JP2008189668A5 - - Google Patents

Description

Sulfonic acid and sulfonic acid derivatives

In particular, the present invention applies various types of radiation such as KrF excimer laser, ArF excimer laser, F ₂ excimer laser, deep ultraviolet rays such as EUV (extreme ultraviolet rays), X-rays such as synchrotron radiation, and charged particle beams such as electron beams. synthesized from a suitable radiation-sensitive acid generator in the radiation-sensitive resin composition used as a useful chemically amplified resist for microfabrication used, or sulfonic acid generated from the thermal acid generator, and the acid generator useful sulfonic acid derivatives as raw materials to intermediates, etc. for about.

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.
As a chemically amplified radiation-sensitive composition, for example, Patent Document 1 contains a polymer having a t-butyl ester group of carboxylic acid or a t-butyl carbonate group of phenol and a radiation-sensitive acid generator. Compositions have 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.
JP-B-2-27660

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 ENVIRONMENTA PROTECTION AGENCY in the United States In (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. long, moderately short and sulfonic acid generated from the dependency is small acid generator to sparse mask pattern, as well as providing a useful sulfonic acid derivative as a starting material to an intermediate or the like to synthesize the acid generator It is in.

The present invention, first,
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^a はノルボルナン骨格を有する基、トリシクロデカン骨格を有する基またはテトラシクロドデカン骨格を有する基からなる炭素数７〜３０の１価の炭化水素基を示し、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), Ra represents ^a monovalent hydrocarbon group having 7 to 30 carbon atoms composed of a group having ^a norbornane skeleton, a group having a tricyclodecane skeleton, or a group having a tetracyclododecane skeleton. , Z ¹ and Z ² each independently represent a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms. ]

The present invention secondly,
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^C は−Ｒ¹¹、−Ｓ−Ｒ¹¹、−ＳＯ−Ｒ¹¹または
−ＳＯ₂ −Ｒ¹¹（但し、Ｒ¹¹は炭素数１〜３０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。）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 General Formula (1C), R ^C represents —R ¹¹ , —S—R ¹¹ , —SO—R ^11, or —SO ₂ —R ¹¹ (where R ¹¹ is a straight chain having 1 to 30 carbon atoms, branched. Z ¹ and Z ² each independently represents a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, and a cyclic or cyclic monovalent hydrocarbon group; M represents Na, K or Li. ]

Third, the present invention
It consists of a sulfonyl halide compound represented by the following general formula (4A) (hereinafter referred to as “sulfonyl halide compound (4A)”).

〔一般式（４Ａ）において、Ｒ^A は−Ｒ¹¹、−Ｓ−Ｒ¹¹、−ＳＯ−Ｒ¹¹または
−ＳＯ₂ −Ｒ¹¹（但し、Ｒ¹¹は炭素数１〜３０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。）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。〕

[In General Formula (4A), R ^A is —R ¹¹ , —S—R ¹¹ , —SO—R ^11, or —SO ₂ —R ¹¹ (where R ¹¹ is a straight chain having 1 to 30 carbon atoms, branched Z ¹ and Z ² each independently represents a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, and a cyclic or cyclic monovalent hydrocarbon group; A represents a halogen atom. ]

Hereinafter, the present invention will be described in detail including embodiments.
The sulfonic acid (Ia), sulfonate (1C) and sulfonyl halide compound (4A) have 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、スルホン酸（Ｉ−ａ）の場合、一般式（Ｉ−ａ）におけるＲ ^a を示し、スルホン酸塩（１Ｃ）の場合、一般式（１Ｃ）におけるＲ ^C を示し、スルホニルハライド化合物（４Ａ）の場合、一般式（４Ａ）におけるＲ ^A を示し、Ｚ¹ およびＺ² は相互に独立に一般式（Ｉ−ａ）、一般式（１Ｃ）または一般式（４Ａ）におけるそれぞれＺ ¹ およびＺ ² と同義である。〕

In [Formula (I), R in the case of sulfonic acid (I-a), shows a R ^a in formula (I-a), when the sulfonate (1C), R in the general formula (1C) ^In the case of the sulfonyl halide compound (4A), R ^A in the general formula (4A) is shown, and Z ¹ and Z ² are each independently of the general formula (Ia), the general formula (1C) or the general formula It is synonymous with Z ¹ and Z ² in (4A), respectively . ]

Since the sulfonic acid (Ia) has a strong fluorine-containing electron withdrawing group at the α-position of the sulfonyl group in its structure, the acidity is high and the boiling point is sufficiently high, so that it is difficult to volatilize in the photolithography process. In addition, the diffusion length in the resist film has a characteristic that it is reasonably short. Furthermore, since the fluorine content is lower than that of perfluoroalkylsulfonic acid, the combustibility is relatively high and the human body accumulation property is also low.

In General Formula (1C) and General Formula (4A) , examples of the linear, branched or cyclic monovalent hydrocarbon group having 1 to 30 carbon atoms represented by R ¹¹ include, for example, a methyl group, an 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, cyclopropyl group, cyclopentyl group, cyclohexyl group, group having norbornene skeleton, group having norbornane skeleton, group having tricyclodecane skeleton, group having tetracyclododecane skeleton, etc. be able to.

R ^C in the general formula ( 1C ) and R ^A in the general formula (4A) are methyl group, ethyl group, n-butyl group, cyclohexyl group, group having norbornene skeleton, group having norbornane skeleton, tricyclodecane skeleton A hydrocarbon group such as a group having a tetracyclododecane skeleton, or a group represented by —S—R ¹¹ , —SO—R ¹¹ or —SO ₂ —R ¹¹ , wherein R ¹¹ is a methyl group, Those having an ethyl group, an n-butyl group, a cyclohexyl group, and the like 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).

As another preferable structure (I), in the case of the structure (I) corresponding to the sulfonic acid (Ia), for example, a structure represented by the following general formula (IB) can be exemplified. In the case of the structure (I) corresponding to the sulfonate (1C) and the sulfonyl halide compound (4A), for example, the structure represented by the following general formula (IA) or general formula (IB) Can be mentioned.

〔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）において、Ｚ¹ およびＺ² は相互に独立に一般式（１Ｃ）または一般式（４Ａ）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の整数であり、一般式（Ｉ−Ｂ）において、Ｚ ¹ およびＺ ² は相互に独立に一般式（Ｉ−ａ）、一般式（１Ｃ）または一般式（４Ａ）におけるそれぞれＺ ¹ およびＺ ² と同義であり、Ｙ ¹ 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 the general formula (I-A), Z ¹ and Z ² have the same meanings as Z ¹ and Z ^2, respectively, in the general formula (1C) or the general formula (4A) independently of one another, Y ¹ is a single bond or a R ′ represents a monovalent substituent, k is an integer of 0 or more, n is an integer of 0 to 5 , and in formula ( IB ), Z ¹ and Z ² Are independently the same as Z ¹ and Z ² in the general formula (Ia), general formula (1C) or general formula (4A) , Y ¹ represents a single bond or a divalent group, R 'Represents a monovalent substituent, k is an integer of 0 or more, and n is an integer of 0 to 5 . ]

Examples of the divalent group represented by Y ¹ include -S-, sulfinyl group, sulfonyl group, methylene group, 1,1-ethylene group, 1,2-ethylene group, propylene group, 1-methylpropylene group, 1- An ethylpropylene group, a trimethylene group, etc. can be mentioned.

  Of these divalent groups, a methylene group and the like are preferable.

Examples of the monovalent substituent for R ′ include a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched vinylidene group having 1 to 10 carbon atoms, and 1 carbon atom. -12 monovalent cyclic hydrocarbon groups and the like.

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 hydrocarbon group having 1 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a norbornyl group.

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 or the like, k is preferably 0, and n is preferably 0 or 1.

Preferred examples of the structure represented by the general formula (IA ) and the structure represented by the general formula (IB) include, for example, the following formula (A-1) , formula (A-4), formula ( A-5), Formula (A-7), Formula (A-10), Formula (A-11) , Formula (B-1) , Formula (B-4), Formula (B-5), Formula (B -7), structures represented by formula (B-10) or formula (B-11) , and the like.

Among the acid generators that generate sulfonic acid (Ia) by exposure or heating , examples of the ionic compound include sulfonic acid onium salt compounds represented by the following general formula (1) (hereinafter referred to as “onium sulfonate”). Salt compound (1) "). 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 ^a 、Ｚ¹ およびＺ² は一般式（Ｉ−ａ）におけるそれぞれ
Ｒ ^a 、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 the general formula (1), R ^a , Z ¹ and Z ² are the same in the general formula (I −a ), respectively.
It is synonymous with R ^a , Z ¹ and Z ² , and 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 a general method described in Non-Patent Document 2, for example.
JV Crivello, Advances in Polymer Science 62, 49, 1984

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

〔一般式（１−Ｂ）において、Ｚ¹ およびＺ² は一般式（Ｉ−ａ）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−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。〕

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

Among the acid generators that generate sulfonic acid (Ia) upon exposure or heating , examples of nonionic compounds include N-sulfonyloxyimide compounds represented by the following general formula (2) (hereinafter, "N-sulfonyloxyimide compound (2)").

〔一般式（２）において、Ｒ ^a 、Ｚ¹ およびＺ² は一般式（Ｉ−ａ）におけるそれぞれ
Ｒ ^a 、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 the general formula (2), R ^a , Z ¹ and Z ² are each in the general formula (I −a )
R ^a , Z ¹ and Z ² are synonymous, and R ⁶ and R ⁷ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent organic group, or R ⁶ and R ⁷ are bonded to each other And Y ² represents a single bond, a double bond or a divalent organic group. ]

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

〔一般式（２−Ｂ）において、Ｚ¹ およびＺ² は一般式（Ｉ−ａ）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−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。〕

[In the 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 -a), Y 1,} R ', k and n have the general formula (I- each Y ^1, R 'in B), has the same meaning as k and n, R ^6, R ⁷ and Y ² have the same meanings as R ^6, R ⁷ and Y ^2, respectively, in the general formula (2). ]

Formula (2) and general formula (2-B), as the preferred imido groups bonded to sulfonyloxy group in each formula (SO ₂ -O-), for example, the following formulas (2-1) to (2 -9) and the like.

  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

〔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 2.
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 exchange 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- B ) is a cyclopentadiene compound corresponding to the corresponding ethylene derivative [2a] as shown in the following reaction formula [2], for example. A norbornene derivative [2b] is synthesized by a Diels-Alder reaction with the compound, 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 derivative [3b] was synthesized by Diels-Alder reaction with the compound , and the norbornene derivative [2b] and norbornene derivative [3b] obtained were synthesized in the reaction solvent in the presence of a hydrogenation catalyst. as the hydrogenated product by contacting with hydrogen gas, with respect to hydrogenated products thereof, reacted in the procedure shown in the reaction formula [1] It can be produced by the. The sulfonic acid onium salt compound (1) having a total of 3 or more norbornane rings can be produced in the same manner as described above after synthesizing a polycyclic norbornene derivative by repeating the procedure shown in the reaction formula [3]. .

〔反応式 [２] において、Ｚ¹ およびＺ² は一般式（Ｉ−ａ）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−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 are each in the general formula (I -a) have the same meanings as Z ¹ and Z ^2, Y ¹ has the same meaning as Y ¹ in the formula (I-B) , X has the same meaning as X in the reaction formula [1]. ]

〔反応式 [３] において、Ｚ¹ およびＺ² は一般式（Ｉ−ａ）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−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 are each in the general formula (I -a) have the same meanings as Z ¹ and Z ^2, Y ¹ has the same meaning as Y ¹ in the formula (I-B) , X has the same meaning as 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.
In the Diels-Alder reaction, the molar ratio of the ethylene derivative [2a] to the cyclopentadiene compound and the molar ratio of the cyclopentadiene compound to the norbornene derivative [2b] are usually 0.01 to 100, preferably 0. .1-10.
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.
Comprehensive Organic Synthesis, BM Trost & I. Fleming, Pergamon Press, New York, 1991, Vol. V, pp 315

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 2 or the method described in Synthesis Example * described later.
In 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 amount of the reaction solvent used relative to 100 parts by weight of the sulfonyl chloride [4a] is usually 5 to 100 parts by weight, preferably 10 to 100 parts by weight, and more preferably 20 to 50 parts by weight.
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.

  The N-sulfonyloxyimide compound (2) represented by the general formula (2-B) is, for example, a method for producing the sulfonic acid onium salt compound (1) represented by the general formula (1-B). The hydrogenated product of norbornene derivatives such as norbornene derivative [2b] and norbornene derivative [3b] described above was used to obtain sulfinate [1b] by the procedure shown in the above reaction formula [1], and then reaction formula [4] It can manufacture in the same manner as the procedure shown in FIG.

Furthermore, examples of acid generators other than the sulfonic acid onium salt compound (1) and the N-sulfonyloxyimide compound (2 ) that generate sulfonic acid (Ia) upon exposure or heating include sulfone compounds and sulfonic acids. Examples include ester compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, and hydrazine sulfonate compounds.
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 ^a 、Ｚ¹ およびＺ² は一般式（Ｉ−ａ）におけるそれぞれＲ ^a 、Ｚ¹ およびＺ² と同義であり、一般式（３−２）における２個のＲ ^a 、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 (3-1) and the general formula ^{(3-2), R a, Z} 1 and Z ² are, respectively, in the general formula (I -a) the same meanings as R ^a, Z ¹ and Z ^2, General Two R ^{a s} , Z ¹ and Z ² in formula (3-2) 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 ^a 、Ｚ¹ およびＺ² は一般式（Ｉ−ａ）におけるそれぞれ
Ｒ ^a 、Ｚ¹ およびＺ² と同義であり、複数存在するＲ ^a 、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 General formula (4), R ^<a> , Z < ¹ > and Z < ² > are respectively in general formula (I <-a> ).
R ^a , Z ¹ and Z ² are synonymous, and a plurality of R ^a , Z ¹ and Z ² may be the same as or different from each other, and A is a j-valent derived from pyrogallol, α-methylolbenzoin, etc. An organic residue is shown, j is an integer of 1-3. ]

  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 ^a 、Ｚ¹ およびＺ² は一般式（Ｉ−ａ）におけるそれぞれ
Ｒ ^a 、Ｚ¹ およびＺ² と同義であり、２個のＲ ^a 、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 (5), R ^a , Z ¹ and Z ² are the same in the general formula (I −a ), respectively.
It is synonymous with R ^<a> , Z < ¹ > and Z < ² >, and two R ^<a> , Z < ¹ > and Z < ² > may mutually be same or different, respectively. ]

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

[In General Formula (6), R ^a , Z ¹ and Z ² are the same in General Formula (I −a ), respectively.
R ^a , Z ¹ and Z ² are the same, and two R ^a , Z ¹ and Z ² may be the same or different from each other, and V and W are independently of each other 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 mutually To form a monocyclic or polycyclic ring having at least one unsaturated bond, or a group represented by the following formula (7) wherein V and W are 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 ^a 、Ｚ¹ およびＺ² は一般式（Ｉ−ａ）におけるそれぞれＲ ^a 、Ｚ¹ およびＺ² と同義であり、一般式（８−２）における２個のＲ ^a 、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 a, Z} 1 and Z ² are, respectively, in the general formula (I -a) the same meanings as R ^a, Z ¹ and Z ^2, General Two R ^{a s} , Z ¹ and Z ² in formula (8-2) 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 ^a 、Ｚ¹ およびＺ² は一般式（Ｉ−ａ）におけるそれぞれＲ ^a 、Ｚ¹ およびＺ² と同義であり、一般式（９−２）における２個のＲ ^a 、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 a, Z} 1 and Z ² are, respectively, in the general formula (I -a) the same meanings as R ^a, Z ¹ and Z ^2, General Two R ^{a s} , Z ¹ and Z ² in formula (9-2) may be the same or different from each other. ]

A positive-type radiation-sensitive resin composition containing an acid generator that generates sulfonic acid (Ia) upon exposure (hereinafter referred to as “acid generator (I)”) ,
(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.

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. ]

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.

<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 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 containing acid generator (I)
(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.
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, sulfonate ester compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, and hydrazine sulfonate compounds.

<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.
The acid diffusion controller can be used alone or in admixture of two or more.

-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.

-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.

-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.
-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.

< Solvent >
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 a total solid content of It is prepared as a composition solution by uniformly dissolving in a solvent so as to be 0.1 to 50% by weight, preferably 1 to 40% by weight, and then filtering through a filter having a pore size of about 0.2 μm, for example.
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-type radiation-sensitive resin composition (A), the positive-type radiation-sensitive resin composition (B) and the negative-type radiation-sensitive resin composition (C), as described above. The prepared composition solution 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, roll coating, etc. A heat treatment (hereinafter referred to as “PB”) is performed at a temperature of about 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 tetraalkyl. 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 sulfonic acid (Ia) of the present invention has a relatively high combustibility, no problem in human body accumulation, sufficiently high acidity and boiling point, and a moderately short diffusion length in the resist film. In particular, a radiation sensitive resin composition useful for a chemically amplified resist that is sensitive to far ultraviolet rays and electron beams typified by KrF excimer laser, ArF excimer laser, F ² excimer laser or EUV. An acid generated from the acid generator (I) by exposure or heating when forming a resist pattern, and a structure of an antireflection film for lower layer or upper layer provided when forming a resist pattern It is useful as a component, and the sulfonate (1C) of the present invention and the sulfonyl halide compound (4A) of the present invention react with the acid generator (I). Are useful as intermediates, further sulfonate (I-a), sulfonate (1C) and sulfonyl halide compound (4A) are also useful as a raw material for the synthesis of various sulfonic acid derivatives.
The radiation-sensitive resin composition containing the acid generator (I) is effective for actinic radiation, particularly far ultraviolet rays and electron beams represented by KrF excimer laser, ArF excimer laser, F ² excimer laser or EUV. Sensitive, high sensitivity, moderately short acid diffusion length in resist film, excellent resolution, and less dependent on mask pattern sparse density. It can be used very suitably in the field of microfabrication represented by the manufacture of integrated circuit elements.