホニルオキシ）ジフェニルマレイミド、Ｎ−（トリフルオロメチルスルホニルオキシ）ビシクロ［２．２．１］ヘプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（トリフルオロメチルスルホニルオキシ）−７−オキサビシクロ［２．２．１］ヘプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（トリフルオロメチルスルホニルオキシ）ビシクロ［２．２．１］ヘプタン−５，６−オキシ−２，３−ジカルボキシイミド、Ｎ−（トリフルオロメチルスルホニルオキシ）ナフチルイミド、
Ｎ−（１０−カンファースルホニルオキシ）スクシンイミド、Ｎ−（１０−カンファースルホニルオキシ）フタルイミド、Ｎ−（１０−カンファースルホニルオキシ）ジフェニルマレイミド、Ｎ−（１０−カンファースルホニルオキシ）ビシクロ［２．２．１］ヘプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（１０−カンファースルホニルオキシ）−７−オキサビシクロ［２．２．１］ヘプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（１０−カンファースルホニルオキシ）ビシクロ［２．２．１］ヘプタン−５，６−オキシ−２，３−ジカルボキシイミド、Ｎ−（１０−カンファースルホニルオキシ）ナフチルイミド、

[In the general formula (28), R ²⁵ represents a monovalent organic group, and R ²⁶ represents a divalent organic group. As specific examples of the sulfonimide compound,
N- (trifluoromethanesulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N -(Trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide,
N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (10-camphorsulfonyloxy) naphthylimide,

N- (n-octanesulfonyloxy) succinimide, N- (n-octanesulfonyloxy) phthalimide, N- (n-octanesulfonyloxy) diphenylmaleimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (n-octanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (n-octanesulfonyloxy) naphthylimide,
N- (p-toluenesulfonyloxy) succinimide, N- (p-toluenesulfonyloxy) phthalimide, N- (p-toluenesulfonyloxy) diphenylmaleimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide,

N- (2-trifluoromethylbenzenesulfonyloxy) succinimide, N- (2-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (2-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N- (2-trifluoro Methylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimi ,
N- (4-trifluoromethylbenzenesulfonyloxy) succinimide, N- (4-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (4-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N- (4-trifluoro Methylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide N- (4-Trifluoromethylbenzenesulfonyloxy) naphthylimi ,

N- (perfluorobenzenesulfonyloxy) succinimide, N- (perfluorobenzenesulfonyloxy) phthalimide, N- (perfluorobenzenesulfonyloxy) diphenylmaleimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] ] Hept-5-ene-2,3-dicarboximide, N- (perfluorobenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (perfluorobenzenesulfonyloxy) naphthylimide,
N- (1-naphthalenesulfonyloxy) succinimide, N- (1-naphthalenesulfonyloxy) phthalimide, N- (1-naphthalenesulfonyloxy) diphenylmaleimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) naphthylimide,
N- (benzenesulfonyloxy) succinimide, N- (benzenesulfonyloxy) phthalimide, N- (benzenesulfonyloxy) diphenylmaleimide, N- (benzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N- (benzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (benzenesulfonyloxy) bicyclo [2 2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (benzenesulfonyloxy) naphthylimide,
N-[(5-methyl-5-methoxycarbonylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] succinimide, N-[(5-methyl-5-methoxycarbonylbicyclo [2.2.1 And heptan-2-yl) sulfonyloxy] bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide.

Onium salt compounds:
Examples of the onium salt compound include iodonium salts, sulfonium salts (including thiophenium salts), phosphonium salts, diazonium salts, ammonium salts, pyridinium salts, and the like.

As a specific example of the onium salt compound,
Bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium pyrenesulfonate, bis (4-tert-butylphenyl) iodonium n-dodecylbenzenesulfonate, bis (4-tert-butyl) Phenyl) iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodoniumbenzenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, bis (4-t-butylphenyl) iodonium n-octanesulfonate Bis (4-t-butylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis (4- - butylphenyl) iodonium perfluoro sulfonate,
Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium n-octanesulfonate, diphenyliodonium2-tri Fluoromethylbenzenesulfonate, diphenyliodonium 4-trifluoromethylbenzenesulfonate, diphenyliodonium perfluorobenzenesulfonate,

Di (p-tolyl) iodonium trifluoromethanesulfonate, di (p-tolyl) iodonium pyrenesulfonate, di (p-tolyl) iodonium n-dodecylbenzenesulfonate, di (p-tolyl) iodonium p-toluenesulfonate, di (p-tolyl) Tolyl) iodonium benzenesulfonate, di (p-tolyl) iodonium 10-camphorsulfonate, di (p-tolyl) iodonium n-octanesulfonate, di (p-tolyl) iodonium 2-trifluoromethylbenzenesulfonate, di (p-tolyl) ) Iodonium 4-trifluoromethylbenzenesulfonate, di (p-tolyl) iodonium perfluorobenzenesulfonate,
Di (3,4-dimethylphenyl) iodonium trifluoromethanesulfonate, di (3,4-dimethylphenyl) iodonium pyrenesulfonate, di (3,4-dimethylphenyl) iodonium n-dodecylbenzenesulfonate, di (3,4-dimethyl) Phenyl) iodonium p-toluenesulfonate, di (3,4-dimethylphenyl) iodoniumbenzenesulfonate, di (3,4-dimethylphenyl) iodonium 10-camphorsulfonate, di (3,4-dimethylphenyl) iodonium n-octanesulfonate Di (3,4-dimethylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, di (3,4-dimethylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, di (3,4 Dimethylphenyl) iodonium perfluoro sulfonate,

4-nitrophenyl phenyliodonium trifluoromethanesulfonate, 4-nitrophenyl phenyliodonium pyrenesulfonate, 4-nitrophenyl phenyliodonium n-dodecylbenzenesulfonate, 4-nitrophenyl phenyliodonium p-toluenesulfonate, 4-nitrophenyl Phenyl iodonium benzene sulfonate, 4-nitrophenyl phenyl iodonium 10-camphor sulfonate, 4-nitrophenyl phenyl iodonium n-octane sulfonate, 4-nitrophenyl phenyl iodonium 2-trifluoromethylbenzene sulfonate, 4-nitrophenyl Phenyliodonium 4-trifluoromethylbenzenesulfonate, 4-nitrophenyl phenyl Over de iodonium perfluoro sulfonate,
Di (3-nitrophenyl) iodonium trifluoromethanesulfonate, di (3-nitrophenyl) iodonium pyrenesulfonate, di (3-nitrophenyl) iodonium n-dodecylbenzenesulfonate, di (3-nitrophenyl) iodonium p-toluenesulfonate, Di (3-nitrophenyl) iodonium benzene sulfonate, di (3-nitrophenyl) iodonium 10-camphor sulfonate, di (3-nitrophenyl) iodonium n-octane sulfonate, di (3-nitrophenyl) iodonium 2-trifluoromethyl Benzenesulfonate, di (3-nitrophenyl) iodonium 4-trifluoromethylbenzenesulfonate, di (3-nitrophenyl) iodonium perfluorobenzenesulfonate Door,

4-methoxyphenyl phenyliodonium trifluoromethanesulfonate, 4-methoxyphenyl phenyliodonium pyrenesulfonate, 4-methoxyphenyl phenyliodonium n-dodecylbenzenesulfonate, 4-methoxyphenyl phenyliodonium p-toluenesulfonate, 4-methoxyphenyl Phenyliodonium benzenesulfonate, 4-methoxyphenyl phenyliodonium 10-camphorsulfonate, 4-methoxyphenyl phenyliodonium n-octanesulfonate, 4-methoxyphenyl phenyliodonium 2-trifluoromethylbenzenesulfonate, 4-methoxyphenyl Phenyliodonium 4-trifluoromethylbenzenesulfonate, 4-methoxy Phenyl iodonium perfluoro sulfonate,
Di (4-chlorophenyl) iodonium trifluoromethanesulfonate, di (4-chlorophenyl) iodonium pyrenesulfonate, di (4-chlorophenyl) iodonium n-dodecylbenzenesulfonate, di (4-chlorophenyl) iodonium p-toluenesulfonate, di (4- Chlorophenyl) iodonium benzenesulfonate, di (4-chlorophenyl) iodonium 10-camphorsulfonate, di (4-chlorophenyl) iodonium n-octanesulfonate, di (4-chlorophenyl) iodonium 2-trifluoromethylbenzenesulfonate, di (4-chlorophenyl) ) Iodonium 4-trifluoromethylbenzenesulfonate, di (4-chlorophenyl) iodonium perfluorobenzenesulfonate Door,

Di (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, di (4-trifluoromethylphenyl) iodonium pyrenesulfonate, di (4-trifluoromethylphenyl) iodonium n-dodecylbenzenesulfonate, di (4-trifluoromethyl) Phenyl) iodonium p-toluenesulfonate, di (4-trifluoromethylphenyl) iodoniumbenzenesulfonate, di (4-trifluoromethylphenyl) iodonium 10-camphorsulfonate, di (4-trifluoromethylphenyl) iodonium n-octanesulfonate Di (4-trifluoromethylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, di (4-trifluoromethylphenyl) iodonium -Trifluoromethylbenzenesulfonate, di (4-trifluoromethylphenyl) iodonium perfluorobenzenesulfonate, di (1-naphthyl) iodonium trifluoromethanesulfonate, di (1-naphthyl) iodonium trifluoromethanesulfonate, di (1-naphthyl) Iodonium nonafluoro-n-butanesulfonate, di (1-naphthyl) iodonium perfluoro-n-octanesulfonate, di (1-naphthyl) iodonium pyrenesulfonate, di (1-naphthyl) iodonium n-dodecylbenzenesulfonate, di (1 -Naphthyl) iodonium p-toluenesulfonate, di (1-naphthyl) iodoniumbenzenesulfonate, di (1-naphthyl) iodonium 10-camphorsulfonate Di (1-naphthyl) iodonium n-octanesulfonate, di (1-naphthyl) iodonium 2-trifluoromethylbenzenesulfonate, di (1-naphthyl) iodonium 4-trifluoromethylbenzenesulfonate, di (1-naphthyl) iodonium Perfluorobenzenesulfonate,

Biphenylene iodonium trifluoromethane sulfonate, biphenylene iodonium pyrene sulfonate, biphenylene iodonium n-dodecylbenzene sulfonate, biphenylene iodonium p-toluene sulfonate, biphenylene iodonium benzene sulfonate, biphenylene iodonium 10-camphor sulfonate, biphenylene iodonium n-octane sulfonate, biphenylene iodonium 2-tri Fluoromethylbenzenesulfonate, biphenyleneiodonium 4-trifluoromethylbenzenesulfonate, biphenyleneiodonium perfluorobenzenesulfonate,
2-chlorobiphenylene iodonium trifluoromethanesulfonate , 2-chlorobiphenyleneiodonium pyrenesulfonate, 2-chlorobiphenyleneiodonium n-dodecylbenzenesulfonate, 2-chlorobiphenyleneiodonium p-toluenesulfonate, 2-chlorobiphenyleneiodoniumbenzenesulfonate, 2-chlorobiphenylene Iodonium 10-camphorsulfonate, 2-chlorobiphenylene iodonium n-octanesulfonate, 2-chlorobiphenyleneiodonium 2-trifluoromethylbenzenesulfonate, 2-chlorobiphenyleneiodonium 4-trifluoromethylbenzenesulfonate, 2-chlorobiphenyleneiodonium perfluorobenzene Sulfonate,

Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium pyrenesulfonate, triphenylsulfonium n-dodecylbenzenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium n-octane Sulfonate, triphenylsulfonium 2-trifluoromethylbenzenesulfonate, triphenylsulfonium 4-trifluoromethylbenzenesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium perfluorobenzenesulfonate,
4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium pyrenesulfonate, 4-t-butylphenyl diphenylsulfonium n-dodecylbenzenesulfonate, 4-t-butylphenyl diphenylsulfonium p -Toluene sulfonate, 4-t-butylphenyl diphenylsulfonium benzene sulfonate, 4-t-butylphenyl diphenylsulfonium 10-camphor sulfonate, 4-t-butylphenyl diphenylsulfonium n-octane sulfonate, 4-t-butylphenyl Diphenylsulfonium 2-trifluoromethylbenzenesulfonate, 4-t-butylphenyl diphenylsulfonium 4-trifluorome Emissions benzenesulfonate, 4-t-butylphenyl diphenyl sulfonium perfluoro sulfonate,

4-t-butoxyphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butoxyphenyl diphenylsulfonium pyrenesulfonate, 4-t-butoxyphenyl diphenylsulfonium n-dodecylbenzenesulfonate, 4-t-butoxyphenyl diphenylsulfonium p -Toluene sulfonate, 4-t-butoxyphenyl diphenylsulfonium benzene sulfonate, 4-t-butoxyphenyl diphenylsulfonium 10-camphor sulfonate, 4-t-butoxyphenyl diphenylsulfonium n-octane sulfonate, 4-t-butoxyphenyl・ Diphenylsulfonium 2-trifluoromethylbenzenesulfonate, 4-t-butoxyphenyl diphenylsulfonium - trifluoromethylbenzene sulfonate, 4-t-butoxyphenyl · diphenylsulfonium perfluoro sulfonate,

4-hydroxyphenyl diphenylsulfonium trifluoromethanesulfonate, 4-hydroxyphenyl diphenylsulfonium pyrenesulfonate, 4-hydroxyphenyl diphenylsulfonium n-dodecylbenzenesulfonate, 4-hydroxyphenyl diphenylsulfonium p-toluenesulfonate, 4-hydroxyphenyl Diphenylsulfonium benzene sulfonate, 4-hydroxyphenyl diphenylsulfonium 10-camphor sulfonate, 4-hydroxyphenyl diphenylsulfonium n-octane sulfonate, 4-hydroxyphenyl diphenylsulfonium 2-trifluoromethylbenzene sulfonate, 4-hydroxyphenyl Diphenylsulfonium 4-trifluorome Le benzenesulfonate, 4-hydroxyphenyl · diphenylsulfonium perfluoro sulfonate,
Tri (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tri (4-methoxyphenyl) sulfonium pyrenesulfonate, tri (4-methoxyphenyl) sulfonium n-dodecylbenzenesulfonate, tri (4-methoxyphenyl) sulfonium p-toluenesulfonate, Tri (4-methoxyphenyl) sulfonium benzene sulfonate, tri (4-methoxyphenyl) sulfonium 10-camphor sulfonate, tri (4-methoxyphenyl) sulfonium n-octane sulfonate, tri (4-methoxyphenyl) sulfonium 2-trifluoromethyl Benzenesulfonate, tri (4-methoxyphenyl) sulfonium 4-trifluoromethylbenzenesulfonate, tri (4-methoxyphenyl) Sulfo sulfonium perfluoro sulfonate,

Di (4-methoxyphenyl) · p-tolylsulfonium trifluoromethanesulfonate, di (4-methoxyphenyl) · p-tolylsulfonium pyrenesulfonate, di (4-methoxyphenyl) · p-tolylsulfonium n-dodecylbenzenesulfonate, di (4-methoxyphenyl) · p-tolylsulfonium p-toluenesulfonate, di (4-methoxyphenyl) · p-tolylsulfonium benzenesulfonate, di (4-methoxyphenyl) · p-tolylsulfonium 10-camphorsulfonate, di ( 4-methoxyphenyl) .p-tolylsulfonium n-octanesulfonate, di (4-methoxyphenyl) .p-tolylsulfonium 2-trifluoromethylbenzenesulfonate, di (4-methoxyphenyl) .p- Lil sulfonium 4-trifluoromethylbenzenesulfonate, di (4-methoxyphenyl) · p-tolyl sulfonium perfluoro sulfonate,
Phenyl biphenylenesulfonium trifluoromethanesulfonate, phenyl biphenylenesulfonium pyrenesulfonate, phenyl biphenylenesulfonium n-dodecylbenzenesulfonate, phenyl biphenylenesulfonium p-toluenesulfonate, phenyl biphenylenesulfonium benzenesulfonate, phenyl biphenylenesulfonium benzenesulfonate, Phenyl biphenylene sulfonium n-octane sulfonate, phenyl biphenylene sulfonium 2-trifluoromethyl benzene sulfonate, phenyl biphenylene sulfonium 4-trifluoromethyl benzene sulfonate, phenyl biphenylene sulfonium perfluorobenzene sulfonate,

(4-phenylthiophenyl) .diphenylsulfonium trifluoromethanesulfonate, (4-phenylthiophenyl) .diphenylsulfonium pyrenesulfonate, (4-phenylthiophenyl) .diphenylsulfonium n-dodecylbenzenesulfonate, (4-phenylthiophenyl) Diphenylsulfonium p-toluenesulfonate, (4-phenylthiophenyl), diphenylsulfonium benzenesulfonate, (4-phenylthiophenyl), diphenylsulfonium 10-camphorsulfonate, (4-phenylthiophenyl), diphenylsulfonium n-octanesulfonate (4-phenylthiophenyl) -diphenylsulfonium 2-trifluoromethylbenzenesulfonate, (4-phenylthiophene) Phenyl) diphenyl sulfonium 4-trifluoromethylbenzenesulfonate, (4-phenylthiophenyl) · diphenylsulfonium perfluoro sulfonate,
4,4′-bis (diphenylsulfoniophenyl) sulfide di (trifluoromethanesulfonate), 4,4′-bis (diphenylsulfoniophenyl) sulfide di (pyrenesulfonate), 4,4′-bis (diphenylsulfoniophenyl) sulfide di (N-dodecylbenzenesulfonate), 4,4′-bis (diphenylsulfoniophenyl) sulfide di (p-toluenesulfonate), 4,4′-bis (diphenylsulfoniophenyl) sulfide di (benzenesulfonate), 4,4 ′ -Bis (diphenylsulfoniophenyl) sulfide di (10-camphorsulfonate), 4,4'-bis (diphenylsulfoniophenyl) sulfide di (n-octanesulfonate), 4,4'-bis (diphenylsulfoniophenyl) sulfur Dodi (2-trifluoromethylbenzenesulfonate), 4,4′-bis (diphenylsulfoniophenyl) sulfide di (4-trifluoromethylbenzenesulfonate), 4,4′-bis (diphenylsulfoniophenyl) sulfide di (perfluoro) Benzenesulfonate),

1-phenyltetrahydrothiophenium trifluoromethanesulfonate, 1- (4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1 -(4-n-butoxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate,
1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxynaphthalene-1- Yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate,
1- (4-methoxymethoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxymethoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- [4- (1- Methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate, 1- [4- (2-methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate, 1- [4- (2- Methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- [4- (2-methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium perfluoro-n-octa Sulfonate,

1- (4-methoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n -Propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-i-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxy Carbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-t-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiofe Ium trifluoromethanesulfonate, 1- (4-benzyloxy-naphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate,
1- (2-naphthalen-1-yl-2-oxoethyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- [4- (2-tetrahydrofuranyloxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate, 1 Examples include-[4- (2-tetrahydropyranyloxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate.

Sulfone compounds:
Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof.
Specific examples of the sulfone compound include phenacylphenylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, 4-trisphenacylsulfone, and the like.
Sulfonic acid ester compounds:
Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.
Specific examples of the sulfonic acid ester compounds include benzoin tosylate, pyrogallol methane sulfonic acid triester, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, α-methylol benzoin tosylate, α-methylol benzoin trifluoromethane sulfonate. , Α-methylol benzoin n-octane sulfonate, α-methylol benzoindodecyl sulfonate, and the like.

Disulfonyldiazomethane compounds:
As a disulfonyl diazomethane compound, the compound represented by the following general formula (29) can be mentioned, for example.

〔一般式（２９）において、各Ｒ²⁷は相互に独立にアルキル基、アリール基、ハロゲン置換アルキル基、ハロゲン置換アリール基等の１価の基を示す。〕

[In General Formula (29), each R ²⁷ independently represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group. ]

  Specific examples of the disulfonyldiazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and bis (2,4-dimethylbenzene). (Sulfonyl) diazomethane, methylsulfonyl p-toluenesulfonyldiazomethane, bis (4-t-butylphenylsulfonyl) diazomethane, bis (4-chlorobenzenesulfonyl) diazomethane, (cyclohexylsulfonyl) (p-toluenesulfonyl) diazomethane, (cyclohexylsulfonyl) ( 1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (1-methylethylsulfonyl) Nyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sulfonyl) diazomethane, bis (1,4-dioxaspiro [4.5] decan-7-sulfonyl) diazomethane, etc. Can be mentioned.

Disulfonylmethane compounds:
As a disulfonylmethane compound, the compound represented by the following general formula (30) can be mentioned, for example.

[In the general formula (30), each R ²⁸ is independently a linear or branched monovalent aliphatic hydrocarbon group, a cycloalkyl group, an aryl group, an aralkyl group or a monovalent group having a hetero atom. V and W each independently represent an aryl group, a hydrogen atom, a linear or branched monovalent aliphatic hydrocarbon group or another monovalent organic group having a hetero atom, And at least one of V and W is an aryl group, or V and W are connected to each other to form a monocyclic or polycyclic ring having at least one unsaturated bond, or V and W are mutually Connected to the following formula (31)

(However, V ′ and W ′ may be the same or different from each other, and a plurality of V ′ and W ′ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, An aryl group or an aralkyl group, or V ′ and W ′ bonded to the same or different carbon atoms are connected to each other to form a carbon monocyclic structure, and b is an integer of 2 to 10. )
The group represented by these is formed. ]

Oxime sulfonate compounds:
As an oxime sulfonate compound, the compound represented by the following general formula (32-1) or general formula (32-2) can be mentioned, for example.

〔一般式（32−１）および一般式（32−２）において、Ｒ²⁹およびＲ³⁰は相互に独立に１価の有機基を示し、一般式（32−２）における２個のＲ²⁹およびＲ³⁰は相互に同一でも異なってもよい。〕

[In General Formula (32-1) and General Formula (32-2), R ²⁹ and R ³⁰ each independently represent a monovalent organic group, and two R ²⁹ in General Formula (32-2) and R ³⁰ may be the same as or different from each other. ]

In General Formula (32-1) and General Formula (32-2), specific examples of R ²⁹ include a methyl group, an ethyl group, an n-propyl group, a phenyl group, and a tosyl group.
In the general formula (32-1) and general formula (32-2), specific examples of R ³⁰ include a phenyl group, a tosyl group, and a naphthyl group.

Hydrazine sulfonate compounds:
Examples of the hydrazine sulfonate compound include bis (benzene) sulfonyl hydrazine, bis (p-toluene) sulfonyl hydrazine, bis (trifluoromethane) sulfonyl hydrazine, bis (nonafluoro-n-butane) sulfonyl hydrazine, and bis (n-propane) sulfonyl. Examples include hydrazine, benzenesulfonyl hydrazine, p-toluenesulfonyl hydrazine, trifluoromethanesulfonyl hydrazine, nonafluoro-n-butanesulfonyl hydrazine, n-propanesulfonyl hydrazine, trifluoromethanesulfonyl p-toluenesulfonyl hydrazine, and the like.

  Among these other acid generators, di (t-butylphenyl) iodonium trifluoromethanesulfonate, di (t-butylphenyl) 10-camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium 10-camphorsulfonate, N -(Trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) succinimide and the like are preferable.

The other acid generators can be used alone or in admixture of two or more.
In the radiation-sensitive resin compositions (a) to (c), the use ratio of the other acid generator is preferably 90 parts by weight per 100 parts by weight in total of the acid generator (I) and the other acid generator. Hereinafter, it is more preferably 80 parts by weight or less.

The compounding ratio of each component constituting the positive-type radiation-sensitive resin composition (A), the positive-type radiation-sensitive resin composition (B) and the negative-type radiation-sensitive resin composition (C) depends on the desired characteristics of the resist. The preferred blending ratio is as follows.
First, in the positive-type radiation-sensitive resin composition (A) and the positive-type radiation-sensitive resin composition (B), the amount of the acid generator (I) is 100 weights of the acid-dissociable group-containing resin or alkali-soluble resin. The amount is preferably 0.01 to 70 parts by weight, more preferably 0.1 to 50 parts by weight, and particularly preferably 0.5 to 20 parts by weight per part. In this case, if the compounding amount of the acid generator (I) is less than 0.01 parts by weight, the sensitivity and resolution tend to decrease. On the other hand, if it exceeds 70 parts by weight, the resist coatability and pattern shape deteriorate. It tends to be easy to do.
In the positive radiation sensitive resin composition (b), the blending amount of the alkali solubility control agent is preferably 5 to 150 parts by weight, more preferably 5 to 100 parts by weight, per 100 parts by weight of the alkali soluble resin. Particularly preferred is 5 to 50 parts by weight. In this case, if the blending amount of the alkali solubility control agent is less than 5 parts by weight, the remaining film rate tends to decrease and the pattern swells easily. There is a tendency to cause a decrease in strength.

Next, in the negative radiation-sensitive resin composition (c), the amount of the acid generator (I) is preferably 0.01 to 70 parts by weight, more preferably 0.8 parts per 100 parts by weight of the alkali-soluble resin. 1 to 50 parts by weight, particularly preferably 0.5 to 20 parts by weight. In this case, if the compounding amount of the acid generator (I) is less than 0.01 parts by weight, the sensitivity and resolution tend to decrease. On the other hand, if it exceeds 70 parts by weight, the resist coatability and pattern shape deteriorate. It tends to be easy to do.
Moreover, the compounding quantity of a crosslinking agent (E) becomes like this. Preferably it is 5-95 weight part per 100 weight part of alkali-soluble resin, More preferably, it is 15-85 weight part, Most preferably, it is 20-75 weight part. In this case, if the blending amount of the crosslinking agent (E) is less than 5 parts by weight, the remaining film ratio tends to decrease, the pattern meanders or swells easily. On the other hand, if it exceeds 95 parts by weight, There exists a tendency for developability to fall.

<Other ingredients>
-Acid diffusion control agent-
The positive-type radiation-sensitive resin composition (a), the positive-type radiation-sensitive resin composition (b) and the negative-type radiation-sensitive resin composition (c) have an acid resist film generated from an acid generator upon exposure. It is preferable to add an acid diffusion control agent that controls the diffusion phenomenon inside and suppresses an undesirable chemical reaction in the non-exposed region.
By using such an acid diffusion control agent, the storage stability of the composition is improved, the resolution is improved as a resist, and due to fluctuations in the holding time (PED) from exposure to heat treatment after exposure. Changes in the line width of the resist pattern can be suppressed, and the process stability is extremely excellent.

As the acid diffusion controller, a nitrogen-containing organic compound whose basicity is not changed by exposure or heat treatment in the resist pattern forming step is preferable.
As such a nitrogen-containing organic compound, for example, a compound represented by the following general formula (33) (hereinafter referred to as “nitrogen-containing compound (α)”).

〔一般式（３３）において、各Ｒ³¹は相互に独立に水素原子、アルキル基、アリール基またはアラルキル基を示し、これらの基は例えばヒドロキシ基等の官能基で置換されていてもよい。〕、

[In the general formula (33), each R ³¹ independently represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and these groups may be substituted with a functional group such as a hydroxy group. ],

A diamino compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (β)”) and a diamino polymer having three or more nitrogen atoms (hereinafter referred to as “nitrogen-containing compound (γ)”). ), Amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like.

  Examples of the nitrogen-containing compound (α) include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; di-n-butylamine, di-n- Dialkylamines such as pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine; triethylamine, tri-n-propylamine, Trialkylamines such as tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine Aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methyl Ruanirin, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, and the like can be given aromatic amines such as 1-naphthylamine.

Examples of the nitrogen-containing compound (β) include ethylenediamine, N, N, N ′,
N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2,2′-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2 -(4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) ) -1-Methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl Mention may be made of benzene, and the like.
Examples of the nitrogen-containing compound (γ) include polymers of polyethyleneimine, polyallylamine, dimethylaminoethylacrylamide, and the like.

Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like. Can be mentioned.
Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tributylthiourea and the like. be able to.

  Examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole; pyridine, 2-methylpyridine, 4-methyl. Such as pyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, acridine, etc. In addition to pyridines, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, phenanthro Mention may be made of the emissions and the like.

Moreover, the nitrogen-containing compound which has an acid dissociable group can also be used as said nitrogen-containing organic compound.
Examples of the nitrogen-containing compound having an acid dissociable group include N- (t-butoxycarbonyl) piperidine, N- (t-butoxycarbonyl) imidazole, N- (t-butoxycarbonyl) benzimidazole, N- (t -Butoxycarbonyl) 2-phenylbenzimidazole, N- (t-butoxycarbonyl) dioctylamine, N- (t-butoxycarbonyl) diethanolamine, N- (t-butoxycarbonyl) dicyclohexylamine, N- (t-butoxycarbonyl) diphenylamine Etc.

Of these nitrogen-containing organic compounds, nitrogen-containing compounds (α), nitrogen-containing compounds (β), nitrogen-containing heterocyclic compounds, nitrogen-containing compounds having an acid-dissociable group, and the like are preferable.
The acid diffusion controller can be used alone or in admixture of two or more.
The compounding amount of the acid diffusion controller is usually 15 parts by weight or less, preferably 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight per 100 parts by weight of the acid dissociable group-containing resin or alkali-soluble resin. Part. In this case, when the compounding amount of the acid diffusion controller exceeds 15 parts by weight, the sensitivity as a resist and the developability of the exposed part tend to be lowered. If the amount of the acid diffusion controller is less than 0.001 part by weight, the pattern shape and dimensional fidelity as a resist may be lowered depending on the process conditions.

-Alkali-soluble resin-
In some cases, an alkali-soluble resin (hereinafter referred to as “alkali-soluble resin (c)”) can be blended with the positive radiation-sensitive resin composition (A).
Examples of the alkali-soluble resin (c) include poly (4-hydroxystyrene), partially hydrogenated poly (4-hydroxystyrene), poly (3-hydroxystyrene), partially hydrogenated poly (3-hydroxystyrene), 4 -Hydroxystyrene / 3-hydroxystyrene copolymer, 4-hydroxystyrene / styrene copolymer, novolak resin, polyvinyl alcohol, polyacrylic acid and the like can be mentioned.
Mw of alkali-soluble resin (c) is 1,000-1,000,000 normally, Preferably it is 2,000-100,000.
The alkali-soluble resin (c) can be used alone or in admixture of two or more.
The blending amount of the alkali-soluble resin (c) is preferably 30 parts by weight or less per 100 parts by weight of the acid-dissociable group-containing resin.

-Surfactant-
The positive-type radiation-sensitive resin composition (A), the positive-type radiation-sensitive resin composition (B) and the negative-type radiation-sensitive resin composition (C) can be used as coating properties, striations, and resists. A surfactant exhibiting an effect of improving developability and the like can be blended.
Examples of such surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenol ether, polyoxyethylene n-nonylphenol ether, polyethylene glycol dilaurate, polyethylene glycol dilaurate. Examples of commercially available products include F-top EF301, EF303, EF352 (manufactured by Tochem Products), Megafax F171, F173 (above, Dainippon Ink & Chemicals, Inc.) )), Fluorad FC430, FC431 (above, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, the SC105, the SC106 (manufactured by Asahi Glass Co., Ltd.), KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).
These surfactants can be used alone or in admixture of two or more.
The compounding amount of the surfactant is preferably 2 parts by weight or less per 100 parts by weight of the acid-dissociable group-containing resin or alkali-soluble resin.

-Sensitizer-
A sensitizer can be mix | blended with positive type radiation sensitive resin composition (I), positive type radiation sensitive resin composition (B), and negative type radiation sensitive resin composition (C).
Preferred sensitizers include, for example, carbazoles, benzophenones, rose bengals, anthracenes and the like.
These sensitizers can be used alone or in admixture of two or more. The blending amount of the sensitizer is preferably 50 parts by weight or less per 100 parts by weight of the acid-dissociable group-containing resin or alkali-soluble resin.

-Additives other than the above-
In addition, by blending dyes and / or pigments, the latent image of the exposed area can be visualized, and the influence of halation during exposure can be alleviated. can do.
Furthermore, as other additives, an antihalation agent such as 4-hydroxy-4′-methylchalcone, a shape improver, a storage stabilizer, an antifoaming agent, and the like can be blended.

The solvent positive type radiation sensitive resin composition (a), the positive type radiation sensitive resin composition (b) and the negative type radiation sensitive resin composition (c) usually have a total solid content concentration in use. 0.1 to 50% by weight, preferably 1 to 40% by weight, after being uniformly dissolved in a solvent, it is prepared as a composition solution by, for example, filtering with a filter having a pore size of about 0.2 μm. .

Examples of the solvent used for the preparation of the composition solution include:
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether, propylene glycol di-n-butyl ether;
Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate;

Lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate;
N-amyl formate, i-amyl formate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, i-propyl propionate Aliphatic carboxylic acid esters such as n-butyl propionate and i-butyl propionate;
Ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl butyrate, Other esters such as methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;
Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
Examples include lactones such as γ-butyrolacun.
These solvents can be used alone or in admixture of two or more.

Formation of resist pattern When forming a resist pattern from the positive radiation sensitive resin composition (A), the positive radiation sensitive resin composition (B) and the negative radiation sensitive resin composition (C), The composition solution thus prepared is applied onto a substrate such as a silicon wafer or a wafer coated with aluminum by an appropriate application means such as spin coating, cast coating, or roll coating. A heat treatment (hereinafter referred to as “PB”) is performed in advance at a temperature of about 70 ° C. to 160 ° C. to form a resist film, and then exposed through a predetermined mask pattern. Examples of radiation used in this case include ultraviolet rays, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), EUV (extreme ultraviolet light, wavelength 13 nm, etc.), etc. Far-ultraviolet rays, charged particle beams such as electron beams, and X-rays such as synchrotron radiation can be appropriately selected and used. Of these, far-ultraviolet rays and electron beams are preferred. Moreover, exposure conditions, such as exposure amount, are suitably selected according to the compounding composition of a radiation sensitive resin composition, the kind of each additive, etc.

In the present invention, in order to stably form a high-precision fine pattern, it is preferable to perform a heat treatment (hereinafter referred to as “PEB”) for 30 seconds or more at a temperature of 70 to 160 ° C. after exposure. In this case, if the temperature of the PEB is less than 70 ° C., there is a possibility that the variation in sensitivity depending on the type of the substrate is widened.
Then, it is developed with an alkali developer usually at 10 to 50 ° C. for 10 to 200 seconds, preferably at 15 to 30 ° C. for 15 to 100 seconds, particularly preferably at 20 to 25 ° C. for 15 to 90 seconds. A predetermined resist pattern is formed.
Examples of the alkali developer include alkali metal hydroxide, aqueous ammonia, mono-, di- or tri-alkylamines, mono-, di- or tri-alkanolamines, heterocyclic amines, and tetraalkyls. Alkaline compounds such as ammonium hydroxides, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene are usually used. An alkaline aqueous solution dissolved so as to have a concentration of 1 to 10% by weight, preferably 1 to 5% by weight, particularly preferably 1 to 3% by weight is used.
In addition, a water-soluble organic solvent such as methanol or ethanol or a surfactant can be appropriately added to the developer composed of the alkaline aqueous solution.
In forming the resist pattern, a protective film can be provided on the resist film to prevent the influence of basic impurities contained in the environmental atmosphere, and an antireflection film for the lower layer or the upper layer is provided. You can also.

The acid generator (I) of the present invention has a relatively high combustibility, has no problem with human accumulation, and has a sufficiently high acidity and boiling point of the generated acid. Further, the acid generator (I) of KrF excimer laser, ArF Radiation sensitive acid generation that excels in transparency to deep ultraviolet rays such as excimer laser, F ² excimer laser or EUV, and electron beam, and generates sulfonic acid (Ia) of the present invention in response to these radiations Radiation-sensitive acid generator in a radiation-sensitive resin composition that is useful as an agent or a thermal acid generator that generates the sulfonic acid (Ia) of the present invention upon heating. Can be used very suitably.
The sulfonic acid (Ia) of the present invention is useful as a constituent component of an antireflection film for a lower layer or an upper layer provided when forming a resist pattern, and the sulfonate (1C) of the present invention and the present invention. The sulfonyl halide compound (4A) is useful as a reaction intermediate for synthesizing the acid generator (I), and the sulfonic acid (Ia), the sulfonate (1C) and the sulfonyl halide compound (4A) are It is also useful as a raw material for the synthesis of various sulfonic acid derivatives.
The radiation-sensitive resin composition of the present invention containing the acid generator (I) is effective for active radiation, particularly far ultraviolet rays and electron beams typified by KrF excimer laser, ArF excimer laser, F ² excimer laser or EUV. The sensitivity of the mask pattern is high, the acid diffusion length in the resist film is moderately short, the resolution is excellent, and the dependency on the sparse density of the mask pattern is small. It can be used very suitably in the field of microfabrication represented by the production of integrated circuit elements.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
Here,% and parts are based on weight unless otherwise specified.
[Synthesis of Acid Generator (I)]
Synthesis example 1
108.5 g of dicyclopentadiene and 322.4 g of 1-bromo-1,1,2,2-tetrafluoro-3-butene were placed in an autoclave, and 0.3 g of 4-methoxyphenol was dissolved in 5 ml of toluene as a polymerization inhibitor. The obtained solution was added, stirred at 170 ° C. for 5 hours, and purified by distillation under reduced pressure at 85 ° C. and 25 mmHg to obtain colorless liquid 1-bromo-1,1,2,2-tetrafluoro-2- 326 g of (norborn-5-en-2-yl) ethane (hereinafter referred to as “compound (1-a)”) was obtained.
Next, a solution obtained by dissolving 62 g of compound (1-a) in 1 liter of ethyl acetate was placed in a 2 liter eggplant flask, 12 g of alumina containing 5% rhodium was added, and the mixture was vigorously stirred for 3 hours in a hydrogen atmosphere. Thereafter, the reaction solution is suction filtered through a glass filter with celite, the filtrate is concentrated under reduced pressure, and the concentrated solution is purified by distillation under reduced pressure to give colorless liquid 1-bromo-1,1,2,2. -56 g of tetrafluoro-2- (norbornan-2-yl) ethane (hereinafter referred to as “compound (1-b)”) was obtained.

  Next, a solution obtained by dissolving 70 g of sodium dithionite and 52 g of sodium hydrogen carbonate in 300 ml of water was placed in a 2-liter three-necked flask sufficiently purged with nitrogen, and 55 g of compound (1-b) was dissolved in acetonitrile. 300 ml of the solution was added dropwise at room temperature over 1 hour and reacted at 75 ° C. for 2 hours. Thereafter, the reaction solution was distilled under reduced pressure to remove acetonitrile, and then 350 mg of sodium tungstate dihydrate and 5.0 g of disodium hydrogen phosphate were added, carefully maintaining 30% hydrogen peroxide while maintaining the pH of the reaction solution. 5.6 ml of water was added dropwise at room temperature. Thereafter, water was removed by distillation under reduced pressure, and the residue was extracted with methanol, and then methanol was removed by distillation under reduced pressure to obtain 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethane. 35 g of sodium sulfonate (hereinafter referred to as “compound (1-c)”) was obtained.

Next, 80 g of 1-n-butoxynaphthalene and 212 g of a phosphorus pentoxide-methanesulfonic acid mixture were placed in a 5-liter eggplant flask and stirred for 15 minutes at room temperature. Then, 47 g of tetramethylene sulfoxide was added dropwise at 0 ° C. and stirred for 20 minutes. After that, the temperature was gradually raised to room temperature and further stirred for 1 hour. Then, it cooled again to 0 degreeC, 2 liters of water was added, pH was adjusted to 7.0 with 25% ammonia water, and it stirred at room temperature for 1 hour. Thereafter, a solution in which 116 g of compound (1-c) was dissolved in 150 ml of water was added, stirred at room temperature for 1 hour, extracted with methylene chloride, and the extract was washed with water. Thereafter, methylene chloride was distilled off under reduced pressure and purified by a silica gel column (methylene chloride: methanol = 20: 1), followed by reprecipitation treatment with methylene chloride / n-hexane system. 76 g of (1-n-butoxynaphth-4-yl) sulfonium 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate was obtained.
The measurement results of ¹ H-NMR analysis and mass spectrometry of this compound are shown in FIGS. 1 and 2, respectively.
This compound is referred to as “acid generator (A-1)”.

Mass analysis of the acid generator (A-1) and the following acid generators (A-2) to (A-6) was performed under the following conditions.
Apparatus: JMS-AX505W type mass spectrometer manufactured by JEOL Ltd. Emitter current: 5 mA (used gas: Xe)
Acceleration voltage: 3.0 kV
10N MULTI: 1.3
Ionization method: Fast atom bombardment method (FAB)
Detection ion: Cation (+)
Measurement mass range: 20-1500 m / z
Scan: 30 sec
Resolution: 1500
Matrix: 3-nitrobenzyl alcohol

Synthesis example 2
A solution prepared by dissolving 20 g of triphenylsulfonium chloride in 500 ml of water was placed in a 2-liter eggplant flask, and 500 ml of an aqueous solution of 20 g of compound (1-c) was added dropwise at room temperature, followed by stirring for 30 minutes. Thereafter, the reaction solution is extracted with ethyl acetate, and the organic layer is washed twice with water, and then concentrated by distillation under reduced pressure to give triphenylsulfonium 1,1,2,2-tetrafluoro as a colorless and highly viscous oil. 16 g of -2- (norbornan-2-yl) ethanesulfonate was obtained. The measurement results of ¹ H-NMR analysis and mass spectrometry of this compound are shown in FIGS. 3 and 4, respectively.
This compound is referred to as “acid generator (A-2)”.

Synthesis example 3
A solution prepared by dissolving 20 g of diphenyliodonium chloride in 1 liter of water was placed in a 2-liter eggplant flask, 500 ml of an aqueous solution of 20 g of compound (1-c) was added dropwise at room temperature, and the mixture was stirred for 15 minutes. Thereafter, the precipitated crystals were filtered through a glass filter, sufficiently washed with water, dried under reduced pressure, and 12 g of diphenyliodonium 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate. Got.
The measurement results of ¹ H-NMR analysis and mass spectrometry of this compound are shown in FIGS. 5 and 6, respectively.
This compound is referred to as “acid generator (A-3)”.

Synthesis example 4
A solution obtained by dissolving 70 g of sodium dithionite and 52 g of sodium hydrogen carbonate in 300 ml of water was placed in a 2-liter three-necked flask sufficiently purged with nitrogen, and a solution 300 of 55 g of compound (1-b) dissolved in acetonitrile. Milliliter was added dropwise at room temperature over 1 hour and reacted at 75 ° C. for 2 hours. Thereafter, the reaction solution was distilled under reduced pressure to remove acetonitrile, the reaction solution was extracted with ethyl acetate, the organic layer was washed with saturated brine, and then dried over anhydrous magnesium sulfate. Thereafter, by distillation under reduced pressure to remove ethyl acetate, sodium 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfinate (hereinafter referred to as “compound (1-d)”). .) 35 g was obtained.

  Next, a solution obtained by dissolving 80 g of compound (1-d) in 250 ml of water was placed in a 2-liter eggplant flask, and excess chlorine gas was bubbled for 15 minutes or more while stirring at room temperature. Thereafter, the oily substance collected at the bottom of the flask was extracted with methylene chloride, and the organic layer was washed with an aqueous sodium hydrogen carbonate solution and then dried over anhydrous magnesium sulfate. Then, 1,2,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonyl chloride (hereinafter referred to as “compound (4-a)”) was removed by distillation under reduced pressure to remove methylene chloride. 68 g was obtained.

Next, 22 g of N-hydroxy-5-norbornene-2,3-dicarboximide was added to a solution of 30 g of compound (4-a) in 150 g of tetrahydrofuran, and 29 g of triethylamine was added dropwise. Then, after stirring a reaction liquid at room temperature for 10 minutes, water was dripped and the reaction product was deposited as a white crystal | crystallization. Thereafter, the precipitate was filtered and dissolved in methylene chloride, and then the solution was washed successively with an aqueous sodium hydrogen carbonate solution, an oxalic acid aqueous solution and water. Thereafter, the solution was dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove methylene chloride, whereby N- (1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethyl sulfone was removed. 35 g of (Nyloxy) -5-norbornene-2,3-dicarboximide was obtained.
The measurement result of ¹ H-NMR analysis of this compound is shown in FIG.
This compound is referred to as “acid generator (A-4)”.

Synthesis example 5
108.5 g of dicyclopentadiene and 322.4 g of 1-bromo-1,1,2,2-tetrafluoro-3-butene were placed in an autoclave, and 0.3 g of 4-methoxyphenol was dissolved in 5 ml of toluene as a polymerization inhibitor. The obtained solution was added, stirred at 170 ° C. for 5 hours, and purified by distillation under reduced pressure at 85 ° C. and 0.1 mmHg to give colorless liquid 1-bromo-1,1,2,2-tetrafluoro- 2- (tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-en-8-yl) ethane (hereinafter referred to as "compound (5-a)".) to give a 226g It was.

Next, a solution obtained by dissolving 93 g of compound (5-a) in 1.5 liters of ethyl acetate was placed in a 3 liter eggplant flask, 18 g of alumina containing 5% rhodium was added, and the mixture was vigorously stirred under a hydrogen atmosphere for 3 hours. did. Thereafter, the reaction solution is suction filtered through a glass filter with celite, the filtrate is concentrated under reduced pressure, and the concentrated solution is purified by distillation under reduced pressure to give colorless liquid 1-bromo-1,1,2,2 -85 g of tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 .1, ^7,10 ] dodecan-8-yl) ethane (hereinafter referred to as “compound (5-b)”) is obtained. It was.

Next, a solution obtained by dissolving 10.2 g of sodium dithionite and 7.4 g of sodium hydrogen carbonate in 170 ml of water was placed in a 2-liter three-necked flask thoroughly purged with nitrogen, and 10 g of compound (5-b) was added. A solution dissolved in 750 ml of acetonitrile was dropped at room temperature over 1 hour and reacted at 100 ° C. for 7 hours. Thereafter, the reaction solution was distilled under reduced pressure to remove acetonitrile, and then the aqueous solution was suction filtered, and the filtrate was concentrated under reduced pressure. Thereafter, the residue was extracted with methanol, and then distilled under reduced pressure to remove methanol, whereby 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 .1 ^{7, 10} ] dodecan-8-yl) ethanesulfinate sodium (henceforth "compound (5-c)") 10.2g was obtained.

Next, a solution of 9 g of compound (5-c) in 75 ml of water was placed in a 500 ml three-necked flask, 50 mg of sodium tungstate dihydrate and 1.2 g of disodium hydrogen phosphate were added, While maintaining the pH of the reaction solution, 3 ml of 30% aqueous hydrogen peroxide was added dropwise at room temperature. Then, after making the reaction liquid react at 60 degreeC for 1 hour, 100 ml of water was added and it stood to cool to room temperature. Thereafter, a solution prepared by dissolving 10 g of triphenylsulfonium chloride in 250 ml of water was added dropwise to the reaction solution at room temperature, followed by stirring for 1 hour. Thereafter, the reaction solution is extracted with ethyl acetate, and the organic layer is washed three times with water, and then distilled under reduced pressure to remove ethyl acetate, and purified by a silica gel column (methylene chloride: methanol = 8: 1). triphenylsulfonium 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane-8-yl) ethanesulfonate 1g.
The measurement results of ¹ H-NMR analysis of this compound are shown in FIG. 8, and the measurement results of mass spectrometry of the cation moiety and the anion moiety are shown in FIGS. 9 and 10, respectively.
This compound is referred to as “acid generator (A-5)”.

Synthesis Example 6
A solution prepared by dissolving 25.2 g of sodium hydrogen carbonate in 500 ml of water was placed in a 2-liter eggplant flask, and 19.2 g of methyl 2- (fluorosulfonyl) difluoroacetate was added dropwise while stirring at room temperature. Stir for 2 hours. Thereafter, water was distilled off under reduced pressure, and the resulting solid was dried overnight at room temperature under vacuum. The solid was then extracted and purified with 200 ml of methanol, and then vacuum dried at room temperature to obtain methoxycarbonyldifluoro. 0.34 g of sodium methanesulfonate (hereinafter referred to as “compound (6-a)”) was obtained.

Next, after adding a solution obtained by dissolving 0.478 g of triphenylsulfonium chloride in 5 ml of water to a solution obtained by dissolving 0.34 g of compound (6-a) in 15 ml of water, the mixture was added with 20 ml of ethyl acetate. Extracted twice. Thereafter, the organic layer was washed with 20 ml of water, dried over anhydrous sodium sulfate, further distilled under reduced pressure to remove ethyl acetate, and then dried under vacuum to give highly viscous oily triphenylsulfonium methoxycarbonyldifluoromethane. 0.25 g of sulfonate was obtained.
The measurement results of the mass spectrometry of the cation portion and the anion portion of this compound are shown in FIGS. 11 and 12, respectively.
This compound is referred to as “acid generator (A-6)”.

[Synthesis of acid-dissociable group-containing resin]
Synthesis example 7
After dissolving 101 g of 4-acetoxystyrene, 5 g of styrene, 42 g of 4-t-butoxystyrene, 6 g of azobisisobutyronitrile (AIBN) and 1 g of t-dodecyl mercaptan in 160 g of propylene glycol monomethyl ether, the reaction was conducted in a nitrogen atmosphere. Polymerization was performed for 16 hours while maintaining the temperature at 70 ° C. After the polymerization, the reaction solution was dropped into a large amount of n-hexane to coagulate and purify the resulting resin.
Next, 150 g of propylene glycol monomethyl ether was added to the purified resin, and then 300 g of methanol, 80 g of triethylamine and 15 g of water were further added, and a hydrolysis reaction was performed for 8 hours while refluxing at the boiling point. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the resulting resin was dissolved in acetone, then dripped into a large amount of water to solidify, and the resulting white powder was filtered and dried at 50 ° C. under reduced pressure overnight. did.
The obtained resin has Mw of 16,000 and Mw / Mn of 1.7. As a result of ¹³ C-NMR analysis, the copolymerization molar ratio of 4-hydroxystyrene, styrene, and 4-t-butoxystyrene is 72: 5: 23.
This resin is referred to as “resin (B-1)”.

Resin Measurement of Mw and Mn of (B-1) and the following resin-(B-2) ~ (B -13) are manufactured by Tosoh Corporation GPC column (G2000H _XL 2 present, one G3000H _XL, G4000H _XL 1 This was measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions of a flow rate of 1.0 ml / min, an elution solvent tetrahydrofuran, and a column temperature of 40 ° C.

Synthesis example 8
100 g of 4-acetoxystyrene, 25 g of t-butyl acrylate, 18 g of styrene, 6 g of AIBN and 1 g of t-dodecyl mercaptan are dissolved in 230 g of propylene glycol monomethyl ether, and the reaction temperature is maintained at 70 ° C. for 16 hours under a nitrogen atmosphere. did. After the polymerization, the reaction solution was dropped into a large amount of hexane to coagulate and purify the resulting resin.
Next, 150 g of propylene glycol monomethyl ether was added to the purified resin, and then 300 g of methanol, 80 g of triethylamine and 15 g of water were further added, and a hydrolysis reaction was performed for 8 hours while refluxing at the boiling point. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the resulting resin was dissolved in acetone, then dripped into a large amount of water to solidify, and the resulting white powder was filtered and dried at 50 ° C. under reduced pressure overnight. did.
The obtained resin has Mw of 11,500 and Mw / Mn of 1.6, and as a result of ¹³ C-NMR analysis, the copolymerization molar ratio of 4-hydroxystyrene, t-butyl acrylate and styrene is 61:19:20.
This resin is referred to as “resin (B-2)”.

Synthesis Example 9
176 g of 4-t-butoxystyrene was anionically polymerized in 500 ml of tetrahydrofuran at −78 ° C. using n-butyllithium as a catalyst. After polymerization, the reaction solution was coagulated in methanol to obtain 150 g of white poly (4-t-butoxystyrene).
Next, 150 g of this poly (4-t-butoxystyrene) is dissolved in 600 g of dioxane, dilute hydrochloric acid is added, a hydrolysis reaction is performed at 70 ° C. for 2 hours, and then the reaction solution is dropped into a large amount of water to obtain a resin. Solidified. Then, after repeating operation which melt | dissolves this resin in acetone and coagulate | solidifies in a lot of water, the produced | generated white powder was filtered and it dried at 50 degreeC under pressure reduction overnight. The obtained resin had an Mw of 10,400 and an Mw / Mn of 1.10. As a result of ¹³ C-NMR analysis, only a part of the t-butyl group in poly (4-t-butoxystyrene) was obtained. It was confirmed to be a copolymer having a hydrolyzed structure and a copolymerization molar ratio of 4-t-butoxystyrene and 4-hydroxystyrene of 68:32.
This resin is referred to as “resin (B-3)”.

Synthesis Example 10
25 g of 4-hydroxystyrene / 4-t-butoxystyrene copolymer having a copolymerization molar ratio of 90:10 was dissolved in 100 g of n-butyl acetate, bubbled with nitrogen gas for 30 minutes, and then ethyl vinyl ether 3 .3 g was added, 1 g of p-toluenesulfonic acid pyridinium salt was added as a catalyst, and the mixture was reacted at room temperature for 12 hours. Thereafter, the reaction solution was dropped into a 1% aqueous ammonia solution to solidify the resin, filtered, and dried overnight in a vacuum dryer at 50 ° C.
The obtained resin had Mw of 13,000 and Mw / Mn of 1.01, and as a result of ¹³ C-NMR analysis, 23 mol% of hydrogen atoms of the phenolic hydroxyl group in poly (4-hydroxystyrene) was found to be The ethoxyxyethyl group had a structure in which 10 mol% was substituted with a t-butyl group.
This resin is referred to as “resin (B-4)”.

Synthesis Example 11
5 g of norbornene, 11 g of maleic anhydride, 8-hydroxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] 11 g of dodec-3-ene and 23 g of 2-methyl-2-adamantyl methacrylate were uniformly dissolved in 50 g of tetrahydrofuran, nitrogen was blown for 30 minutes, 3 g of AIBN was added, and the mixture was heated to 65 ° C. The polymerization was carried out for 6 hours while maintaining the same temperature. After completion of the polymerization, the reaction solution was cooled to room temperature, diluted with 50 g of tetrahydrofuran, poured into 1,000 ml of n-hexane, and the precipitated white powder was filtered and dried to obtain a resin. It was.
This resin has an Mw of 6,100, norbornene, maleic anhydride and 8-hydroxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3-ene and 2-methyl-2-adamantyl methacrylate copolymer had a copolymer molar ratio of 15: 35: 20: 30.
This resin is referred to as "resin (B-5)".

Synthesis Example 12
46.31 g of 2-methyl-2-adamantyl methacrylate and 53.69 g of the compound of the following formula (34) were uniformly dissolved in 200 g of 2-butanone, and 4.04 g of methyl azobisisovalerate was added as a polymerization initiator. A monomer solution was prepared.
Separately, nitrogen was blown into a 1 liter three-necked flask charged with 100 g of 2-butanone for 30 minutes, heated to 80 ° C. with stirring, and then the monomer solution was added dropwise at a rate of 10 mm / 5 minutes. For 5 hours. Thereafter, the reaction solution was cooled to 30 ° C. or lower, poured into 2,000 g of methanol, and the precipitated white powder was filtered off, and then mixed with 400 g of methanol and washed twice. Thereafter, the white powder was filtered off and dried at 50 ° C. for 17 hours to obtain a resin.
This resin was a copolymer having an mW of 12,200 and a copolymerization molar ratio of 2-methyl-2-adamantyl methacrylate and the compound of the formula (34) of 40.6: 59.4.
This resin is referred to as “resin (B-6)”.

Synthesis Example 13
40.90 g of 2-methyl-2-adamantyl methacrylate, 15.47 g of 3-hydroxy-1-adamantyl methacrylate and 43.64 g of the compound of the above formula (34) are uniformly dissolved in 200 g of 2-butanone, and azobisiso A monomer solution to which 4.02 g of methyl valerate was added was prepared.
Separately, nitrogen was blown into a 1 liter three-necked flask charged with 100 g of 2-butanone for 30 minutes, heated to 80 ° C. with stirring, and then the monomer solution was added dropwise at a rate of 10 mm / 5 minutes. For 5 hours. Thereafter, the reaction solution was cooled to 30 ° C. or lower, poured into 2,000 g of methanol, and the precipitated white powder was filtered off, and then mixed with 400 g of methanol and washed twice. Thereafter, the white powder was filtered off and dried at 50 ° C. for 17 hours to obtain a resin.
This resin has an Mw of 9,200, and a copolymerization molar ratio of 2-methyl-2-adamantyl methacrylate, 3-hydroxy-1-adamantyl methacrylate and the compound of the formula (34) is 36.2: 15. 2: 48.6 copolymer.
This resin is referred to as “resin (B-7)”.

Synthesis Example 14
50.55 g of 2-methyl-2-adamantyl methacrylate, 25.49 g of 3-hydroxy-1-adamantyl methacrylate and 23.97 g of the compound of the above formula (34) were uniformly dissolved in 200 g of 2-butanone, and azobisiso A monomer solution to which 3.97 g of methyl valerate was added was prepared.
Separately, nitrogen was blown into a 1 liter three-necked flask charged with 100 g of 2-butanone for 30 minutes, heated to 80 ° C. with stirring, and then the monomer solution was added dropwise at a rate of 10 mm / 5 minutes. For 5 hours. Thereafter, the reaction solution was cooled to 30 ° C. or lower, poured into 2,000 g of methanol, and the precipitated white powder was filtered off, and then mixed with 400 g of methanol and washed twice. Thereafter, the white powder was filtered off and dried at 50 ° C. for 17 hours to obtain a resin.
This resin has an Mw of 9,800, and a copolymerization molar ratio of 2-methyl-2-adamantyl methacrylate, 3-hydroxy-1-adamantyl methacrylate and the compound of the formula (34) is 45.2: 25. 6: 29.2 copolymer.
This resin is referred to as “resin (B-8)”.

Synthesis Example 15
46.17 g of 2-methyl-2-adamantyl methacrylate, 5.179 g of 3-hydroxy-1-adamantyl methacrylate and 48.65 g of the compound of the above formula (34) are uniformly dissolved in 200 g of 2-butanone, and further azobisiso A monomer solution to which 4.03 g of methyl valerate was added was prepared.
Separately, nitrogen was blown into a 1 liter three-necked flask charged with 100 g of 2-butanone for 30 minutes, heated to 80 ° C. with stirring, and then the monomer solution was added dropwise at a rate of 10 mm / 5 minutes. For 5 hours. Thereafter, the reaction solution was cooled to 30 ° C. or lower, poured into 2,000 g of methanol, and the precipitated white powder was filtered off, and then mixed with 400 g of methanol and washed twice. Thereafter, the white powder was filtered off and dried at 50 ° C. for 17 hours to obtain a resin.
This resin has an Mw of 9,400 and a copolymerization molar ratio of 2-methyl-2-adamantyl methacrylate, 3-hydroxy-1-adamantyl methacrylate and the compound of formula (34) of 39.2: 5. .4: 55.4 copolymer.
This resin is referred to as “resin (B-9)”.

Synthesis Example 16
Monomer solution in which 47.76 g of 2-ethyl-2-adamantyl methacrylate and 52.24 g of the compound of the formula (34) are uniformly dissolved in 200 g of 2-butanone, and 3.93 g of methyl azobisisovalerate are further added. Prepared.
Separately, nitrogen was blown into a 1 liter three-necked flask charged with 100 g of 2-butanone for 30 minutes, heated to 80 ° C. with stirring, and then the monomer solution was added dropwise at a rate of 10 mm / 5 minutes. For 5 hours. Thereafter, the reaction solution was cooled to 30 ° C. or lower, poured into 2,000 g of methanol, and the precipitated white powder was filtered off, and then mixed with 400 g of methanol and washed twice. Thereafter, the white powder was filtered off and dried at 50 ° C. for 17 hours to obtain a resin.
This resin was a copolymer having an Mw of 11,600 and a copolymerization molar ratio of 2-ethyl-2-adamantyl methacrylate and the compound of formula (34) of 39.8: 60.2.
This resin is referred to as “resin (B-10)”.

Synthesis Example 17
A monomer solution was prepared by uniformly dissolving 41.95 g of 1-ethylcyclohexyl methacrylate and 58.05 g of the compound of formula (34) in 200 g of 2-butanone, and further adding 4.37 g of methyl azobisisovalerate. .
Separately, nitrogen was blown into a 1 liter three-necked flask charged with 100 g of 2-butanone for 30 minutes, heated to 80 ° C. with stirring, and then the monomer solution was added dropwise at a rate of 10 mm / 5 minutes. For 5 hours. Thereafter, the reaction solution was cooled to 30 ° C. or lower, poured into 2,000 g of methanol, and the precipitated white powder was filtered off, and then mixed with 400 g of methanol and washed twice. Thereafter, the white powder was filtered off and dried at 50 ° C. for 17 hours to obtain a resin.
This resin was a copolymer having an Mw of 13,400 and a copolymerization molar ratio of 1-ethylcyclohexyl methacrylate and the compound of the formula (34) of 42.1: 57.9.
This resin is referred to as “resin (B-11)”.

Synthesis Example 18
22.00 g of 2-ethyl-2-adamantyl methacrylate, 24.74 g of 3-hydroxy-1-adamantyl methacrylate and 23.26 g of the compound of the formula (34) were uniformly dissolved in 200 g of 2-butanone, and azobisiso A monomer solution to which 3.85 g of methyl valerate was added was prepared.
Separately, nitrogen was blown into a 1-liter three-necked flask charged with 100 g of 2-butanone for 30 minutes and heated to 80 ° C. with stirring, and then the monomer solution was added dropwise at a rate of 10 mm / 5 minutes. Polymerized for hours. Thereafter, the reaction solution was cooled to 30 ° C. or lower, poured into 2,000 g of methanol, and the precipitated white powder was filtered off, and then mixed with 400 g of methanol and washed twice. Thereafter, the white powder was filtered off and dried at 50 ° C. for 17 hours to obtain a resin.
This resin has an Mw of 8,700, and a copolymerization molar ratio of 2-ethyl-2-adamantyl methacrylate, 3-hydroxy-1-adamantyl methacrylate and the compound of the formula (34) is 44.4: 25. .3: 30.3 copolymer.
This resin is referred to as “resin (B-12)”.

Synthesis Example 19
In a three-necked flask, 1.52 g of a silane compound represented by the following formula (35), 1.57 g of a silane compound represented by the following formula (36), 1.91 g of methyltriethoxysilane, 4-methyl-2- After adding 15 g of pentanone and 1.31 g of 1.75% oxalic acid aqueous solution and reacting at 80 ° C. for 6 hours with stirring, the reaction vessel was ice-cooled to stop the reaction. Thereafter, the reaction solution was transferred to a separatory funnel, the aqueous layer was discarded, and ion-exchanged water was further added and washed, and washing was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain a resin.
This resin had a Mw of 2,500.
This resin is referred to as “resin (B-13)”.

Synthesis Example 20
To a solution obtained by dissolving 12 g of poly (4-hydroxystyrene) and 5 g of triethylamine in 50 g of dioxane, 7 g of di-t-butyl carbonate was added with stirring. After stirring for 6 hours at room temperature, oxalic acid was added and triethylamine was added. Neutralized. Thereafter, the reaction solution was dropped into a large amount of water to solidify the resin, the solidified resin was washed several times with pure water, filtered, and dried overnight at 50 ° C. under reduced pressure.
The obtained resin has an Mw of 9,200 and an Mw / Mn of 1.8. As a result of ¹³ C-NMR analysis, 30 mol% of hydrogen atoms of the phenolic hydroxyl group in poly (4-hydroxystyrene) , And a structure substituted with a t-butoxycarbonyl group.
This resin is referred to as “resin (B-14)”.

[Radiation sensitive resin composition]
The evaluation of each resist in Examples and Comparative Examples was performed as follows.
sensitivity:
The resist film formed on the silicon wafer is exposed to light, immediately subjected to PEB, alkali-developed, washed with water, and dried to form a resist pattern. When a resist pattern is formed, a line-and-space pattern with a line width of 0.22 μm ( 1L1S) was formed as an optimum exposure dose, and the sensitivity was evaluated based on this optimum exposure dose. However, in the example using an ArF excimer laser, the exposure amount for forming a line-and-space pattern (1L1S) having a line width of 0.16 μm in a one-to-one line width was set as the optimum exposure amount.
resolution:
The minimum dimension of the line-and-space pattern (1L1S) resolved when exposed at the optimum exposure amount was taken as the resolution.
Mask pattern dependency:
When the line width of a 1L10S pattern (0.22 um line / 2.2 um space) having a design dimension of 0.22 um exceeds 70% of the design dimension (0.22 um) when exposed at an optimal exposure amount, the condition is “good”. When it was less than%, it was judged as “bad”. However, when the ArF exposure apparatus is used, the mask design dimension (0.16 um) of the line width of the 1L / 10S pattern (0.16 um line / 1.6 um space) having the design dimension of 0.16 um at the optimum exposure amount is used. When it exceeded 70%, it was judged as “good”, and when it was less than 70%, it was judged as “bad”.
Mask pattern fidelity:
When exposure is performed at the optimum exposure amount, the difference (absolute value) between the line width of the 1L5S pattern (0.22 um line / 1.1 um space) having a design dimension of 0.22 um and the design dimension (0.22 um) It was sex.

Examples 1 to 19 and Comparative Example 1
Each component shown in Table 1 was mixed to obtain a uniform solution, and then filtered through a membrane filter having a pore size of 0.2 μm to prepare a composition solution. Then, after spin-coating each composition solution on the silicon wafer, PB was performed on the conditions shown in Table 2, and the resist film of the film thickness shown in Table 2 was formed.
Next, in an example using a KrF excimer laser (indicated as “KrF” in Table 2) as an exposure light source, a stepper NSR2205 EX12B (numerical aperture: 0.55) manufactured by Nikon Corporation was used, and an ArF excimer laser was used as the exposure light source. In Examples using “ArF” in Table 1, a Nikon ArF excimer laser exposure apparatus (numerical aperture: 0.55) is used, and an F ₂ excimer laser (“F2” in Table 1) is used as an exposure light source. In the example using Ultratech F ₂ excimer laser exposure apparatus XLS (numerical aperture 0.60), and in the example using electron beam as the exposure light source, Using a drawing electron beam lithography apparatus HL700 (apparatus whose acceleration voltage was improved from 30 KeV to 50 KeV), exposure was performed under the conditions shown in Table 2, and then PEB was performed under the conditions shown in Table 2.
Next, a 2.38 wt% tetramethylammonium hydroxide aqueous solution was used and developed at 23 ° C. for 1 minute by the paddle method, followed by washing with pure water and drying to form a resist pattern. Table 3 shows the evaluation results of each resist.

Examples 20-23
Each component shown in Table 4 was mixed to obtain a uniform solution, and then filtered through a membrane filter having a pore size of 0.2 μm to prepare a composition solution. Then, after spin-coating each composition solution on the silicon wafer, PB was performed on the conditions shown in Table 5, and the resist film of the film thickness shown in Table 5 was formed.
Next, using a stepper NSR2205 EX12B (numerical aperture: 0.55) manufactured by Nikon Corporation, exposure was performed with a KrF excimer laser, and then PEB was performed under the conditions shown in Table 5. Thereafter, a 2.38 wt% tetramethylammonium hydroxide aqueous solution was used and developed by the paddle method at 23 ° C. for 1 minute, and then washed with pure water and dried to form a resist pattern. Table 6 shows the evaluation results of each resist.

In Tables 1 and 4, other acid generators, alkali-soluble resins, acid diffusion control agents, crosslinking agents, other additives, and solvents are as follows.
Other acid generators a-1: N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide a-2: triphenylsulfonium trifluoromethanesulfonate a -3: Bis (cyclohexylsulfonyl) diazomethane

Alkali-soluble resin C-1: 4-hydroxystyrene / styrene copolymer (copolymerization molar ratio = 78/22, Mw = 3,100, Mw / Mn = 1.13, Nippon Soda Co., Ltd. VPS3020)
Acid diffusion control agent D-1: tri-n-octylamine D-2: triethanolamine D-3: 2-phenylbenzimidazole D-4: 2,6-dimethylaminopyridine D-5: Nt-butoxy Carbonyl-2-phenylbenzimidazole
Cross - linking agent E-1: N, N, N, N-tetra (methoxymethyl) glycoluril
Other additives F-1: t-butyl deoxycholate F-2: t-butoxycarbonylmethyl deoxycholate
Solvent G-1: Ethyl lactate G-2: Ethyl 3-ethoxypropionate G-3: Propylene glycol monomethyl ether acetate G-4: 2-heptanone G-5: Cyclohexanone G-6: γ-Butyrolactone

It is a figure which shows the measurement result of the < ¹ > H-NMR analysis of an acid generator (A-1). It is a figure which shows the measurement result of the mass spectrometry of the cation part of an acid generator (A-1). It is a figure which shows the measurement result of the mass spectrometry of the anion part of an acid generator (A-1). It is a figure which shows the measurement result of the < ¹ > H-NMR analysis of an acid generator (A-2). It is a figure which shows the measurement result of the mass spectrometry of the cation part of an acid generator (A-2). It is a figure which shows the measurement result of the mass spectrometry of the anion part of an acid generator (A-2). It is a figure which shows the measurement result of the < ¹ > H-NMR analysis of an acid generator (A-3). It is a figure which shows the measurement result of the mass spectrometry of the cation part of an acid generator (A-3). It is a figure which shows the measurement result of the mass spectrometry of the anion part of an acid generator (A-3). It is a figure which shows the measurement result of the < ¹ > H-NMR analysis of an acid generator (A-4). It is a figure which shows the measurement result of the < ¹ > H-NMR analysis of an acid generator (A-5). It is a figure which shows the measurement result of the mass spectrometry of the cation part of an acid generator (A-5). It is a figure which shows the measurement result of the mass spectrometry of the anion part of an acid generator (A-5). It is a figure which shows the measurement result of the mass spectrometry of the cation part of an acid generator (A-6). It is a figure which shows the measurement result of the mass spectrometry of the anion part of an acid generator (A-6).

Claims (11)

Radiation sensitive acid generator comprising a compound having the structure represented by the following general formula (I) (however, radiation sensitive acid generator having 1,1,2,2-tetrafluorobutanesulfonyl structure and 1,1 , Does not include a radiation sensitive acid generator having a 2,2-tetrafluorooctanesulfonyl structure.

[In General Formula (I), R is a monovalent organic group having a fluorine content of 50% by weight or less, and is —R ¹¹ , —CO—R ¹¹ , —COO—R ¹¹ , —CON (R ¹¹ ) (R ¹² ), -S-R ¹¹ ,
—SO—R ¹¹ or —SO ₂ —R ¹¹ (wherein R ¹¹ and R ¹² are each independently a substituted or unsubstituted linear or branched monovalent hydrocarbon group having 1 to 30 carbon atoms. And R is a substituted linear or branched monovalent hydrocarbon group having 1 to 30 carbon atoms, the substituent of the monovalent hydrocarbon group is a cyclic monovalent hydrocarbon group. No hydrocarbon group is contained, and Z ¹ and Z ² each independently represent a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms. ] A radiation sensitive acid generator comprising a compound having a structure represented by the following general formula (I-1), general formula (I-2) or general formula (I-3) [however, the general formula (I-1) The radiation-sensitive acid generator comprising a compound having the structure represented by formula (1) is a radiation-sensitive acid generator having a 1,1,2,2-tetrafluorobutanesulfonyl structure and 1,1,2,2-tetrafluoro. Does not contain a radiation sensitive acid generator having an octanesulfonyl structure. ].

[In General Formula (I-1), General Formula (I-2) and General Formula (I-3), each R is a monovalent organic group having a fluorine content of 50% by weight or less independently of each other. -R ¹¹ ,
—CO—R ¹¹ , —COO—R ¹¹ , —CON (R ¹¹ ) (R ¹² ), —S—R ¹¹ , —SO—R ¹¹ or —SO ₂ —R ¹¹ (where R ¹¹ and R ¹² are Each independently represents a substituted or unsubstituted linear or branched monovalent hydrocarbon group having 1 to 30 carbon atoms, and R is a substituted linear chain having 1 to 30 carbon atoms or When it is a branched monovalent hydrocarbon group, the substituent of the monovalent hydrocarbon group does not include a cyclic monovalent hydrocarbon group. ] A radiation sensitive acid generator comprising a sulfonic acid onium salt compound represented by the following general formula (1) (however, a radiation sensitive acid generator having a 1,1,2,2-tetrafluorobutanesulfonyl structure and 1, It does not include a radiation-sensitive acid generator having a 1,2,2-tetrafluorooctanesulfonyl structure.)

[In the general formula (1), R is a monovalent organic group having a fluorine content of 50% by weight or less, and is —R ¹¹ , —CO—R ¹¹ , —COO—R ¹¹ , —CON (R ¹¹ ) (R ¹² ), -S-R ¹¹ ,
—SO—R ¹¹ or —SO ₂ —R ¹¹ (wherein R ¹¹ and R ¹² are each independently a substituted or unsubstituted linear or branched monovalent hydrocarbon group having 1 to 30 carbon atoms. And R is a substituted linear or branched monovalent hydrocarbon group having 1 to 30 carbon atoms, the substituent of the monovalent hydrocarbon group is a cyclic monovalent hydrocarbon group. It contains no hydrocarbon group and M ⁺ represents a monovalent onium cation. ] The radiation-sensitive acid generator according to claim 3, wherein M ⁺ is a sulfonium cation represented by the following general formula (i).

[In General Formula (i), R ¹ , R ² and R ³ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted carbon number of 6 Or an aryl group of ˜18, or any two or more of R ¹ , R ² and R ³ are bonded to each other to form a ring together with the sulfur atom in the formula. ] The acid generator according to claim 3, wherein M ⁺ is an iodonium cation represented by the following general formula (ii).

[In the general formula (ii), R ⁴ and R ⁵ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted 6 to 18 carbon atoms. It represents an aryl group, or R ⁴ and R ⁵ are bonded to each other to form a ring together with the iodine atom in the formula. ] The sulfonic acid represented by the following general formula (Ia).

[In the general formula (Ia), R is a monovalent organic group having a fluorine content of 50% by weight or less, and includes —R ¹¹ , —CO—R ¹¹ , —COO—R ¹¹ , —CON ( R ¹¹ ) (R ¹² ), —S—R ¹¹ , —SO—R ^11, or —SO ₂ —R ¹¹ (where R ¹¹ and R ¹² are independently substituted or unsubstituted C 1-30. A linear or branched monovalent hydrocarbon group.) And R is a substituted linear or branched monovalent hydrocarbon group having 1 to 30 carbon atoms. The substituent of the valent hydrocarbon group does not include a cyclic monovalent hydrocarbon group, and Z ¹ and Z ² are each independently a fluorine atom or a linear or branched perfluoroalkyl having 1 to 10 carbon atoms. Indicates a group. ] A sulfonate represented by the following general formula (1C).

[In General Formula (1C), R is a monovalent organic group having a fluorine content of 50% by weight or less, and is —R ¹¹ , —CO—R ¹¹ , —COO—R ¹¹ , —CON (R ¹¹ ) (R ¹² ), —S—R ¹¹ , —SO—R ¹¹ or —SO ₂ —R ¹¹ (wherein R ¹¹ and R ¹² are each independently a substituted or unsubstituted straight chain of 1 to 30 carbon atoms) And R represents a substituted linear or branched monovalent hydrocarbon group having 1 to 30 carbon atoms. The substituent of the hydrocarbon group does not include a cyclic monovalent hydrocarbon group, and Z ¹ and Z ² are each independently a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms. M represents Na, K or Li. ] A sulfonyl halide compound represented by the following general formula (4A).

[In General Formula (4A), R is a monovalent organic group having a fluorine content of 50% by weight or less, and is —R ¹¹ , —CO—R ¹¹ , —COO—R ¹¹ , —CON (R ¹¹ ) (R ¹² ), —S—R ¹¹ , —SO—R ¹¹ or —SO ₂ —R ¹¹ (wherein R ¹¹ and R ¹² are each independently a substituted or unsubstituted straight chain of 1 to 30 carbon atoms) And R represents a substituted linear or branched monovalent hydrocarbon group having 1 to 30 carbon atoms. The substituent of the hydrocarbon group does not include a cyclic monovalent hydrocarbon group, and Z ¹ and Z ² are each independently a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms. A represents a halogen atom. ]   (A) A radiation-sensitive acid generator according to claim 1 and (B) an alkali-insoluble or alkali-insoluble resin having an acid-dissociable group, which is alkali-soluble when the acid-dissociable group is dissociated. A positive-type radiation-sensitive resin composition comprising:   The positive radiation sensitive resin composition according to claim 9, further comprising (D) an alkali solubility control agent.   (A) A negative-type sensation comprising the radiation-sensitive acid generator according to claim 1, (C) an alkali-soluble resin, and (E) a compound capable of crosslinking the alkali-soluble resin in the presence of an acid. Radiation resin composition.

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