JP4577354B2 - Positive radiation-sensitive resin composition and negative radiation-sensitive resin composition - Google Patents

Description

The present invention relates to a radiation-sensitive resin composition, and more particularly, X-rays such as KrF excimer laser, ArF excimer laser, F ₂ excimer laser or EUV (extreme ultraviolet), synchrotron radiation, etc. The present invention relates to a positive-type and negative-type radiation-sensitive resin composition used as a chemically amplified resist useful for fine processing using various types of radiation such as charged particle beams such as electron beams.

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), F ₂ excimer laser (wavelength 157 nm), EUV (wavelength 13 nm, etc.), electron beam, and the like are attracting 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.
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 problems. The US Environmental Protection Agency (ENVIRONMENTAL In a report by PROTECTION AGENCY (see Non-Patent Document 1), a proposal for restricting use has been made.
In addition, when the device design dimension is sub-half micron or smaller and the line width control needs to be performed more precisely, using a chemically amplified resist with inferior film surface smoothness results in etching or other treatment on the substrate. When the resist pattern is transferred, an uneven shape (hereinafter referred to as “nano edge roughness”) on the film surface is transferred to the substrate. As a result, the dimensional accuracy of the pattern is lowered, and there is a possibility that the electrical characteristics of the device are eventually impaired (for example, see Non-Patent Document 2, Non-Patent Document 3, and Non-Patent Document 4). Therefore, when the design dimension is sub-half micron or less, it is important that the chemically amplified resist has not only excellent resolution performance but also excellent film surface smoothness after resist pattern formation. It has become.

  Therefore, in the field of microfabrication, there is no drawback as in the case of the perfluoroalkylsulfonyl structure, and it is possible to realize a better chemically amplified resist with excellent resolution performance and small nanoedge roughness. There is an urgent need to develop an alternative component that is also excellent in function as a radiation-sensitive acid generator.

JP-B-2-27660 Perfluorooctyl Sulfonates; Proposed Significant New Use Rule J. Photopolym. Sci. Tech., P.571 (1998) Proc.SPIE, Vol.3333, p.313 Proc.SPIE, Vol.3333, p.634 J. Vac. Sci. Technol. B16 (1), p.69 (1998)

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, the combustibility is relatively high, there is no problem with human accumulation, the acidity and boiling point of the acid generated are sufficiently high, and the diffusion length in the resist film is moderately short. Positive-type and negative-type radiation-sensitive resin compositions containing a radiation-sensitive acid generator capable of obtaining a resist pattern having a small dependence on the sparse density of the mask pattern and excellent surface and side wall smoothness Is to provide.

The present invention provides, firstly, (A) a radiation-sensitive acid generator and (B) an alkali-insoluble or hardly-alkali-soluble resin having an acid-dissociable group, and the alkali-dissociating group when the acid-dissociable group is dissociated. A compound (hereinafter referred to as “acid generator (A)” ) containing a resin that is easily soluble and having one or more structures represented by the following general formula (1) or the following general formula (2): (B1) wherein the component (B) comprises only a repeating unit represented by the following general formula (42) and a repeating unit in which the phenolic hydroxyl group in the repeating unit is protected with an acid-dissociable group. And one or more of the repeating units represented by the following general formula (43) or the following general formula (44) and the resin (B2) group consisting only of the repeating units represented by the following general formula (45). Positive-type release characterized by It consists of a radiation resin composition .
Here, “having one or more structures represented by the general formula (1) or the following general formula (2)” means that when having only one or more structures represented by the general formula (1), the general formula When having only one or more structures represented by (2), and having one or more structures represented by general formula (1) and one or more structures represented by general formula (2) It is a concept that includes
Hereinafter, the structure represented by the general formula (1) is referred to as “structure (1)”, and the structure represented by the general formula (2) is referred to as “structure (2)”.

〔一般式（４２）において、Ｒ ¹⁷ は水素原子または１価の有機基を示し、複数存在する
Ｒ ¹⁷ は相互に同一でも異なってもよく、ａおよびｂはそれぞれ１〜３の整数である。〕

〔一般式（４３）、一般式（４４）および一般式（４５）において、Ｒ ¹⁸ 、Ｒ ²⁰ および
Ｒ ²¹ は相互に独立に水素原子またはメチル基を示し、一般式（４３）において、Ｒ ¹⁹ は相互に独立に水素原子、水酸基、シアノ基または−ＣＯＯＲ ²³ 基（但し、Ｒ ²³ は水素原子、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炭素数３〜２０の脂環式のアルキル基を示す。）を示す。
一般式（４５）において、Ｒ ²² は相互に独立に炭素数４〜２０の１価の脂環式炭化水素基もしくはその誘導体または１〜４の直鎖状もしくは分岐状のアルキル基を示し、かつＲ ²² の少なくとも１つが該脂環式炭化水素基もしくはその誘導体であるか、あるいは何れか２つのＲ ²² 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炭素数４〜２０の２価の脂環式炭化水素基もしくはその誘導体を形成し、残りのＲ ²² 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炭素数４〜２０の１価の脂環式炭化水素基もしくはその誘導体を示す。〕 [In the general formula (1), R ¹ represents a hydrogen atom or a monovalent substituent, p is an integer of 1 or more, and when R ² is present, R ¹ O— and R ² are included therein. In the presence of a plurality of R ¹ O— groups, at least two R ¹ O— may be bonded to each other via atoms contained in at least two R ^1. To form a ring.
In General Formula (1) and General Formula (2), Z ¹ and Z ² each independently represent a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, and Y ¹ is a single atom. A bond or a divalent group; R ² represents a monovalent or divalent substituent; q is an integer of 0 or more; and n is an integer of 0 to 5. ]

[In the general formula (42), R ¹⁷ represents a hydrogen atom or a monovalent organic group, and a plurality of R ¹⁷ exist.
R ¹⁷ may be the same as or different from each other, and a and b are each an integer of 1 to 3. ]

[In General Formula (43), General Formula (44), and General Formula (45), R ¹⁸ , R ²⁰ and
R ²¹ represents a hydrogen atom or a methyl group independently of each other. In the general formula (43), R ¹⁹ independently represents a hydrogen atom, a hydroxyl group, a cyano group or a —COOR ²³ group (provided that R ²³ represents a hydrogen atom, Represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic alkyl group having 3 to 20 carbon atoms.).
In the general formula (45), R ²² each independently represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof or a linear or branched alkyl group having 1 to 4 carbon atoms, and At least one of R ²² is the alicyclic hydrocarbon group or a derivative thereof, or any two R ²² are bonded to each other, and each having 2 to 4 carbon atoms together with the carbon atoms to which each is bonded. A valent alicyclic hydrocarbon group or a derivative thereof, and the remaining R ²² is a linear or branched alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon having 4 to 20 carbon atoms Represents a group or a derivative thereof. ]

Secondly, the present invention comprises (A) a radiation-sensitive acid generator, (C) an alkali-soluble resin and (D) a compound capable of crosslinking the alkali-soluble resin in the presence of an acid, and (A) a component Is composed of a compound having one or more structures represented by the following general formula (1) or the following general formula (2), and the component (C) is a repeating unit represented by the following general formulas (49) to (51). Polymeric unsaturated bond of resin (C1) consisting of only one or more and one or more repeating units represented by the following general formulas (49) to (51) and a vinyl aromatic compound or (meth) acrylic ester It is selected from the group of resins (C2) consisting of only one or more of the repeating units cleaved by a negative radiation-sensitive resin composition .
Here, “having one or more structures represented by the general formula (1) or the following general formula (2)” means that when only one structure (1) is present, only one structure (2) is present. It is a concept including the case where it has the above and the case where it has one or more structures (1) and one or more structures (2).

[In the general formula ( 1 ), R ¹ represents a hydrogen atom or a monovalent substituent, p is an integer of 1 or more, and when R ² is present, R ¹ O— and R ² are included therein. In the presence of a plurality of R ¹ O— groups, at least two R ¹ O— may be bonded to each other via atoms contained in at least two R ^1. To form a ring .
In the general formula ( 1 ) and the general formula ( 2 ), Z ¹ and Z ² each independently represent a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, and Y ¹ is a single atom. A bond or a divalent group; R ² represents a monovalent or divalent substituent; q is an integer of 0 or more; and n is an integer of 0 to 5 . ]

[In General Formula (49) and General Formula (50), R ^{twenty five} And R ²⁷ Each independently represents a hydrogen atom or a methyl group, R ²⁶ Is a hydroxyl group, a carboxyl group, -R ²⁸ COOH,
-OR ²⁸ COOH, -OCOR ²⁸ COOH or -COOR ²⁸ COOH {however, each R ²⁸ Are independently of each other-(CH ₂ ) _c -, C is an integer of 1-4. }. ]

〔一般式（１１）において、Ｒ ¹ およびｐは一般式（１）におけるそれぞれＲ ¹ およびｐと同義である。
一般式（１１）および一般式（１２）において、Ｚ ¹ 、Ｚ ² 、Ｙ ¹ 、Ｒ ² 、ｑおよびｎは一般式（１）および一般式（２）におけるそれぞれＺ ¹ 、Ｚ ² 、Ｙ ¹ 、Ｒ ² 、ｑおよびｎと同義である。〕
酸発生剤（Ａ）は、その構造（１）および構造（２）中のスルホニル基のα−位に強い含フッ素系電子吸引基をもつため、発生するスルホン酸等の酸の酸性度が高く、また沸点が十分高いためフォトリソグラフィ工程中で揮発し難く、かつレジスト被膜中での酸の拡散長も適度に短く、表面および側壁の平滑性に優れたレジストパターンを得ることができる特性を有する。さらに、発生するスルホン酸中のフッ素含有量がパーフルオロアルキルスルホン酸に比べて少ないため、燃焼性が比較的高く、また人体蓄積性も低いものである。 Hereinafter, the present invention will be described in detail including embodiments of the invention.
Acid generator (A)
Acid generator (A), by exposure, Ri component der generating sulfonic acid (12) represented by the sulfonic acid represented by the following general formula (11) (11) or the following general formula (12), The sulfonic acid (11) and the sulfonic acid (12) are components having an action as an acid catalyst in the process of forming a resist pattern using a positive type radiation sensitive resin composition and a negative type radiation sensitive resin composition described later. Oh Ru.

[In General formula (11), R < ¹ > and p are synonymous with R < ¹ > and p in General formula (1), respectively .
In the general formula (11) and the general formula ^{(12), Z 1, Z} 2, Y 1, R 2, q and n have the general formula (1) and, respectively, in the general formula ^{(2) Z 1, Z 2} , Y 1 , R ² , q and n. ]
Since the acid generator (A) has a strong fluorine-containing electron withdrawing group at the α-position of the sulfonyl group in the structures (1) and (2), the acidity of the acid such as sulfonic acid generated is high. In addition, since it has a sufficiently high boiling point, it is difficult to volatilize in the photolithography process, and the acid diffusion length in the resist film is moderately short, and it has the characteristics that a resist pattern with excellent surface and sidewall smoothness can be obtained. . Furthermore, since the fluorine content in the generated sulfonic 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 (1), examples of the monovalent substituent for R ¹ include -R ⁷ ,
—CO—R ⁷ , —COO—R ⁷ , —CON (R ⁷ ) (R ⁸ ), —SO ₂ —R ⁷ (wherein R ⁷ and R ⁸ are independently substituted or unsubstituted carbon number 1 -30 linear, branched or cyclic monovalent hydrocarbon group, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or substituted or unsubstituted monovalent heterocyclic organic group having 4 to 30 carbon atoms Group)) and the like.

Examples of the unsubstituted linear, branched or cyclic monovalent hydrocarbon group having 1 to 30 carbon atoms of R ⁷ and R ⁸ include, for example, methyl group, ethyl group, n-propyl group, i-propyl Group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl 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, 4-t-butylcyclohexyl group, cyclohexenyl group, A group having a norbornene skeleton, a group having a norbornane skeleton, a group having an isobornyl skeleton, a group having a tricyclodecane skeleton, a group having a tetracyclododecane skeleton And a group having an adamantane 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 substituted, straight-chain, branched or cyclic monovalent hydrocarbon group having 1 to 30 carbon atoms for R ⁷ and R ⁸ include:
Methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, methoxyethoxymethyl group, benzyloxymethyl group, benzylthiomethyl group, phenoxymethyl group, acetylmethyl group, trifluoroacetylmethyl group, trichloroacetylmethyl group Phenacyl group, 4-bromophenacyl group, 4-methoxyphenyl group, 4-methylthiophenyl group, α-methylphenyl group, fluoromethyl group, trifluoromethyl group, chloromethyl group, trichloromethyl group, cyclopropylmethyl group, diphenyl Methyl group, triphenylmethyl group, adamantylmethyl group, benzyl group, 4-bromobenzyl group, 4-nitrobenzyl group, 4-methoxybenzyl group, 4-methylthiobenzyl group, 4-ethoxybenzyl group, 4-ethylthioben Group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl group, n-butoxycarbonylmethyl group, t-butoxycarbonylmethyl group, pentafluorobenzoylmethyl group, Substituted methyl groups such as aminomethyl group, cyclohexylaminomethyl group, diphenylphosphinomethyl group, trimethylsilylmethyl group;

1-phenethyl group, 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl group, 1-phenoxy Ethyl 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-butoxycarbonyl Ethyl group, 1-t-butoxycarbonylethyl group, 1-cyclohexyloxycarbonyl group 1-substituted ethyl group such as Le group;
2-substituted ethyl groups such as 2-phenethyl group, 2-methoxyethyl group, 2-methylthioethyl group, 2-aminoethyl group;

1-substituted-n-propyl groups such as 1-methoxy-n-propyl group and 1-ethoxy-n-propyl group;
2-substituted-n-propyl groups such as 2-fluoro-n-propyl group;
3-substituted-n-propyl groups such as 3-phenyl-n-propyl group;
A substituted cycloalkyl group such as a 4-methoxycyclohexyl group;

Trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, i-propyldimethylsilyl group, methyldi-i-propylsilyl group, tri-i-propylsilyl group, t-butyldimethylsilyl group, methyldi-t -Silyl groups such as butylsilyl group, tri-t-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilyl group, triphenylsilyl group;
Trimethylgermyl group, ethyldimethylgermyl group, methyldiethylgermyl group, triethylgermyl group, i-propyldimethylgermyl group, methyldi-i-propylgermyl group, tri-i-propylgermyl group, t- Examples thereof include germyl groups such as a butyldimethylgermyl group, a methyldi-t-butylgermyl group, a tri-t-butylgermyl group, a phenyldimethylgermyl group, a methyldiphenylgermyl group, and a triphenylgermyl group.

Examples of the unsubstituted aryl group having 6 to 30 carbon atoms of R ⁷ and R ⁸ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, and a 1-phenanthryl group. Can do.
Examples of the unsubstituted monovalent heterocyclic organic group having 4 to 30 carbon atoms represented by R ⁷ and R ⁸ include a furyl group, a thienyl group, a pyranyl group, a pyrrolyl group, a thiantenyl group, a pyrazolyl group, an isothiazolyl group, Examples thereof include an isoxazolyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, a tetrahydrothiofuranyl group, and a 3-tetrahydrothiophene-1,1-dioxide 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 of R ⁷ and R ⁸ include, for example, o-tolyl group, m-tolyl group, p-tolyl group, p-methoxyphenyl group, mesityl group, o-cumenyl group. 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 of R ⁷ and R ⁸ include 2-bromofuryl group, 3-methoxythienyl group, 3-bromotetrahydropyranyl group, 4- Examples thereof include a methoxytetrahydropyranyl group and a 4-methoxytetrahydrothiopyranyl group.

In the general formula (1), R ¹ can be bonded to any carbon atom constituting the norbornane ring in the formula, and a plurality of R ¹ may be the same or different from each other.

In general formula (1), R ¹ is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a methoxymethyl group, 1-ethoxyethyl group, tetrahydropyranyl group, tetrahydrofuranyl group, methylcarbonyl group, ethylcarbonyl group, 1-propylcarbonyl group, 2-propylcarbonyl group, 1-butylcarbonyl group, 2-butylcarbonyl group, isobutylcarbonyl group , T-butylcarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, 1-butoxycarbonyl group, 2-butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group Methanesulfonyl group, ethanesulfonyl group, n A propanesulfonyl group, an i-propanesulfonyl group, an n-butanesulfonyl group, an n-pentanesulfonyl group, an n-hexanesulfonyl group and the like are preferable, and a hydrogen atom, a t-butyl group, a tetrahydropyranyl group, and a methylcarbonyl are more preferable. Group, t-butylcarbonyl group, t-butoxycarbonyl group, methanesulfonyl group, i-propanesulfonyl group, n-hexanesulfonyl group and the like, and p is preferably 1 or 2.

In the general formula (1) and the general formula (2), examples of the monovalent or divalent substituent of R ² include an oxo group (═O), a hydroxyl group, a carboxyl group, a formyl group, and a carbon number of 1 to 10. A linear or branched alkyl group, a linear or branched vinylidene group having 1 to 10 carbon atoms, a monovalent cyclic organic group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon A linear or branched alkoxyl group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a linear or branched alkylcarbonyl group having 2 to 10 carbon atoms, and an arylcarbonyl group having 7 to 20 carbon atoms And a linear or branched alkoxycarbonyl group having 1 to 10 carbon atoms 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 one or more arbitrary substituents, for example, the above-described substituents.

In General Formula (1) and General Formula (2), R ² can be bonded to any carbon atom constituting the norbornane ring in each formula, and a plurality of R ² may be the same or different from each other. Good.
In general formula (1) and general formula (2), q is preferably 0.

In General Formula (1) and General Formula (2), examples of the perfluoroalkyl group having 1 to 10 carbon atoms of Z ¹ and Z ² include a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoro-n-propyl group. And nonafluoro-n-butyl group.
In General Formula (1) and General Formula (2), Z ¹ and Z ² are preferably a fluorine atom, a trifluoromethyl group, or the like.

In the general formula (1) and the general formula (2), examples of the divalent group represented by Y ¹ include —O—, 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 and the like.
Of these divalent groups, a carbonyl group, a methylene group, a difluoromethylene group, a tetrafluoro-1,2-ethylene group and the like are preferable.

In General Formula (1) and General Formula (2), Y ¹ is preferably a single bond, a methylene group, a carbonyl group, a carbonyl group, a methylene group, a difluoromethylene group, a tetrafluoro-1,2-ethylene group, or the like.
In general formulas (1) and (2), n is preferably 0 or 1.

  In the present invention, examples of the preferable structure (1) include structures represented by the following formulas (1-1) to (1-126). Examples of the preferable structure (2) include the following: Examples include structures represented by formulas (2-1) to (2-14).

  Among these structures, Formula (1-1), Formula (1-2), Formula (1-4), Formula (1-8), Formula (1-9), Formula (1-11), Formula ( 1-15), Formula (1-16), Formula (1-18), Formula (1-29), Formula (1-30), Formula (1-32), Formula (1-36), Formula (1) -37), Formula (1-39), Formula (1-43), Formula (1-44), Formula (1-46), Formula (1-50), Formula (1-57), Formula (1- 58), Formula (1-60), Formula (1-64), Formula (1-65), Formula (1-67), Formula (1-71), Formula (1-72), Formula (1-74) ), Formula (1-78), Formula (1-79), Formula (1-81), Formula (1-92), Formula (1-93), Formula (1-95), Formula (1-99) , Formula (1-100), Formula (1-102), Formula (1-106), Formula (1-107), Formula (1-109), Formula (1-113), Formula (1-114) or Structure (1) represented by Formula (1-116): Formula (2-1), Formula (2-2), Formula (2-4), Formula (2-8), Formula (2-9) or The structure (2) represented by the formula (2-11) is preferable.

  Of the compounds forming the acid generator (A), preferred ionic compounds include, for example, sulfonic acid onium salt compounds represented by the following general formula (3) or general formula (4).

[In General formula (3), R < ¹ > and p are synonymous with R < ¹ > and p in General formula (1), respectively.
In the general formula (3) and the general formula ^{(4), Z 1, Z} 2, Y 1, R 2, q and n have the general formula (1) and, respectively, in the general formula ^{(2) Z 1, Z 2} , Y 1 , R ² , q and n, and M ⁺ represents a monovalent onium cation. ]

Hereinafter, the sulfonic acid onium salt compound represented by the general formula (3) is referred to as “sulfonic acid onium salt compound (3)”, and the sulfonic acid onium salt compound represented by the general formula (4) is referred to as “onium sulfonate”. Salt compound (4) ".
The sulfonic acid onium salt compound (3) is a compound in which a sulfonyl group in the structure (1) is bonded to an oxygen anion to form a sulfonic acid anion, and the sulfonic acid onium salt compound (4) is a structure (2). It is a compound in which a sulfonyl group is bonded to an oxygen anion to form a sulfonate anion.

In the general formulas (3) and (4), examples of the monovalent onium cation of M ⁺ include onium cations such as O, S, Se, N, P, As, Sb, Cl, Br, and I. The onium cation of S and the onium cation of I are particularly preferable.

In general formula (3) and general formula (4), preferable examples of M ⁺ include those represented by the following general formula (5) or general formula (6).

〔一般式（５）において、各Ｒ³ は相互に独立に置換もしくは非置換の炭素数１〜１０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６〜１８のアリール基を示すか、あるいは何れか２つ以上のＲ³ が相互に結合して式中の硫黄原子と共に環を形成している。〕

[In General Formula (5), each R ³ is independently a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms. Or any two or more of R ³ are bonded to each other to form a ring together with the sulfur atom in the formula. ]

〔一般式（６）において、各Ｒ⁴ は相互に独立に置換もしくは非置換の炭素数１〜１０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６〜１８のアリール基を示すか、あるいは２つのＲ⁴ 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 (6), each R ⁴ is independently a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms. Or two R ^{4 's} 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 6, for example.

Advances in Polymer Science, Vol.62, p.1-48 (1984)

  Preferred monovalent onium cations include, for example, sulfonium cations represented by the following formulas (5-1) to (5-64) and iodonium cations represented by the following formulas (6-1) to (6-39). Etc.

  Among these monovalent onium cations, the above formula (5-1), formula (5-2), formula (5-6), formula (5-8), formula (5-13), formula (5- 19), a sulfonium cation represented by the formula (5-25), the formula (5-27), the formula (5-29), the formula (5-51) or the formula (5-54); ) Or an iodonium cation represented by the formula (6-11) is preferable.

  Of the compounds forming the acid generator (A), preferred nonionic compounds include, for example, N-sulfonyloxyimide compounds represented by the following general formula (7) or general formula (8). it can.

[In General formula (7), R < ¹ > and p are synonymous with R < ¹ > and p in General formula (1), respectively.
In the general formula (7) and the general formula ^{(8), Z 1, Z} 2, Y 1, R 2, q and n have the general formula (1) and, respectively, in the general formula ^{(2) Z 1, Z 2} , Y 1 , R ² , q and n, and R ⁵ and R ⁶ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent organic group, or R ⁵ and R ⁶ are bonded to each other And Y ² represents a single bond, a double bond or a divalent group. ]
Hereinafter, the N-sulfonyloxyimide compound represented by the general formula (7) is referred to as “N-sulfonyloxyimide compound (7)”, and the N-sulfonyloxyimide compound represented by the general formula (8) is represented by “ It is referred to as “N-sulfonyloxyimide compound (8)”.

In the general formula (7) and the general formula (8), preferred imide groups attached to the sulfonyl group in each formula (SO ₂ -O-), for example, the following formulas (i-1) ~ (i -9 ) And the like.

  Of these imide groups, groups represented by formula (i-1), formula (i-4), formula (i-8) or formula (i-9) are preferred.

  The acid generator (A) of the present invention has an action of generating sulfonic acid (11) or sulfonic acid (12) by exposure or heating, and particularly generates radiation-sensitive acid in a radiation-sensitive resin composition described later. It can be used very suitably as an agent.

-Synthesis method of sulfonic acid onium salt compound (3)-
The sulfonic acid onium salt compound (3) can be synthesized, for example, according to the general methods described in Non-Patent Document 6 and Non-Patent Document 7 below.

Inorganic Chemistry, Vol.32, p.5007-5011 (1993)

That is, as shown in the following reaction formula [1], the corresponding precursor compound (3a) is converted to a sulfinate (3b) by reacting with sodium dithionite in the presence of an inorganic base, This is oxidized to an sulfonate (3c) by oxidizing with an oxidizing agent such as hydrogen peroxide, and then subjected to an ion exchange reaction with a counter ion exchange precursor M ⁺ D ⁻ to give an onium sulfonate compound ( 3) can be obtained.

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

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

In the precursor compound (3a), examples of the detachable monovalent group for B 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 (3a) with sodium dithionite, the molar ratio of sodium dithionite to the precursor compound (3a) is usually 0.01 to 100, preferably 1.0 to 10.

Examples of the inorganic base 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 preferable, N, 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 parts by weight or more, preferably 10 parts by weight or more, and more preferably 20 to 90 parts by weight with respect to a total of 100 parts by weight 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 sulfinate (3b), as an oxidizing agent, in addition to hydrogen peroxide, metachloroperbenzoic acid, t-butyl hydroperoxide, potassium peroxysulfate, potassium permanganate, sodium perborate, sodium metaiodic acid Sodium, chromic acid, sodium dichromate, halogen, iodobenzene dichloride, iodobenzene diacetate, osmium oxide (VIII), ruthenium oxide (VIII), sodium hypochlorite, sodium chlorite, oxygen gas, ozone gas, etc. Preferred are hydrogen peroxide, metachloroperbenzoic acid, t-butyl hydroperoxide, and the like.
The molar ratio of the oxidizing agent to the sulfinate (3b) 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 (3b) 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 buffer may be used 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 (3b) 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. Is methanol, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide or the like, and particularly preferably methanol.
Further, if necessary, an organic solvent and water can be used in combination, and the use ratio of the organic solvent in that case is usually 5 parts by weight or more, preferably 100 parts by weight in total of the organic solvent and water. Is 10 parts by weight or more, more preferably 20 to 90 parts by weight. The usage-amount with respect to 100 weight part of sulfinates (3b) 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.

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, in the process of converting the precursor compound (3a) to the sulfinate (3b), potassium dithionite or lithium dithionite can be used instead of sodium dithionite. In these cases, Produces a sulfonate in which sodium is replaced with potassium or lithium in the sulfonate (3c).

The ion exchange reaction of the sulfonate (3c) can be performed by a method such as ion exchange chromatography according to the general method described in Non-Patent Document 6, for example.
Examples of the monovalent anion of D ⁻ in the counter ion exchange precursor include F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , HSO ₄ ⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ , and the like.
PF ₆ ⁻ , SbF ₆ ⁻ , aliphatic sulfonate anion, aromatic sulfonate anion, trifluoromethanesulfonate anion, fluorosulfonate anion and the like can be mentioned, preferably Cl ⁻ , Br ⁻ , HSO ₄ ⁻ , BF ₄ ⁻ , aliphatic sulfonate ions, and the like, and more preferably Cl ⁻ , Br ⁻ , and HSO ₄ ^— .
The molar ratio of the counter ion exchange precursor to the sulfonate (3c) 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.
Further, if necessary, water and an organic solvent can be used in combination. The use ratio of the organic solvent in this case is usually 5 parts by weight or more, preferably 100 parts by weight of water and the organic solvent in total. Is 10 parts by weight or more, more preferably 20 to 90 parts by weight. 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.
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 (3) thus obtained can be purified by extraction with an organic solvent, if necessary.
The organic solvent is preferably an organic solvent that does not mix 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.

Further, the R ¹ is sulfonic acid onium salt compound is a group other than a hydrogen atom (3), the precursor compound R ¹ is a hydrogen atom (3a) as a starting material, in the same manner as in the above reaction formula [1] , Conversion to sulfinate (3b) by reaction with sodium dithionite, conversion to sulfonate (3c) by oxidation of sulfinate (3b), and counterion exchange with sulfonate (3c) After an ionic exchange reaction with the precursor M ⁺ D ⁻ , the sulfonic acid onium salt compound (3 ′) in which R ¹ is a hydrogen atom is obtained, and this is converted into the corresponding carboxylic acid chloride in the presence of a base, for example. Or by reacting with the corresponding organic sulfonyl chloride or the like to replace the hydrogen atom of the hydroxyl group.

The reaction of the sulfonic acid onium salt compound (3 ′) with carboxylic acid chloride or organic sulfonyl chloride can be carried out according to a known method.
In these reactions, the molar ratio of carboxylic acid chloride or organic sulfonyl chloride to the sulfonic acid onium salt compound (3 ′) is usually 0.1 to 10.0, preferably 1.0 to 5.0, more preferably 1.0 to 2.5.
In addition, it can replace with carboxylic acid chloride and organic sulfonyl chloride, and can also use a corresponding acid anhydride, a corresponding sulfonic acid anhydride, etc.

These reactions are usually performed in a reaction solvent.
The reaction solvent is preferably an organic solvent such as benzene, toluene, xylene, acetonitrile, pyridine, dimethylformamide, tetrahydrofuran, dioxane, dimethyl sulfoxide, methylene chloride, methylene bromide, chloroform, and more preferably acetonitrile, tetrahydrofuran. , Methylene chloride and the like.
The usage-amount with respect to 100 weight part of sulfonic-acid onium salt compounds (3 ') 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 include triethylamine, pyridine, N, N-di-i-propyl / ethylamine, 2,6-lutidine, N, N-diethylaniline, 4-dimethylaminopyridine, diazabicycloundecene, and the like. Are more preferable, and triethylamine, 4-dimethylaminopyridine and the like are more preferable.
The molar ratio of the base to the sulfonic acid onium salt compound (3 ′) 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 0.5 to 24 hours, preferably 1 to 12 hours.

-Synthesis method of sulfonic acid onium salt compound (4)-
The sulfonic acid onium salt compound (4) can be produced, for example, according to the general methods described in Non-Patent Document 6 and Non-Patent Document 7.
That is, as shown in the following reaction formula [2], the corresponding precursor compound (4a) is converted to an acetal compound (4b) by reacting with an alcohol compound or a phenol compound in the presence of an acid catalyst, for example. Is reacted with sodium dithionite in the presence of an inorganic base to convert it to a sulfinate (4c), which is oxidized with an oxidizing agent such as hydrogen peroxide to give a sulfonate (4d ), And then deprotecting the acetal group with an acid catalyst to convert it to a carbonyl group to obtain a sulfonate (4e), which is subjected to an ion exchange reaction with the counter ion exchange precursor M ⁺ D ^−. Thus, the sulfonic acid onium salt compound (4) can be obtained.

〔反応式 [２] において、Ｂは脱離性の１価の置換基を示し、Ｄ^- は１価のアニオンを示し、Ｒ’は１価の有機基を示し、２個のＲ’はそれらに含まれる原子を介して相互に結合して環を形成してもよい。〕

[In the reaction formula [2], B represents a detachable monovalent substituent, D ⁻ represents a monovalent anion, R ′ represents a monovalent organic group, and two R ′ represent these. A ring may be formed by bonding to each other via atoms contained in the ring. ]

Examples of the alcohol compound or phenol compound used in the acetalization reaction of the precursor compound (4a) include monohydric alcohols such as methanol, ethanol, n-propanol, n-butanol, and benzyl alcohol; ethylene glycol, 1, 2 -Dihydric alcohols such as propanediol, 1,3-propanediol, 2,3-butanediol; dihydric phenols such as catechol, etc., preferably ethylene glycol, 1,2-propanediol , Dihydric alcohols such as 1,3-propanediol.
The molar ratio of the alcohol compound or phenol compound to the precursor compound (4a) is usually 0.01 to 100, preferably 2.0 to 10.

Examples of the acid catalyst include hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, camphorsulfonic acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonate, trifluoromethanesulfonic acid, trifluoroacetic acid, trichloroacetic acid, acetic acid, and the like. Preferred examples include camphorsulfonic acid and p-toluenesulfonic acid.
The molar ratio of the acid catalyst to the precursor compound (4a) is usually 0.001 to 1.0, preferably 0.005 to 0.5, and more preferably 0.01 to 0.1.
In addition, a dehydrating agent can be used in combination with the acid catalyst.
Examples of the dehydrating agent include formic acid orthoesters such as trimethyl orthoformate and triethyl orthoformate, and water absorbing agents such as molecular sieves, preferably trimethyl orthoformate and triethyl orthoformate.
The molar ratio of the dehydrating agent to the precursor compound (4a) is usually 0.1 to 20.0, preferably 1 to 10.0, and more preferably 2.0 to 6.0.

This reaction is usually performed in a reaction solvent.
Examples of the reaction solvent include hydrocarbons such as benzene, toluene and xylene; ethers such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane and diethoxyethane, N, N-dimethylformamide, N, N- Organic solvents such as dimethylacetamide, acetonitrile, dimethylsulfoxide and the like are preferable, and benzene, toluene, xylene, tetrahydrofuran, dioxane, dimethoxyethane and the like are more preferable.
Moreover, the said alcohol compound itself can also be used as a solvent.
The usage-amount with respect to 100 weight part of precursor compounds (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.
The reaction temperature is usually 5 to 200 ° C., preferably 20 to 100 ° C., and the reaction time is usually 0.5 to 72 hours, preferably 1 to 24 hours. When the reaction temperature is higher than the boiling point of the reaction solvent, a pressure vessel such as an autoclave is used.

  Further, the conversion of the acetal compound (4b) into the sulfinate (4c) and the oxidation reaction of the sulfinate (4c) are carried out by converting the precursor compound (3a) into the sulfinate (3b) and the sulfinate ( It can be carried out according to the oxidation reaction of 3b).

Examples of the acid catalyst used for the conversion reaction of the sulfonate (4d) to the sulfonate (4e) include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, methanesulfonic acid, camphorsulfonic acid, p-toluenesulfonic acid, Examples thereof include pyridinium p-toluenesulfonate, trifluoromethanesulfonic acid, trifluoroacetic acid and the like, preferably hydrochloric acid, sulfuric acid, acetic acid and the like.
This reaction is usually performed in a reaction solvent.
The reaction solvent is preferably water or an organic solvent such as lower alcohols, tetrahydrofuran, dioxane, acetonitrile, dimethyl sulfoxide, acetic acid, trifluoroacetic acid, more preferably water, methanol, acetonitrile, dimethyl sulfoxide, or the like. Particularly preferred are water and methanol.
Further, if necessary, the organic solvent and water can be used in combination, and the use ratio of the organic solvent in that case is usually 5 parts by weight or more with respect to a total of 100 parts by weight of the organic solvent and water. Preferably it is 10 weight part or more, More preferably, it is 20-90 weight part.
The usage-amount with respect to 100 weight part of sulfonate (4d) 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.

The reaction temperature is usually 5 to 100 ° C., preferably 5 to 80 ° C., more preferably 5 to 50 ° C., and the reaction time is usually 0.5 to 72 hours, preferably 2 to 24 hours.
In the process of converting the acetal compound (4b) into the sulfinate (4c), potassium dithionite or lithium dithionite can be used instead of sodium dithionite. Produces a sulfonate salt in which sodium is replaced with potassium or lithium in the sulfonate salt (4d).
Moreover, the ion exchange reaction of a sulfonate (4e) can be performed according to the ion exchange reaction of the said sulfonate (3c).

—Synthesis Method of N-Sulfonyloxyimide Compound (7) —
The N-sulfonyloxyimide compound (7) can be synthesized using the sulfinate (3b) shown in the reaction formula [1].
That is, as shown in the following reaction formula [10], the sulfinate (3b) is converted into a sulfonyl halide compound such as a sulfonyl chloride compound (7a) using a halogenating agent such as chlorine gas, and this is handled. The N-sulfonyloxyimide compound (7) can be obtained by reacting with the N-hydroxyimide compound to be reacted in the presence of a base catalyst.

The reaction of the sulfinate (3b) and the halogenating agent can be carried out according to, for example, the general method described in Non-Patent Document 6 or the method described in each synthesis example described later.
As a method of adding a halogenating agent, for example, in the case of a gaseous halogenating agent such as chlorine gas, a method of blowing into a reaction solution can be adopted, and liquid or solid halogenation of bromine or iodine can be employed. In the case of an agent, it is possible to employ a method in which it is put into the reaction solution as it is, or dissolved in a reaction solvent described later and dropped.
The amount of the halogenating agent used relative to the sulfinate (3b) 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, dimethylsulfoxide, and more preferably water, methanol, N, Organic solvents such as N-dimethylacetamide, acetonitrile and dimethyl sulfoxide are preferred, and water is particularly preferred.
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 parts by weight or more with respect to a total of 100 parts by weight of the water and the organic solvent. Preferably it is 10 weight part or more, More preferably, it is 20-90 weight part.
The usage-amount with respect to 100 weight part of sulfinates (3b) 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.
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 compound (7a) with the N-hydroxyimide compound, the molar ratio of the N-hydroxyimide compound to the sulfonyl chloride compound (7a) is usually 0.1 to 10.0, preferably 0.00. It is 3-5.0, More preferably, it is 0.5-2.0.
This reaction is usually performed in a reaction solvent.
The reaction solvent is preferably an organic solvent such as acetonitrile, dimethylformamide, pyridine, tetrahydrofuran, dioxane, dimethyl sulfoxide, methylene chloride, methylene bromide, chloroform, and more preferably acetonitrile, tetrahydrofuran, methylene chloride, or the like. .
The usage-amount with respect to 100 weight part of sulfonyl chloride compounds (7a) 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-propylethylamine, 2,6-lutidine, N, N-diethylaniline, 4-dimethylaminopyridine, diazabicycloundecene. Etc. are preferred, and triethylamine, 4-dimethylaminopyridine and the like are more preferred. The molar ratio of the base catalyst to the sulfonyl chloride compound (7a) 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.

-Synthesis method of N-sulfonyloxyimide compound (8)-
The N-sulfonyloxyimide compound (8) can be synthesized using the sulfinate (4c) shown in the reaction formula [2].
That is, as shown in the following reaction formula [11], the sulfinate (4c) is converted to a sulfonyl halide compound such as a sulfonyl chloride compound (8a) by reacting with a halogenating agent such as chlorine gas, for example. This is converted into the sulfonyl chloride compound (8b) in the same manner as the procedure shown in the conversion reaction of the sulfonate (4d) to the sulfonate (4e) shown in the above reaction formula [2]. [10] By reacting with the corresponding N-hydroxyimide compound in the same manner as shown in [10], the N-sulfonyloxyimide compound (8) can be obtained.

〔反応式 [１１] において、Ｒ’は１価の有機基を示し、２個のＲ’はそれらに含まれる原子を介して相互に結合して環を形成してもよい。〕

[In the reaction formula [11], R ′ represents a monovalent organic group, and two R ′ may be bonded to each other via atoms contained therein to form a ring. ]

Other acid generators (A)
Furthermore, as an acid generator (A) other than the sulfonic acid onium salt compound (3), the sulfonic acid onium salt compound (4), the N-sulfonyloxyimide compound (7) and the N-sulfonyloxyimide compound (8), For example, a sulfone compound, a sulfonic acid ester compound, a disulfonyldiazomethane compound, a disulfonylmethane compound, an oxime sulfonate compound, a hydrazine sulfonate compound, and the like can be given.
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 (17), general formula (18), general formula (19), or general formula (20).

〔一般式（１７）および一般式（１８）において、Ｚ¹ 、Ｚ² 、Ｙ¹ 、Ｒ¹ 、ｐ、Ｒ² 、ｑおよびｎは、一般式（１）におけるそれぞれＺ¹ 、Ｚ² 、Ｙ¹ 、Ｒ¹ 、ｐ、Ｒ² 、ｑおよびｎと同義である。但し、各式中に複数存在するＺ¹ 、Ｚ² 、Ｙ¹ 、Ｒ¹ 、ｐ、Ｒ² 、ｑおよびｎはそれぞれ相互に同一でも異なってもよい。〕

[In General Formula (17) and General Formula (18), Z ¹ , Z ² , Y ¹ , R ¹ , p, R ² , q, and n are Z ¹ , Z ² , Y in General Formula (1), respectively. ¹ , R ¹ , p, R ² , q and n are synonymous. However, a plurality of Z ¹ , Z ² , Y ¹ , R ¹ , p, R ² , q and n existing in each formula may be the same as or different from each other. ]

〔一般式（１９）および一般式（２０）において、Ｚ¹ 、Ｚ² 、Ｙ¹ 、Ｒ² 、ｑおよびｎは、一般式（２）におけるそれぞれＺ¹ 、Ｚ² 、Ｙ¹ 、Ｒ² 、ｑおよびｎと同義である。但し、各式中に複数存在するＺ¹ 、Ｚ² 、Ｙ¹ 、Ｒ² 、ｑおよびｎはそれぞれ相互に同一でも異なってもよい。〕

[In the general formula (19) and the general formula ^{(20), Z 1, Z} 2, Y 1, R 2, q and n are each Z ¹ in the general formula ^{(2), Z 2, Y} 1, R 2, It is synonymous with q and n. However, a plurality of Z ¹ , Z ² , Y ¹ , R ² , q and n existing in each formula 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 (21) or general formula (22).

〔一般式（２１）において、Ｒ ¹ およびｐは、一般式（１）におけるそれぞれＲ ¹ およびｐと同義である。
一般式（２１）および一般式（２２）において、Ｚ¹ 、Ｚ² 、Ｙ¹ 、Ｒ² 、ｑおよびｎは、一般式（１）および一般式（２）におけるそれぞれＺ¹ 、Ｚ² 、Ｙ¹ 、Ｒ² 、ｑおよびｎと同義であり、Ｑ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。
但し、各式中に複数存在するＺ¹ 、Ｚ² 、Ｙ¹ 、Ｒ¹ 、ｐ、Ｒ² 、ｑおよびｎはそれぞれ相互に同一でも異なってもよい。〕

[In General formula (21), R < ¹ > and p are synonymous with R < ¹ > and p in General formula (1), respectively .
In the general formula (21) and the general formula ^{(22), Z 1, Z} 2, Y 1, R 2, q and n are each in the general formulas (1) and (2) Z ^1, Z ^2, Y ¹ , R ² , q and n are synonymous, Q represents a j-valent organic residue derived from pyrogallol, α-methylolbenzoin, etc., and j is an integer of 1 to 3.
However, a plurality of Z ¹ , Z ² , Y ¹ , R ¹ , p, R ² , q and n existing in each formula may be the same as or different from each other. ]

  Examples of the disulfonyldiazomethane compound include compounds represented by the following general formula (23) or general formula (24).

〔一般式（２３）において、Ｒ ¹ およびｐは、一般式（１）におけるそれぞれＲ ¹ およびｐと同義である。
一般式（２３）および一般式（２４）において、Ｚ¹ 、Ｚ² 、Ｙ¹ 、Ｒ² 、ｑおよびｎは、一般式（１）および一般式（２）におけるそれぞれＺ¹ 、Ｚ² 、Ｙ¹ 、Ｒ² 、ｑおよびｎと同義である。
但し、各式中に複数存在するＺ¹ 、Ｚ² 、Ｙ¹ 、Ｒ¹ 、ｐ、Ｒ² 、ｑおよびｎはそれぞれ相互に同一でも異なってもよい。〕

[In General formula (23), R < ¹ > and p are synonymous with R < ¹ > and p in General formula (1), respectively .
In the general formula (23) and the general formula ^{(24), Z 1, Z} 2, Y 1, R 2, q and n are each in the general formulas (1) and (2) Z ^1, Z ^2, Y ¹ , R ² , q and n are synonymous.
However, a plurality of Z ¹ , Z ² , Y ¹ , R ¹ , p, R ² , q and n existing in each formula may be the same as or different from each other. ]

  Examples of the disulfonylmethane compound include compounds represented by the following general formula (25) or general formula (26).

[In General formula (25), R < ¹ > and p are synonymous with R < ¹ > and p in General formula (1), respectively .
In the general formula (25) and the general formula ^{(26), Z 1, Z} 2, Y 1, R 2, q and n are each in the general formulas (1) and (2) Z ^1, Z ^2, Y ¹ , R ² , q and n have the same meanings, and V and W are each independently a monovalent group having an aryl group, a hydrogen atom, a linear or branched monovalent aliphatic hydrocarbon group or a heteroatom. Other organic groups, 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 a group represented by the following formula (ii) in which 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, an aralkyl group, or V ′ bonded to the same or different carbon atom. 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 k is an integer of 2 to 10.)
Is forming. However, a plurality of Z ¹ , Z ² , Y ¹ , R ¹ , p,
R ² , q, n, V ′ and W ′ may be the same or different from each other. ]

  Examples of the oxime sulfonate compound include compounds represented by general formula (27), general formula (28), general formula (29), or general formula (30).

〔一般式（２７）および一般式（２８）において、Ｚ¹ 、Ｚ² 、Ｙ¹ 、Ｒ¹ 、ｐ、Ｒ² 、ｑおよびｎは、一般式（１）におけるそれぞれＺ¹ 、Ｚ² 、Ｙ¹ 、Ｒ¹ 、ｐ、Ｒ² 、ｑおよびｎと同義であり、Ｒ⁹ は１価の有機基を示す。但し、各式中に複数存在するＺ¹ 、Ｚ² 、Ｙ¹ 、Ｒ¹ 、ｐ、Ｒ² 、ｑ、ｎおよびＲ⁹ はそれぞれ相互に同一でも異なってもよい。〕

[In General Formula (27) and General Formula (28), Z ¹ , Z ² , Y ¹ , R ¹ , p, R ² , q, and n are Z ¹ , Z ² , Y in General Formula (1), respectively. ¹ , R ¹ , p, R ² , q and n are synonymous, and R ⁹ represents a monovalent organic group. However, a plurality of Z ¹ , Z ² , Y ¹ , R ¹ , p, R ² , q, n and R ⁹ present in each formula may be the same as or different from each other. ]

〔一般式（２９）および一般式（３０）において、Ｚ¹ 、Ｚ² 、Ｙ¹ 、Ｒ² 、ｑおよびｎは、一般式（２）におけるそれぞれＺ¹ 、Ｚ² 、Ｙ¹ 、ｐ、Ｒ² 、ｑおよびｎと同義であり、Ｒ⁹ は１価の有機基を示す。但し、各式中に複数存在するＺ¹ 、Ｚ² 、Ｙ¹ 、Ｒ² 、ｑ、ｎおよびＲ⁹ はそれぞれ相互に同一でも異なってもよい。〕

[In General Formula (29) and General Formula (30), Z ¹ , Z ² , Y ¹ , R ² , q, and n are Z ¹ , Z ² , Y ¹ , p, R in General Formula ( 2 ), respectively. ² , q and n have the same meaning, and R ⁹ represents a monovalent organic group. However, a plurality of Z ¹ , Z ² , Y ¹ , R ² , q, n and R ⁹ present in each formula may be the same or different from each other. ]

  Examples of the hydrazine sulfonate compound include compounds represented by general formula (31), general formula (32), general formula (33), or general formula (34).

〔一般式（３１）および一般式（３２）において、Ｚ¹ 、Ｚ² 、Ｙ¹ 、Ｒ¹ 、ｐ、Ｒ² 、ｑおよびｎは、一般式（１）におけるそれぞれＺ¹ 、Ｚ² 、Ｙ¹ 、Ｒ¹ 、ｐ、Ｒ² 、ｑおよびｎと同義である。但し、各式中に複数存在するＺ¹ 、Ｚ² 、Ｙ¹ 、Ｒ¹ 、ｐ、Ｒ² 、ｑおよびｎはそれぞれ相互に同一でも異なってもよい。〕

[In General Formula (31) and General Formula (32), Z ¹ , Z ² , Y ¹ , R ¹ , p, R ² , q, and n are Z ¹ , Z ² , Y in General Formula (1), respectively. ¹ , R ¹ , p, R ² , q and n are synonymous. However, a plurality of Z ¹ , Z ² , Y ¹ , R ¹ , p, R ² , q and n existing in each formula may be the same as or different from each other. ]

〔一般式（３３）および一般式（３４）において、Ｚ¹ 、Ｚ² 、Ｙ¹ 、Ｒ² 、ｑおよびｎは、一般式（２）におけるそれぞれＺ¹ 、Ｚ² 、Ｙ¹ 、Ｒ² 、ｑおよびｎと同義である。但し、各式中に複数存在するＺ¹ 、Ｚ² 、Ｙ¹ 、Ｒ² 、ｑおよびｎはそれぞれ相互に同一でも異なってもよい。〕

[In General Formula (33) and General Formula (34), Z ¹ , Z ² , Y ¹ , R ² , q and n are Z ¹ , Z ² , Y ¹ , R ² , respectively in General Formula ( 2 ). It is synonymous with q and n. However, a plurality of Z ¹ , Z ² , Y ¹ , R ² , q and n existing in each formula may be the same or different from each other. ]

In the positive radiation sensitive resin composition and the negative radiation sensitive resin composition of the present invention, the acid generator (A) can be used alone or in admixture of two or more.
When the acid generator (A) is composed of a single compound having the structure (1) and the structure (2), and when it is a mixture of the compound having the structure (1) and the compound having the structure (2) ^{, Z 1, Z 2, Y} 1 in the structure (1), Z ¹ in R ^2, q and n and structure ^{(2), Z 2, Y} 1, R 2, and q and n are also identical to each other, respectively May be different.

Other acid generators The positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition of the present invention include a radiation-sensitive acid generator other than the acid generator (A) (hereinafter referred to as “other acid generators”). One or more kinds of "agents") can be used in combination.
Examples of other acid generators include onium salt compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, diazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, and the like.

Examples of the onium salt compounds include iodonium salts, sulfonium salts (including tetrahydrothiophenium salts), phosphonium salts, diazonium salts, ammonium salts, pyridinium salts, and the like.
Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof.
Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.
Moreover, as said sulfonimide compound, the compound represented by following General formula (35) can be mentioned, for example.

〔一般式（３５）において、Ｒ¹⁰は２価の有機基を示し、Ｒ¹¹は１価の有機基を示す。〕

[In the general formula (35), R ¹⁰ represents a divalent organic group, and R ¹¹ represents a monovalent organic group. ]

In the general formula (35), as R ¹⁰ , for example, a methylene group, a linear or branched alkylene group having 2 to 20 carbon atoms, an aralkylene group having 2 to 20 carbon atoms, a difluoromethylene group, 2 to 2 carbon atoms, 20 linear or branched perfluoroalkylene groups, cyclohexylene groups, phenylene groups, divalent groups having an optionally substituted norbornane skeleton, and these groups are aryl groups or carbon atoms having 6 or more carbon atoms. Examples thereof include a group substituted with an alkoxyl group having a number of 1 or more.

R ¹¹ may be, for example, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, or a perfluoroalkyl group having 3 to 10 carbon atoms. Examples thereof include a fluorocycloalkyl group, a monovalent bicyclo ring-containing hydrocarbon group having 7 to 15 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

  Examples of the diazomethane compound include a compound represented by the following general formula (36).

〔一般式（３６）において、各Ｒ¹²は相互に独立に直鎖状もしくは分岐状のアルキル基、シクロアルキル基、アリール基、ハロゲン置換アルキル基、ハロゲン置換シクロアルキル基、ハロゲン置換アリール基等の１価の基を示す。〕

[In the general formula (36), each R ¹² is independently a linear or branched alkyl group, cycloalkyl group, aryl group, halogen-substituted alkyl group, halogen-substituted cycloalkyl group, halogen-substituted aryl group, etc. A monovalent group is shown. ]

  Examples of the disulfonylmethane compound include a compound represented by the following general formula (37).

[In the general formula (37), each R ¹³ is independently a linear or branched monovalent aliphatic hydrocarbon group, cycloalkyl group, aryl group, aralkyl group or other monovalent group having a hetero atom. Wherein T and U are each independently a monovalent group having an aryl group, a hydrogen atom, a linear or branched monovalent aliphatic hydrocarbon group, a cycloalkyl group, an aralkyl group or a heteroatom. Represents another organic group, and at least one of T and U is an aryl group, or Y and U are connected to each other to form a monocyclic or polycyclic ring having at least one unsaturated bond, Or a group represented by the following formula (iii) wherein T and U are connected to each other

(However, T ′ and U ′ are each independently a hydrogen atom, a halogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a T bonded to the same or different carbon atom. When 'and U' are connected to each other to form a carbon monocyclic structure, and there are a plurality of T 'and U', the plurality of T 'and the plurality of U' may be the same as or different from each other. , K is an integer from 2 to 10.)
Is forming. ]

  Moreover, as an oxime sulfonate compound, the compound etc. which are represented with the following general formula (38) or general formula (39) can be mentioned, for example.

〔一般式（３８）および一般式（３９）において、各Ｒ¹⁴および各Ｒ¹⁵は相互に独立に１価の有機基を示す。〕

[In General Formula (38) and General Formula (39), each R ¹⁴ and each R ¹⁵ independently represent a monovalent organic group. ]

In the general formula (38) and the general formula (39), specific examples of the monovalent organic group represented by R ¹⁴ include a methyl group, an ethyl group, an n-propyl group, a phenyl group, and a p-toluyl group. it can.
In the general formula (38) and general formula (39), specific examples of the monovalent organic group represented by R ¹⁵ include a phenyl group, a p-toluyl group, and a 1-naphthyl group.

  Also. Examples of the hydrazine sulfonate compound include compounds represented by the following general formula (40) or general formula (41).

〔一般式（４０）および一般式（４１）において、各Ｒ¹⁶は相互に独立に１価の有機基を示す。〕

[In General Formula (40) and General Formula (41), each R ¹⁶ independently represents a monovalent organic group. ]

In the general formula (40) and general formula (41), specific examples of the monovalent organic group represented by R ¹⁶ include a methyl group, an ethyl group, an n-propyl group, a phenyl group, a p-toluyl group, and a trifluoromethyl group. And nonafluoro-n-butyl group.

Other acid generators are preferably one or more of the group of onium salt compounds, sulfonimide compounds and diazomethane compounds.
Particularly preferred other acid generators include, for example,
Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium 2-trifluoromethylbenzenesulfonate, diphenyliodonium 4-trifluoromethylbenzenesulfonate, Diphenyliodonium 2,4-difluorobenzenesulfonate, diphenyliodonium 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate,
Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4 -T-butylphenyl) iodonium 10-camphorsulfonate, bis (4-t-butylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis ( 4-t-butylphenyl) iodonium 2,4-difluorobenzenesulfonate, bis (4-t-butylphenyl) iodonium 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate Door,

Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium 2-trifluoromethylbenzenesulfonate, triphenylsulfonium 4- Trifluorobenzenesulfonate, triphenylsulfonium 2,4-difluoromethylbenzenesulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate,
1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate,

N- (trifluoromethanesulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) succinimide, N-[(5-methyl-5-carboxymethanebicyclo [2.2.1] heptan-2-yl) sulfonyloxy] Succinimide,
N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- [1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonyloxy] bicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
Mention may be made of at least one selected from the group of bis (cyclohexanesulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane and bis (1,4-dioxaspiro [4.5] -decan-7-sulfonyl) diazomethane.

  The proportion of the other acid generator used can be appropriately selected according to the type of each other acid generator, but the total amount of the acid generator (A) and the other acid generator is 100 parts by weight. Usually, it is 95 parts by weight or less, preferably 90 parts by weight or less, and more preferably 80 parts by weight or less. In this case, if the use ratio of the other acid generator exceeds 95 parts by weight, the expected effect in the present invention may be impaired.

Acid-dissociable group-containing resin (B)
The component (B) in the positive radiation sensitive resin composition of the present invention includes only the repeating unit represented by the general formula (42) and the repeating unit in which the phenolic hydroxyl group in the repeating unit is protected with an acid dissociable group. Resin (B2) consisting of only one or more of the repeating units represented by the general formula (43) or the general formula (44) and the repeating unit represented by the general formula (45) (B2) ) Selected from the group consisting of alkali-insoluble or alkali-insoluble resins having an acid-dissociable group, which are readily alkali-soluble when the acid-dissociable group is dissociated (hereinafter referred to as “acid-dissociable group-containing”). Resin (B) ").
The term “alkali-insoluble or alkali-insoluble” as used herein is employed when a resist pattern is formed from a resist film formed using a radiation-sensitive resin composition containing the acid-dissociable group-containing resin (B). When developing a film using only the acid-dissociable group-containing resin (B) instead of the resist film under alkaline development conditions, 50% or more of the initial film thickness of the film remains after development. means.
Hereinafter, the repeating unit represented by the general formula (42) is referred to as “repeating unit (42)”, the repeating unit represented by the general formula (43), the repeating unit represented by the general formula (44), and the general unit. The repeating units represented by formula (45) are referred to as “repeating unit (43)”, “repeating unit (44)” and “repeating unit (45)”, respectively.

The acid dissociable group in the resin (B1) is a group in which a hydrogen atom in a phenolic hydroxyl group is substituted, and means a group that dissociates in the presence of an acid.
Examples of such acid dissociable groups include substituted methyl groups, 1-substituted ethyl groups, 1-substituted n-propyl groups, 1-branched alkyl groups, alkoxycarbonyl groups, acyl groups, and cyclic acid dissociable groups. Etc.

  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, 4-bromobenzyl group, 4-nitrobenzyl group, 4 -Methoxybenzyl group, 4-methylthiobenzyl group, 4-ethoxybenzyl group, 4-ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl group , N-but Aryloxycarbonyl 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 Groups, 1-n-butoxycarbonylethyl group, 1-t-butoxycarbonylethyl group, etc. Can.

Examples of the 1-substituted-n-propyl group include 1-methoxy-n-propyl group and 1-ethoxy-n-propyl group.
Examples of the 1-branched alkyl group include i-propyl group, 1-methylpropyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, and the like. Can be mentioned.
Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an i-propoxycarbonyl group, and a t-butoxycarbonyl group.

  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.

  Examples of the cyclic acid dissociable group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 4-methoxycyclohexyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, and a tetrahydro group. A thiofuranyl group, 3-bromotetrahydropyranyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, 3-tetrahydrothiophene-1,1-dioxide group and the like can be mentioned.

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, t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group and the like are preferable.
In the resin (B1) , one or more acid-dissociable groups can be present.

The rate of introduction of acid dissociable groups in the resin (B1) ( ratio of the number of acid dissociable groups to the total number of acidic functional groups and acid dissociable groups in the resin (B1)) Although it can select suitably by the kind of resin in which group is introduce | transduced, Preferably it is 5 to 100%, More preferably, it is 10 to 100%.
Further, the structure of the resin (B1) is not particularly limited as long as it has the above-described properties, and various structures can be used. In particular, one of the hydrogen atoms of the phenolic hydroxyl group in poly (p-hydroxystyrene). A resin or the like in which part or all is substituted with an acid dissociable group can be preferably used.

The resin (B1) can be particularly suitably used for , for example, a positive radiation sensitive resin composition using a KrF excimer laser. The resin (B1) can also be suitably used for a positive-type radiation-sensitive resin composition that uses other radiation such as ArF excimer laser, F ₂ excimer laser, and electron beam.

  As the repeating unit (42), a unit in which a non-aromatic double bond of p-hydroxystyrene is cleaved is particularly preferable.

The resin (B2) can be particularly suitably used for, for example, a positive radiation sensitive resin composition using an ArF excimer laser. The resin (B2) can also be suitably used for a positive-type radiation-sensitive resin composition that uses other radiation such as KrF excimer laser, F ₂ excimer laser, and electron beam.

  Preferable repeating units (43) include, for example, (meth) acrylic acid 3-hydroxyadamantan-1-yl, (meth) acrylic acid 3, 5-dihydroxyadamantan-1-yl, (meth) acrylic acid 3-cyanoadamantane -1-yl, (meth) acrylic acid 3-carboxyladamantan-1-yl, (meth) acrylic acid 3,5-dicarboxyladamantan-1-yl, (meth) acrylic acid 3-carboxyl-5-hydroxyadamantane- Examples thereof include 1-yl and (meth) acrylic acid 3-methoxycarbonyl-5-hydroxyadamantan-1-yl.

  Moreover, as a preferable repeating unit (45), (meth) acrylic acid 1-methyl-1-cyclopentyl, (meth) acrylic acid 1-ethyl-1-cyclopentyl, (meth) acrylic acid 1-methyl-1- Cyclohexyl, 1-ethyl-1-cyclohexyl (meth) acrylate, 2-methyladamantan-2-yl (meth) acrylate, 2-ethyladamantan-2-yl (meth) acrylate, 2- (meth) acrylic acid 2- n-propyladamantan-2-yl, (meth) acrylic acid 2-i-propyladamantan-2-yl, (meth) acrylic acid 2-methyladamantan-2-yl, (meth) acrylic acid 1- (adamantane-1 -Yl) -1-methylethyl and the like can be mentioned.

The molecular weight of the acid-dissociable group-containing resin resin (B) is not particularly limited and may be appropriately selected. The polystyrene-reduced weight molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC). ) is usually 1,000 to 500,000, preferably 1, 000 to 15 0,000, more preferably from 3,000 to 1 00,000. By using the acid dissociable group-containing resin resin (B) having Mw in such a range, the obtained resist has excellent development characteristics.

  The ratio (Mw / Mn) between the Mw of the acid-dissociable group-containing resin (B) and the polystyrene-equivalent molecular weight (hereinafter referred to as “Mn”) measured by GPC is not particularly limited, and should be appropriately selected. However, it is usually 1 to 10, preferably 1 to 8, and more preferably 1 to 5. By using the acid dissociable group-containing resin (B) having Mw / Mn in such a range, the resulting resist has excellent resolution performance.

  In the positive radiation sensitive resin composition of the present invention, the amount of the radiation sensitive acid generator used can be variously selected according to the desired characteristics of the resist, but the acid dissociable group-containing resin (B ) Preferably it is 0.001-70 weight part with respect to 100 weight part, More preferably, it is 0.01-50 weight part, Most preferably, it is 0.1-20 mass part. In this case, when the amount of the radiation-sensitive acid generator used is 0.001 part by weight or more, a decrease in sensitivity and resolution can be suppressed, and when it is 70 parts by weight or less, the resist coatability and pattern shape are reduced. Can be prevented.

(C) Alkali-soluble resin (C) component in the negative radiation sensitive resin composition of this invention is resin (C1 which consists only of 1 or more types of the repeating unit represented by the said General formula (49)-(51). ), And one or more repeating units represented by the general formulas (49) to (51) and one or more repeating units in which the polymerizable unsaturated bond of the vinyl aromatic compound or (meth) acrylic acid ester is cleaved. It consists of alkali-soluble resin soluble in an alkali developing solution chosen from the group of resin (C2) which consists only of .

  The content of the repeating unit represented by the general formulas (49) to (51) in the alkali-soluble resin is preferably 10 to 100 mol%, more preferably 20 to 100 mol%.

As the alkali-soluble resin in the present invention, poly (4-hydroxystyrene), 4-hydroxystyrene / 4-hydroxy-α-methylstyrene copolymer, 4-hydroxystyrene / styrene copolymer and the like are particularly preferable.
The Mw of the alkali-soluble resin varies depending on the desired properties of the negative radiation-sensitive resin composition, 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.

(D) Crosslinking agent
(D) component in the negative radiation sensitive resin composition of this invention consists of a compound (henceforth a "crosslinking agent") which can bridge | crosslink alkali-soluble resin in presence of an acid.
Examples of the crosslinking agent include compounds having at least one functional group having a crosslinking reactivity with an alkali-soluble resin (hereinafter referred to as “crosslinkable functional group”).

  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 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 group-containing Phenol resins, 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, methylol group-containing phenol compounds, methoxymethyl group-containing melamine compounds, methoxymethyl group-containing phenol compounds, methoxymethyl group-containing glycoluril compounds, methoxymethyl group-containing urea compounds and acetoxymethyl group-containing phenol compounds are preferred. More preferred are methoxymethyl group-containing melamine compounds (for example, hexamethoxymethyl melamine), methoxymethyl group-containing glycoluril compounds, methoxymethyl group-containing urea compounds, and the like. The methoxymethyl group-containing melamine compound is a trade name such as CYMEL300, 301, 303, 305 (manufactured by Mitsui Cyanamid Co., Ltd.). 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.).

  Moreover, as the crosslinking agent, a resin imparted with a property as a crosslinking agent by substituting the hydrogen atom of the 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 in the present invention, a methoxymethyl group-containing compound, more specifically dimethoxymethylurea, tetramethoxymethylglycoluril and the like are particularly preferable.
The said crosslinking agent can be used individually or in mixture of 2 or more types.

In the negative radiation-sensitive resin composition of the present invention, the amount of the radiation-sensitive acid generator used is preferably 0.01 to 70 parts by weight, more preferably 0.1 to 50 parts per 100 parts by weight of the alkali-soluble resin. Part by weight, particularly preferably 0.5 to 20 parts by weight. In this case, if the amount of the radiation-sensitive acid generator 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.
The amount of the crosslinking agent used is preferably 5 to 95 parts by weight, more preferably 15 to 85 parts by weight, and particularly preferably 20 to 75 parts by weight per 100 parts by weight of the alkali-soluble resin. In this case, if the amount of the crosslinking agent used 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 the amount exceeds 95 parts by weight, the developability of the exposed part is increased. There is a tendency to decrease.

Other Additives The positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition of the present invention control the diffusion phenomenon in the resist film of the acid generated from the radiation-sensitive acid generator upon exposure, It is preferable to blend an acid diffusion controller having an action of suppressing an undesirable chemical reaction in the exposed region. By blending such an acid diffusion controller, the storage stability of the radiation-sensitive resin composition can be improved, the resolution as a resist is further improved, and the holding time from exposure to development processing is also improved. Changes in the line width of the resist pattern due to fluctuations in (PED) can be suppressed, and as a result, a radiation-sensitive resin composition having extremely excellent process stability can be obtained.

As such an 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.
Examples of the nitrogen-containing organic compound include a compound represented by the following general formula (52) (hereinafter referred to as “nitrogen-containing compound (α)”), a diamino compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (α)”). , “Nitrogen-containing compound (β)”), polyamino compounds and polymers having three or more nitrogen atoms (hereinafter referred to as “nitrogen-containing compound (γ)”), amide group-containing compounds, urea compounds, nitrogen-containing compounds. A heterocyclic compound etc. can be mentioned.

〔一般式（５２）において、各Ｒ²⁹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、これらの各基は置換されてもよい。〕

[In General Formula (52), each R ²⁹ independently represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and each of these groups may be substituted. ]

In the general formula (52), examples of the optionally substituted alkyl group represented by R ²⁹ include those having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, and n-propyl. Group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n-heptyl group, n -An octyl group, n-ethylhexyl group, n-nonyl group, n-decyl group etc. can be mentioned.

Examples of the aryl group which may be substituted for R ²⁹ include those having 6 to 12 carbon atoms, specifically, phenyl group, tolyl group, xylyl group, cumenyl group, 1-naphthyl group and the like. Can do.
Furthermore, examples of the aralkyl group which may be substituted for R ²⁹ include those having 7 to 19 carbon atoms, preferably 7 to 13 carbon atoms, specifically, benzyl group, α-methylbenzyl group, phenethyl group, naphthylmethyl. Groups 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, aromatic amines such as 1-naphthylamine; ethanolamine, diethanolamine, can be exemplified alkanolamines such as triethanolamine and the like.

Examples of the nitrogen-containing compound (β) include ethylenediamine, N, N, N ′,
N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxyethyl) ethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ) Ethylenediamine, 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] Examples thereof include benzene and 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene.
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 imidazole, benzimidazole, 2-methylimidazole, 4-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, 4-phenylimidazole, 4-methyl-2- Imidazoles such as phenylimidazole and 2-phenylbenzimidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4 -In addition to pyridines such as phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, acridine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, 1-piperidineethanol, - piperidineethanol, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, and 1,4-diazabicyclo [2.2.2] octane.

In addition, as the nitrogen-containing organic compound, a compound having an acid dissociable group can also be used.
Examples of the nitrogen-containing organic 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) di-n-octylamine, N- (t-butoxycarbonyl) diethanolamine, N- (t-butoxycarbonyl) dicyclohexylamine, N- And (t-butoxycarbonyl) diphenylamine.

  Of these nitrogen-containing organic compounds, nitrogen-containing compounds (α), nitrogen-containing compounds (β), nitrogen-containing heterocyclic compounds, nitrogen-containing organic 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 preferably 15 parts by mass or less, more preferably 0.001 to 10 parts by mass, particularly preferably 0.005 to 100 parts by mass of the acid dissociable group-containing resin (B). 5 parts by mass. In this case, by setting the compounding amount of the acid diffusion controller to 0.001 part by mass or more, it is possible to suppress a decrease in pattern shape and dimensional fidelity as a resist depending on process conditions, and to 15 parts by mass or less. Thus, the sensitivity as a resist and the developability of the exposed portion can be further improved.

The positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition of the present invention can be blended with a dissolution control agent having a property of increasing the solubility in an alkali developer by the action of an acid.
As such a dissolution control agent, for example, a compound having an acidic functional group such as a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group, or a compound in which the hydrogen atom of the acidic functional group in the compound is substituted with an acid dissociable group Etc.
The said dissolution control agent can be used individually or in mixture of 2 or more types. The blending amount of the dissolution control agent is usually 50 parts by weight or less, preferably 20 parts by weight or less, with respect to 100 parts by weight of the total resin components in the radiation-sensitive resin composition.

The positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition of the present invention are blended with a surfactant exhibiting the action of improving the coating property, striation, developability, etc. of the radiation-sensitive resin composition. You can also
As such a surfactant, any of anionic, cationic, nonionic or amphoteric surfactants can be used, but nonionic surfactants are preferred. Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, polyethylene glycol higher fatty acid diesters, and the following trade names “KP” (Shin-Etsu Chemical Co., Ltd.). ), "Polyflow" (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), "F Top" (manufactured by Tokemu Products), "Megafuck" (manufactured by Dainippon Ink & Chemicals), "Florard" (manufactured by Sumitomo 3M), "Asahi Guard" ”And“ Surflon ”(manufactured by Asahi Glass).
The surfactants can be used alone or in admixture of two or more. The compounding amount of the surfactant is usually 2 parts by weight or less, preferably 1.5 parts by weight or less as an active ingredient of the surfactant with respect to 100 parts by weight of the total resin components in the radiation-sensitive resin composition. .

The positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition of the present invention absorbs radiation energy and transmits the energy to the radiation-sensitive acid generator, thereby generating an amount of acid. A sensitizer capable of increasing the apparent sensitivity and improving the apparent sensitivity of the radiation-sensitive resin composition can be blended.
Examples of such sensitizers include acetophenones, benzophenones, naphthalene, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines and the like.
These sensitizers can be used alone or in admixture of two or more. The blending amount of the sensitizer is usually 50 parts by weight or less, preferably 30 parts by weight or less, with respect to 100 parts by weight of the total resin components in the radiation-sensitive resin composition.

Furthermore, in the positive radiation sensitive resin composition and the negative radiation sensitive resin composition of the present invention, additives other than those described above, for example, dyes, are included as long as the effects of the present invention are not impaired. A pigment, an adhesion assistant, an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improving agent, etc., specifically, 4-hydroxy-4′-methylchalcone can be blended.
In this case, by blending a dye or pigment, the latent image in the exposed area can be visualized, and the influence of halation during exposure can be mitigated, and the adhesion to the substrate can be improved by blending an adhesion assistant. be able to.

Preparation of Composition Solution The positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition of the present invention are usually prepared by dissolving each component in a solvent at the time of use to obtain a uniform solution. A composition solution is prepared by filtering with a filter having a pore size of about 0.2 μm.

  Examples of the solvent include ethers, esters, ether esters, ketones, ketone esters, amides, amide esters, lactams, lactones, and (halogenated) hydrocarbons. More specifically, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, acetate esters , Hydroxyacetic acid esters, lactic acid esters, alkoxyacetic acid esters, (non) cyclic ketones, acetoacetic acid esters, pyruvic acid esters, propionic acid esters, N, N Dialkyl formamides, N, N- dialkyl acetamides, N- alkylpyrrolidones, .gamma.-lactones, may be mentioned (halogenated) aliphatic hydrocarbons, and (halogenated) aromatic hydrocarbons, and the like.

  Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether. , Diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, isopropenyl acetate, isopropenyl Propionate Toluene, xylene, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy- Methyl 3-methylbutyrate, methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion Methyl acid, - ethyl ethoxypropionate, N- methylpyrrolidone, N, N- dimethylformamide, N, can be mentioned N- dimethylacetamide.

Among these solvents, propylene glycol monoalkyl ether acetates, 2-heptanone, lactic acid esters, 2-hydroxypropionic acid esters, 3-alkoxypropionic acid esters, etc. have good in-plane uniformity during coating. Is preferable in that.
The said solvent can be used individually or in mixture of 2 or more types.

If necessary, other solvents such as benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1- Use high-boiling solvents such as octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate, etc. Can do.
These other solvents can be used alone or in admixture of two or more.
The proportion of other solvents used is usually 50% by weight or less, preferably 30% by weight or less, based on the total solvent.

  The total amount of the solvent used is such that the total solid content of the solution is usually 5 to 50% by weight, preferably 10 to 50% by weight, more preferably 10 to 40% by weight, particularly preferably 10 to 30% by weight. The amount is 10 to 25% by weight. By setting the total solid content concentration of the solution within this range, it is preferable in that the in-film uniformity during coating is good.

Formation of resist pattern When forming a resist pattern from the positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition of the present invention, the composition solution prepared as described above is spin-coated, A resist film is formed by applying on a substrate such as a silicon wafer or a wafer coated with aluminum by an appropriate application means such as cast coating or roll coating. Thereafter, a heat treatment (hereinafter referred to as “PB”) is performed in advance in some cases, and then the resist film is exposed through a predetermined mask pattern.
The radiation that can be used in the exposure includes the emission line spectrum of a mercury lamp (wavelength 254 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength), depending on the type of radiation-sensitive acid generator used. 193 nm), far ultraviolet rays such as F ₂ excimer laser (wavelength 157 nm), EUV (wavelength 13 nm, etc.), X-rays such as synchrotron radiation, charged particle beams such as electron beams, etc., preferably far ultraviolet rays And a charged particle beam, particularly preferably a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F ₂ excimer laser (wavelength 157 nm) and an electron beam.
The exposure conditions such as the radiation dose are appropriately selected according to the composition of the positive radiation sensitive resin composition and the negative radiation sensitive resin composition, the type of additive, and the like.
In forming a resist pattern, it is preferable to perform a heat treatment after exposure (hereinafter, this heat treatment is referred to as “PEB”) from the viewpoint of improving the apparent sensitivity of the resist.
The heating conditions for PEB vary depending on the composition of the radiation-sensitive resin composition, the type of additive, and the like, but are usually 30 to 200 ° C, preferably 50 to 150 ° C.

Thereafter, the exposed resist film is developed with an alkaline developer to form a predetermined positive or negative resist pattern.
Examples of the alkali developer include alkali metal hydroxides, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo [5.4. 0.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene and the like, an alkaline aqueous solution in which one or more alkaline compounds are dissolved is used. An aqueous solution of ammonium hydroxides.
The concentration of the alkaline aqueous solution is preferably 10% by weight or less, more preferably 1 to 10% by weight, and particularly preferably 2 to 5% by weight. In this case, by setting the concentration of the alkaline aqueous solution to 10% by weight or less, dissolution of the non-exposed portion in the developer can be suppressed.
Further, it is preferable to add an appropriate amount of a surfactant or the like to the developer composed of the alkaline aqueous solution, whereby the wettability of the developer with respect to the resist can be enhanced.
In addition, after developing with the developing solution which consists of the said alkaline aqueous solution, generally it wash | cleans with water and dries.

The acid generator (A) has a relatively high combustibility, has no problem with human accumulation, and has a sufficiently high acidity and boiling point of the generated acid. Also, a KrF excimer laser, an ArF excimer laser, It is a component that generates excellent sulfonic acid (11) or sulfonic acid (12) in response to these radiations and is excellent in transparency to far ultraviolet rays such as F ₂ excimer laser or EUV and electron beam.

The positive radiation-sensitive resin composition and negative radiation-sensitive resin composition of the present invention containing the acid generator (A) are active radiation, particularly KrF excimer laser, ArF excimer laser, F ₂ excimer laser or EUV. Effectively sensitive to deep ultraviolet rays and electron beams typified by, the sensitivity is high, the acid diffusion length in the resist film is moderately short, the resolution is excellent, and the dependence on the sparse density of the mask pattern is small It is excellent in smoothness and can be used very suitably in the field of microfabrication represented by the manufacture of integrated circuit elements that are expected to be further miniaturized in the future.

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 (A)]
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 then purified by distillation under reduced pressure at 85 ° C. and 25 mmHg to give colorless liquid 5- (2-bromo-1,1,2,2-tetrafluoro 326 g of ethyl) bicyclo [2.2.1] hept-2-ene (hereinafter referred to as “compound (1-a)”) was obtained.

  Next, 150 g of compound (1-a) and 253 g of formic acid were placed in a 1 liter eggplant flask and stirred for 15 hours under reflux conditions. Then, after removing excess formic acid by atmospheric distillation and allowing to cool to room temperature, 1,500 ml of ethyl acetate and saturated aqueous sodium hydrogen carbonate solution were added, and the mixture was stirred at the same temperature for 5 minutes. Thereafter, the ethyl acetate layer is separated, washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give pale yellow liquid 2- (2-bromo-1,1,2,2- Tetrafluoroethyl) -5-formyloxybicyclo [2.2.1] heptane (hereinafter referred to as “compound (1-b)”) and 2- (2-bromo-1,1,2,2-tetra). 180 g of a mixture of fluoroethyl) -6-formoxybicyclo [2.2.1] heptane (hereinafter referred to as “compound (1-b ′)”) was obtained.

Next, a solution obtained by dissolving 180 g of a mixture of the compound (1-b) and the compound (1-b ′) in 1500 g of methanol was placed in a 2-liter eggplant flask, and 220 g of anhydrous potassium carbonate was added at room temperature. Stir for hours. Thereafter, the reaction solution is suction filtered, the filtrate is concentrated under reduced pressure, 1,500 ml of ethyl acetate is added, washed with ion-exchanged water, further washed with saturated brine, dried over anhydrous magnesium sulfate, and then subjected to reduced pressure. Concentrated under. Then, the obtained residue was purified by distillation under reduced pressure at 121 ° C. and 8 mmHg, whereby 2- (2-bromo-1,1,2,2-tetrafluoroethyl) -5-hydroxybicyclo of pale yellow liquid was obtained. [2.2.1] Heptane (hereinafter referred to as “compound (1-c)”) and 2- (2-bromo-1,1,2,2-tetrafluoroethyl) -6-hydroxybicyclo [2] 2.1] 150 g of a mixture of heptane (hereinafter referred to as “compound (1-c ′)”) was obtained.
The measurement result of ¹ H-NMR analysis of this mixture is shown in FIG.

  Next, a solution prepared by dissolving 20 g of the mixture of the compound (1-c) and the compound (1-c ′) and 0.42 g of 4-dimethylaminopyridine in 100 ml of methylene chloride was put in a 300 ml eggplant flask, and di-t- After 15 g of butyl dicarbonate was added dropwise at room temperature, the mixture was stirred at the same temperature for 12 hours. Thereafter, 400 ml of methylene chloride was added to the reaction solution, washed successively with 5% oxalic acid aqueous solution, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and pale yellow Liquid 2- (2-bromo-1,1,2,2-tetrafluoroethyl) -5-t-butoxycarbonyloxybicyclo [2.2.1] heptane (hereinafter referred to as “compound (1-d)”) And 2- (2-bromo-1,1,2,2-tetrafluoroethyl) -6-t-butoxycarbonyloxybicyclo [2.2.1] heptane (hereinafter referred to as “compound (1-d ′”). ) ") Was obtained.

  Next, a solution obtained by dissolving 27.3 g of sodium dithionite and 19.7 g of sodium hydrogen carbonate in 150 ml of ion-exchanged water was placed in a 500 ml three-necked flask thoroughly purged with nitrogen, and compound (1-d) And a solution of 25 g of the mixture of compound (1-d ′) in 150 ml of acetonitrile was added dropwise at room temperature, and the mixture was stirred at 60 ° C. for 7 hours in a nitrogen atmosphere. Thereafter, the reaction solution was concentrated under reduced pressure to remove acetonitrile, and then 90 mg of sodium tungstate dihydrate and 4.5 g of disodium hydrogen phosphate were added to maintain the pH of the reaction solution, while maintaining a 30% hydrogen peroxide solution. After 8.5 g was carefully added dropwise at room temperature, the mixture was stirred at 60 ° C. for 1 hour. Thereafter, water was removed by concentration under reduced pressure, and the residue was extracted twice with methanol, and then concentrated under reduced pressure to remove methanol, whereby 2- (5-t-butoxycarbonyloxybicyclo [2.2.1]. Hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonic acid sodium (hereinafter referred to as “compound (1-e)”) and 2- (6-t-butoxycarbonyloxybicyclo [2] 2.2.1] 20 g of a mixture of hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonic acid sodium (hereinafter referred to as “compound (1-e ′)”) was obtained.

Next, a solution obtained by dissolving 4.2 g of triphenylsulfonium bromide in 75 ml of ion-exchanged water was placed in a 200 ml eggplant flask, and 4.14 g of a mixture of the compound (1-e) and the compound (1-e ′) and methylene chloride. 75 ml was added at room temperature and stirred at the same temperature for 1 hour. Thereafter, the organic layer was separated, washed 5 times with ion-exchanged water, and concentrated under reduced pressure to give white solid triphenylsulfonium 2- (5-t-butoxycarbonyloxybicyclo [2.2.1] hept. -2-yl) -1,1,2,2-tetrafluoroethanesulfonate and triphenylsulfonium 2- (5-t-butoxycarbonyloxybicyclo [2.2.1] hept-2-yl) -1,1 , 2,2-tetrafluoroethanesulfonate 6.5 g was obtained.
The measurement results of ¹ H-NMR analysis of this mixture are shown in FIG. 2, and the measurement results of mass spectrometry of the cation moiety and the anion moiety are shown in FIGS. 3 and 4, respectively.
This mixture is referred to as “acid generator (A-1)”.

The ¹ H-NMR analysis of the acid generator (A-1) and the acid generators (A1-2) to (A1-10) described below uses “JNM-EX270” manufactured by JEOL Ltd. as a measurement solvent. Performed using CDCl ₃ .
Moreover, the mass analysis of the acid generator (A-1) and the following acid generators (A1-2) to (A1-10) was carried out 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
4 g of 1-n-butoxynaphthalene and 10.6 g of phosphorus pentoxide-methanesulfonic acid mixture were placed in a 300 ml eggplant flask and stirred for 15 minutes at room temperature. Then, 2.4 g of tetramethylene sulfoxide was added dropwise at 0 ° C. Stir for minutes. Thereafter, the temperature was gradually raised to room temperature, and the mixture was further stirred for 1 hour. Then, it cooled again to 0 degreeC, 100 ml of ion-exchange water was added, pH was adjusted to 7.0 with 25% ammonia water, and it stirred at room temperature for 1 hour. Thereafter, the obtained aqueous solution was washed with ether, and then 4.14 g of a mixture of the compounds (1-e) and (1-e ′) and 100 ml of methylene chloride were added at room temperature, followed by stirring at the same temperature for 1 hour. . Thereafter, the organic layer is separated, washed 5 times with ion exchange ion exchange water, concentrated under reduced pressure, and the resulting crude product is subjected to reprecipitation treatment in a methylene chloride / n-hexane system to obtain 1 -(4-n-Butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (5-t-butoxycarbonyloxybicyclo [2.2.1] hept-2-yl) -1,1,2,2- Tetrafluoroethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (6-t-butoxycarbonyloxybicyclo [2.2.1] hept-2-yl) -1, 6.3 g of a mixture of 1,2,2-tetrafluoroethanesulfonate was obtained.
The measurement result of the mass spectrometry of the cation part of this mixture is shown in FIG.
This mixture is referred to as “acid generator (A-2)”.

Synthesis example 3
A solution prepared by dissolving 3.8 g of diphenyliodonium chloride in 80 ml of ion-exchanged water is placed in a 300 ml eggplant flask, and 4.14 g of a mixture of compound (1-e) and compound (1-e ′) and 80 ml of methylene chloride are added. Was added at room temperature and stirred at the same temperature for 1 hour. Thereafter, the organic layer was separated, washed with ion-exchanged water 5 times, and then concentrated under reduced pressure to give white solid diphenyliodonium 2- (5-t-butoxycarbonyloxybicyclo [2.2.1] hept- 2-yl) -1,1,2,2-tetrafluoroethanesulfonate and diphenyliodonium 2- (6-tert-butoxycarbonyloxybicyclo [2.2.1] hept-2-yl) -1,1,2 6.4 g of a mixture of 2-tetrafluoroethanesulfonate was obtained.
The measurement result of the mass spectrometry of the cation part of this mixture is shown in FIG.
This mixture is referred to as “acid generator (A-3)”.

Synthesis example 4
A solution prepared by dissolving 15 g of the mixture of compound (1-c) and compound (1-c ′), 10.4 g of triethylamine, and 0.35 g of 4-dimethylaminopyridine in 60 ml of methylene chloride was placed in a 200 ml eggplant flask. After cooling to 5 ° C. and adding 9.3 g of pivaloyl chloride at the same temperature, the mixture was stirred at room temperature for 12 hours. Thereafter, 250 ml of methylene chloride was added to the reaction solution, washed successively with 5% oxalic acid aqueous solution, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and pale yellow Liquid 2- (2-bromo-1,1,2,2-tetrafluoroethyl) -5-pivaloyloxybicyclo [2.2.1] heptane (hereinafter referred to as “compound (1-f)”) ) And 2- (2-bromo-1,1,2,2-tetrafluoroethyl) -6-pivaloyloxybicyclo [2.2.1] heptane (hereinafter “compound (1-f ′)”) ) Was obtained.

  Next, a solution obtained by dissolving 17.7 g of sodium dithionite and 12.8 g of sodium hydrogen carbonate in 130 ml of ion-exchanged water was placed in a 500 ml three-necked flask thoroughly purged with nitrogen, and compound (1-f) and A solution prepared by dissolving 19.1 g of the mixture of the compound (1-f ′) in 130 ml of acetonitrile was added dropwise at room temperature, and the mixture was stirred at 60 ° C. for 7 hours in a nitrogen atmosphere. Thereafter, the reaction solution was concentrated under reduced pressure to remove acetonitrile, and then 84 mg of sodium tungstate dihydrate and 3.0 g of disodium hydrogen phosphate were added to maintain the pH of the reaction solution, while maintaining a 30% hydrogen peroxide solution. 7 g was carefully added dropwise at room temperature and then stirred at 60 ° C. for 1 hour. Thereafter, the reaction solution was concentrated under reduced pressure to remove water, the residue was extracted twice with methanol, and then distilled under reduced pressure to remove methanol, whereby 2- (5-pivaloyloxybicyclo [2.2. 1] Sodium hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate (hereinafter referred to as “compound (1-g)”) and 2- (6-pivaloyloxybicyclo [ 2.2.1] 15 g of a mixture of sodium hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate (hereinafter referred to as “compound (1-g ′)”) was obtained.

Next, a solution obtained by dissolving 4.2 g of triphenylsulfonium bromide in 75 ml of ion-exchanged water was placed in a 200 ml eggplant flask, 4 g of a mixture of the compound (1-g) and the compound (1-g ′) and 75 ml of methylene chloride. Was added at room temperature and stirred at the same temperature for 1 hour. Thereafter, the organic layer was separated, washed 5 times with ion exchange water, and then concentrated under reduced pressure to give white solid triphenylsulfonium 2- (5-pivaloyloxy-bicyclo [2.2.1] hept-2-yl. Yl) -1,1,2,2-tetrafluoroethanesulfonate and triphenylsulfonium 2- (6-pivaloyloxy-bicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetra 6.0 g of a mixture of fluoroethanesulfonate was obtained.
The measurement result of ¹ H-NMR analysis of this mixture is shown in FIG. 7, and the measurement result of mass spectrometry of the anion portion is shown in FIG.
This mixture is referred to as “acid generator (A-4)”.

Synthesis example 5
A solution prepared by dissolving 36 g of sodium dithionite and 26 g of sodium hydrogen carbonate in 260 ml of ion-exchanged water was placed in a 1-liter three-necked flask thoroughly purged with nitrogen, and the compounds (1-c) and (1-c A solution prepared by dissolving 30 g of the mixture of ') in 260 ml of acetonitrile was added dropwise at room temperature, and the mixture was reacted at 60 ° C for 7 hours under a nitrogen stream. Thereafter, the reaction solution was distilled under reduced pressure to remove acetonitrile, and then 130 mg of sodium tungstate dihydrate and 6.0 g of disodium hydrogen phosphate were added to maintain 30% aqueous hydrogen peroxide while maintaining the pH of the reaction solution. After 14 g was carefully added dropwise at room temperature, the mixture was stirred at 60 ° C. for 1 hour. Thereafter, water was removed by concentration under reduced pressure, and the residue was extracted twice with methanol, and then concentrated under reduced pressure to remove methanol, whereby 2- (5-hydroxybicyclo [2.2.1] hept-2-yl. Yl) sodium 1,1,2,2-tetrafluoroethanesulfonate (hereinafter referred to as “compound (1-h)”) and 2- (6-hydroxybicyclo [2.2.1] hept-2 -Yl) sodium 1,1,2,2-tetrafluoroethanesulfonate "compound (1-h ')". ) Was obtained.

Next, a solution obtained by dissolving 16.8 g of triphenylsulfonium bromide in 400 ml of water was placed in a 2 liter eggplant flask, 12.6 g of a mixture of compound (1-h) and compound (1-h ′) and 300 ml of methylene chloride. At room temperature and stirred for 1 hour. Thereafter, the organic layer was separated, washed 5 times with ion-exchanged water, and concentrated under reduced pressure to give highly viscous oily triphenylsulfonium 2- (5-hydroxybicyclo [2.2.1] hept-2-yl. ) -1,1,2,2-tetrafluoroethanesulfonate (hereinafter referred to as “compound (1-i)”) and triphenylsulfonium 2- (6-hydroxybicyclo [2.2.1] hept-2 35 g of a mixture of -yl) -1,1,2,2-tetrafluoroethanesulfonate (hereinafter referred to as “compound (1-i ′)”) was obtained.
The measurement result of ¹ H-NMR analysis of this mixture is shown in FIG. 9, and the measurement result of mass spectrometry of the anion portion is shown in FIG.
This mixture is referred to as “acid generator (A-5)”.

Synthesis Example 6
A solution prepared by dissolving 10 g of the mixture of compound (1-i) and compound (1-i ′), 3.7 g of triethylamine and 110 mg of 4-dimethylaminopyridine in 20 ml of methylene chloride was placed in a 100 ml eggplant flask and brought to 5 ° C. After cooling and adding 3.1 g of methanesulfonyl chloride at the same temperature, the mixture was stirred at room temperature for 12 hours. Thereafter, 150 ml of methylene chloride was added to the reaction solution, and the organic layer was washed successively with 5% aqueous oxalic acid solution and ion-exchanged water, and concentrated under reduced pressure. Thereafter, the obtained residue was purified by silica gel column chromatography (methylene chloride: methanol = 10: 1) to give triphenylsulfonium 2- (5-methanesulfonyloxybicyclo [2.2.1] heptoid as a highly viscous oil. -2-yl) -1,1,2,2-tetrafluoroethanesulfonate and triphenylsulfonium 2- (6-methanesulfonyloxybicyclo [2.2.1] hept-2-yl) -1,1,2 , 2-tetrafluoroethanesulfonate mixture 7.7g was obtained.
The measurement result of ¹ H-NMR analysis of this mixture is shown in FIG. 11, and the measurement result of mass spectrometry of the anion portion is shown in FIG.
This mixture is referred to as “acid generator (A-6)”.

Synthesis example 7
A solution prepared by dissolving 10 g of the mixture of compound (1-i) and compound (1-i ′), 3.7 g of triethylamine and 110 mg of 4-dimethylaminopyridine in 20 ml of methylene chloride was placed in a 100 ml eggplant flask and brought to 5 ° C. After cooling, 3.9 g of i-propanesulfonyl chloride was added at the same temperature, followed by stirring at room temperature for 12 hours. Thereafter, 150 ml of methylene chloride was added to the reaction solution, and the organic layer was washed successively with 5% aqueous oxalic acid solution and ion-exchanged water, and concentrated under reduced pressure. Thereafter, the obtained residue was purified by silica gel column chromatography (methylene chloride: methanol = 10: 1) to give highly viscous oily triphenylsulfonium 2- (5-i-propanesulfonyloxybicyclo [2.2.1]. ] Hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate and triphenylsulfonium 2- (6-i-propanesulfonyloxybicyclo [2.2.1] hept-2-yl) -1 , 1,2,2-tetrafluoroethanesulfonate 6.3 g of a mixture was obtained.
The measurement result of ¹ H-NMR analysis of this mixture is shown in FIG. 13, and the measurement result of mass spectrometry of the anion portion is shown in FIG.
This mixture is referred to as “acid generator (A-7)”.

Synthesis example 8
A solution prepared by dissolving 10 g of the mixture of compound (1-i) and compound (1-i ′), 3.7 g of triethylamine and 110 mg of 4-dimethylaminopyridine in 20 ml of methylene chloride was placed in a 100 ml eggplant flask and brought to 5 ° C. After cooling and adding 5.0 g of n-hexanesulfonyl chloride at the same temperature, the mixture was stirred at room temperature for 12 hours. Thereafter, 150 ml of methylene chloride was added to the reaction solution, and the organic layer was washed successively with 5% oxalic acid aqueous solution and ion-exchanged water, and then concentrated under reduced pressure. Thereafter, the obtained residue was purified by silica gel column chromatography (methylene chloride: methanol = 15: 1) to give highly viscous oily triphenylsulfonium 2- (5-n-hexanesulfonyloxybicyclo [2.2.1]. ] Hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate and triphenylsulfonium 2- (6-n-hexanesulfonyloxybicyclo [2.2.1] hept-2-yl) -1 , 1,2,2-tetrafluoroethane sulfonate 7.2 g was obtained.
The measurement result of ¹ H-NMR analysis of this mixture is shown in FIG. 15, and the measurement result of mass spectrometry of the anion portion is shown in FIG.
This mixture is referred to as “acid generator (A-8)”.

Synthesis Example 9
A solution prepared by dissolving 62 g of a mixture of compound (1-c) and compound (1-c ′) and 140 g of triethylamine in 1000 ml of dimethyl sulfoxide was placed in a 2-liter three-necked flask equipped with a thermometer, and the reaction solution temperature was adjusted. While maintaining the temperature at 30 ° C. or lower, 102 g of sulfur trioxide-pyridine complex was added, followed by stirring at room temperature for 3 hours. Thereafter, 7 liters of cold water and 6M hydrochloric acid were added to the reaction solution to adjust the pH to around 2, and then the aqueous layer was extracted four times with ethyl acetate. Thereafter, the organic layer was washed successively with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Thereafter, the obtained residue was purified by distillation under reduced pressure at 115 ° C. and 8 mmHg, whereby 2- (2-bromo-1,1,2,2-tetrafluoroethyl) -bicyclo [2. 2.1] Heptane-5-one (hereinafter referred to as “compound (2-a)”) and 2- (2-bromo-1,1,2,2-tetrafluoroethyl) -bicyclo [2.2 .1] 49 g of a mixture of heptane-6-one (hereinafter referred to as “compound (2-a ′)”) was obtained.
The measurement result of ¹ H-NMR analysis of this mixture is shown in FIG.

  Next, a solution prepared by dissolving 32 g of a mixture of compounds (2-a) and (2-a ′), 18.3 g of ethylene glycol and 18.3 g of trimethyl orthoformate in 61 g of tetrahydrofuran was placed in a 500 ml eggplant flask, and p-toluene. A solution of 0.472 g of sulfonic acid monohydrate dissolved in 18.5 ml of tetrahydrofuran was added dropwise at room temperature, and the mixture was stirred at the same temperature for 12 hours. Thereafter, 15.6 g of triethylamine was added, and the mixture was concentrated under reduced pressure, ion-exchanged water was added, and the aqueous layer was extracted twice with n-hexane. Thereafter, the organic layer was concentrated under reduced pressure to give 2- (2-bromo-1,1,2,2-tetrafluoroethyl) -5- (1,3-dioxolanspiro) -bicyclo [2 2.1] heptane (hereinafter referred to as “compound (2-b)”) and 2- (2-bromo-1,1,2,2-tetrafluoroethyl) -6- (1,3-dioxolane) 39.3 g of a mixture of (spiro) -bicyclo [2.2.1] heptane (hereinafter referred to as “compound (2-b ′)”) was obtained.

  Next, a solution prepared by dissolving 37.5 g of sodium dithionite and 27.3 g of sodium hydrogen carbonate in 240 ml of ion-exchanged water was placed in a 1-liter three-necked flask thoroughly purged with nitrogen, and compound (2-b) And a solution of 39 g of the mixture of the compound (2-b ′) in 240 ml of acetonitrile was added dropwise at room temperature, followed by stirring at 80 ° C. for 7 hours under a nitrogen stream. Thereafter, the reaction solution was concentrated under reduced pressure to remove acetonitrile, and then the aqueous layer was extracted with ethyl acetate. The organic layer was washed three times with saturated brine and concentrated under reduced pressure to give a white solid. 2- {5- (1,3-dioxolanspiro) -bicyclo [2.2.1] hept-2-yl} -1,1,2,2-tetrafluoroethanesulfinate (hereinafter referred to as “compound (2 -C) ")) and 2- {6- (1,3-dioxolanspiro) -bicyclo [2.2.1] hept-2-yl} -1,1,2,2-tetrafluoroethanesulfine. 39.8 g of a mixture of sodium acid (hereinafter referred to as “compound (2-c ′)”) was obtained.

  Next, a solution of 39.8 g of the mixture of compound (2-c) and compound (2-c ′) in 240 ml of ion-exchanged water was placed in a 1-liter eggplant flask, and 210 mg of sodium tungstate dihydrate and phosphorus were added. 6.0 g of disodium oxyhydrogen was added and 20 g of 30% aqueous hydrogen peroxide was carefully added dropwise at room temperature while maintaining the pH of the reaction solution, followed by stirring at the same temperature for 2 hours. Thereafter, 93 g of 35% hydrochloric acid was added dropwise to the reaction solution and stirred at the same temperature for 3 hours, and then 120 g of sodium chloride was added to the reaction solution and further stirred for 1 hour. Thereafter, the reaction solution was suction filtered to collect a white solid, and the obtained solid was washed with a small amount of saturated brine and extracted twice with methanol. Thereafter, the solution was concentrated under reduced pressure to remove methanol, whereby sodium 2- (5-oxobicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate (hereinafter, , And “compound (2-d)”) and sodium 2- (6-oxobicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate ( Hereinafter, 30 g of a mixture of “compound (2-d ′)” was obtained.

Next, a solution obtained by dissolving 26.3 g of triphenylsulfonium bromide in 600 ml of water is placed in a 2 liter eggplant flask, and 20 g of a mixture of the compound (2-d) and the compound (2-d ′) and 500 ml of methylene chloride are added. The mixture was added at room temperature and stirred at the same temperature for 1 hour. Thereafter, the organic layer was separated, washed with ion-exchanged water 5 times, and concentrated under reduced pressure to give highly viscous oily triphenylsulfonium 2- (5-oxobicyclo [2.2.1] hept-2-yl. ) -1,1,2,2-tetrafluoroethanesulfonate and triphenylsulfonium 2- (6-oxobicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethane 32 g of a mixture of sulfonates was obtained.
The measurement result of ¹ H-NMR analysis of this mixture is shown in FIG. 18, and the measurement result of mass spectrometry of the anion portion is shown in FIG.
This mixture is referred to as “acid generator (A-9)”.

Synthesis Example 10
A solution of 39.8 g of the mixture of compound (2-c) and compound (2-c ′) in 84 ml of ion-exchanged water was placed in a 300 ml eggplant flask and cooled to 5 ° C. Chlorine gas was bubbled for 15 minutes or more. Thereafter, the aqueous layer was removed by decantation, and the oily substance accumulated at the bottom of the flask was dissolved in 185 g of methanol, and 93 g of 35% hydrochloric acid was added dropwise at room temperature, followed by stirring at the same temperature for 1 hour. Thereafter, the reaction solution was concentrated under reduced pressure to remove methanol, 120 ml of methylene chloride was added, and then the organic layer was washed four times with ion-exchanged water. Thereafter, the mixture was concentrated under reduced pressure to remove methylene chloride, whereby 2- (5-oxobicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonyl chloride (hereinafter referred to as “(2-oxobicyclo [2.2.1] hept-2-yl)”). , “Compound (2-e)”) and 2- (6-oxobicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonyl chloride (hereinafter referred to as “compound (2-e)”). , 28.9 g of a mixture of “compound (2-e ′)”.

Next, 28.9 g of a mixture of the compound (2-e) and the compound (2-e ′), 173 g of acetone, and N-hydroxybicyclo [2.2.1] hept-5-ene-2,3-dicarboximide 16 .8 g was sequentially put into a 500 ml eggplant flask and cooled to 5 ° C., a solution of 10 g of triethylamine dissolved in 20 g of acetone was added dropwise at the same temperature, and the mixture was stirred at the same temperature for 3 hours. Thereafter, the reaction solution is dropped into a large amount of water, the obtained precipitate is recrystallized twice in a methanol / water system, the obtained crystal is dissolved in methylene chloride, and the organic layer is dissolved in 5% oxalic acid aqueous solution and ions. After sequentially washing with exchanged water, the solution was concentrated under reduced pressure to remove methylene chloride, whereby N- {2- (5-oxobicyclo [2.2.1] hept-2-yl) -1,1,2, 2-tetrafluoroethanesulfonyloxy} bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and N- {2- (6-oxobicyclo [2.2.1] hept-2 1-g of a mixture of -yl) -1,1,2,2-tetrafluoroethanesulfonyloxy} bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide was obtained.
The measurement result of ¹ H-NMR analysis and the measurement result of mass spectrometry of this mixture are shown in FIGS. 20 and 21, respectively.
This mixture is referred to as “acid generator (A-10)”.

[Synthesis of acid-dissociable group-containing resin (B)]
Synthesis Example 11
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 performed in a nitrogen atmosphere. Polymerization was carried out 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 solidify and purify the resulting resin.
Next, 150 g of propylene glycol monomethyl ether was again 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 dropped 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 had an Mw of 16,000 and an 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 was It was confirmed that the copolymer was 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 -11) 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 13
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 14
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 It was confirmed that 10 mol% of the ethoxyethyl group was substituted with a t-butyl group.
This resin is referred to as “resin (B-4)”.

Synthesis Example 15
2-butanone (200 g) was obtained by adding 53.69 g of 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl methacrylate and 46.31 g of 2-methyladamantan-2-yl methacrylate. And a monomer solution charged with 4.04 g of dimethylazobisbutyrate was prepared.
Separately, a 1,000 ml three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes. Thereafter, the contents were heated to 80 ° C. while stirring, and the monomer solution was added dropwise over 4 hours using a dropping funnel. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After the polymerization, the reaction solution was cooled with water and cooled to 30 ° C. or lower, poured into 2,000 g of methanol, and the precipitated white powder was filtered off. Thereafter, the obtained white powder was mixed twice with 400 g of methanol and washed in a slurry state, then separated in a furnace and dried at 50 ° C. for 17 hours to obtain a white powder resin.
This resin has Mw of 9,700, and as a result of ¹³ C-NMR analysis, 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl methacrylate and methacrylic acid It was confirmed that the copolymer was a copolymer having a molar ratio of 59.6: 40.4 with 2-methyladamantan-2-yl acid.
This resin is referred to as "resin (B-5)".

Synthesis Example 16
40.90 g of 2-methyladamantan-2-yl methacrylate, 15.47 g of 3-hydroxyadamantan-1-yl methacrylate and 5-oxo-4-oxatricyclomethacrylate [4.2.1.0 ^3,7 A monomer solution was prepared by dissolving 43.64 g of nonan-2-yl in 200 g of 2-butanone and adding 4.02 g of dimethylazobisbutyrate.
Separately, a 1,000 ml three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes. Thereafter, the contents were heated to 80 ° C. while stirring, and the monomer solution was added dropwise over 4 hours using a dropping funnel. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After the polymerization, the reaction solution was cooled with water and cooled to 30 ° C. or lower, poured into 2,000 g of methanol, and the precipitated white powder was filtered off. Thereafter, the obtained white powder was mixed twice with 400 g of methanol and washed in a slurry state, then separated in a furnace and dried at 50 ° C. for 17 hours to obtain a white powder resin.
This resin has Mw of 9,200, and as a result of ¹³ C-NMR analysis, 2-methyladamantan-2-yl methacrylate, 3-hydroxyadamantan-1-yl methacrylate and 5-oxo-4-methacrylate. It was confirmed that the copolymer was a copolymer having a molar ratio of copolymerization with oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl of 36.2: 15.2: 48.6. This resin is referred to as "resin (B-6)".

Synthesis Example 17
43.66 g of 1- (adamantan-1-yl) -1-methylethyl methacrylate, 14.74 g of 3-hydroxyadamantan-1-yl methacrylate and 5-oxo-4-oxatricyclomethacrylate [4.2. 1.0 ^3,7 ] 43.66 g of nonan-2-yl was dissolved in 200 g of 2-butanone, and a monomer solution charged with 3.83 g of dimethylazobisisobutyrate was prepared.
Separately, a 1,000 ml three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes. Thereafter, the contents were heated to 80 ° C. while stirring, and the monomer solution was added dropwise over 4 hours using a dropping funnel. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After the polymerization, the reaction solution was cooled with water and cooled to 30 ° C. or lower, poured into 2,000 g of methanol, and the precipitated white powder was filtered off. Thereafter, the obtained white powder was mixed twice with 400 g of methanol and washed in a slurry state, then separated in a furnace and dried at 50 ° C. for 17 hours to obtain a white powder resin.
This resin has an Mw amount of 9,600, and as a result of ¹³ C-NMR analysis, 1- (adamantan-1-yl) -1-methylethyl methacrylate, 3-hydroxyadamantan-1-yl methacrylate and methacrylic acid are obtained. Copolymer with acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl in a copolymer having a molar ratio of 35.6: 15.1: 49.3 It was confirmed that there was.
This resin is referred to as "resin (B-7)".

Synthesis Example 18
16.13 g of 2-ethyladamantan-2-yl methacrylate, 40.58 g of 2-methyladamantan-2-yl methacrylate and 5-oxo-4-oxatricyclo methacrylate [4.2.1.0 ^3,7 A monomer solution was prepared by dissolving 3.29 g of nonan-2-yl in 200 g of 2-butanone and adding 3.99 g of dimethylazobisisobutyrate.
Separately, a 1,000 ml three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes. Thereafter, the contents were heated to 80 ° C. while stirring, and the monomer solution was added dropwise over 4 hours using a dropping funnel. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After the polymerization, the reaction solution was cooled with water and cooled to 30 ° C. or lower, poured into 2,000 g of methanol, and the precipitated white powder was filtered off. Thereafter, the obtained white powder was mixed twice with 400 g of methanol and washed in a slurry state, then separated in a furnace and dried at 50 ° C. for 17 hours to obtain a white powder resin.
This resin has an Mw of 8,900, and as a result of ¹³ C-NMR analysis, 2-ethyladamantan-2-yl methacrylate, 2-methyladamantan-2-yl methacrylate, and 5-oxo-4-methacrylate. It was confirmed that the copolymer had a copolymer molar ratio with oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl of 13.7: 38.2: 48.1.
This resin is referred to as "resin (B-8)".

Synthesis Example 19
42.44 g of 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl acrylate, 15.10 g of 3-hydroxyadamantan-1-yl acrylate and 2-acrylic acid 2- A monomer solution was prepared by dissolving 42.46 g of ethyladamantan-2-yl in 200 g of 2-butanone and adding 4.17 g of dimethylazobisbutyrate. Separately, a 1,000 ml three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes. Thereafter, the contents were heated to 80 ° C. while stirring, and the monomer solution was added dropwise over 4 hours using a dropping funnel. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After the polymerization, the reaction solution was cooled with water and cooled to 30 ° C. or lower, poured into 2,000 g of methanol, and the precipitated white powder was filtered off. Thereafter, the obtained white powder was mixed twice with 400 g of methanol and washed in a slurry state, then separated in a furnace and dried at 50 ° C. for 17 hours to obtain a white powder resin.
This resin had an Mw of 10,200, and as a result of ¹³ C-NMR analysis, 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl acrylate and acrylic It was confirmed that the copolymer had a molar ratio of copolymerization of 3-hydroxyadamantan-1-yl acid and 2-ethyladamantan-2-yl acrylate of 49.2: 15.3: 35.5.
This resin is referred to as "resin (B-9)".

Synthesis Example 20
5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] non-2-yl methacrylate 55.00 g, 11.70 g 3-hydroxyadamantan-1-yl methacrylate and 1-acrylic acid 1- A monomer solution was prepared by dissolving 33.31 g of ethylcyclopentyl in 200 g of 2-butanone and adding 4.56 g of dimethylazobisbutyrate.
Separately, a 1,000 ml three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes. Thereafter, the contents were heated to 80 ° C. while stirring, and the monomer solution was added dropwise over 4 hours using a dropping funnel. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After the polymerization, the reaction solution was cooled with water and cooled to 30 ° C. or lower, poured into 2,000 g of methanol, and the precipitated white powder was filtered off. Thereafter, the obtained white powder was mixed twice with 400 g of methanol and washed in a slurry state, then separated in a furnace and dried at 50 ° C. for 17 hours to obtain a white powder resin.
This resin has an Mw of 8,500, and as a result of ¹³ C-NMR analysis, 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl methacrylate and methacrylic acid It was confirmed that the copolymer was a copolymer having a molar ratio of copolymerization of 3-hydroxyadamantan-1-yl acid and 1-ethylcyclopentyl acrylate of 53.7: 11.1: 35.2.
This resin is referred to as “resin (B-10)”.

[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 case of exposure with 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 determined 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 exposed with an ArF excimer laser, the line width of a 1L / 10S pattern (0.16 um line / 1.6 um space) having a design dimension of 0.16 um exceeds 70% of the mask design dimension (0.16 um). “Good” and “bad” when 70% or less.

Nano edge roughness:
A line pattern of a line and space pattern (1L1S) having a design dimension of 0.22 μm was observed with a scanning electron microscope. FIG. 22 shows a schematic diagram of the pattern (however, the unevenness is exaggerated from the actual state). For the shape observed in each example, the difference ΔCD between the line width at the most marked portion of the unevenness generated along the lateral surface of the line pattern and the design line width 0.22 μm was measured, and the ΔCD was 0.044 μm. When it was less than 0.044 μm, it was judged as “bad”. However, when exposed with an ArF excimer laser, a line pattern of a line-and-space pattern (1L1S) having a design dimension of 0.16 μm was observed with a scanning electron microscope, and was generated along the lateral surface of the line pattern. The difference ΔCD with respect to the design line width of 0.16 μm at the most conspicuous portion of the irregularities was measured.
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.

Example 1 ～7,9～21 and 23-25 and Comparative Examples 1-4
Each component shown in Table 1-1 and Table 1-2 was mixed to make 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 Nikon stepper NSR2205 EX12B (numerical aperture: 0.55) was used, and an ArF excimer laser was used as the exposure light source. In the examples using “ArF” in Table 1, a Nikon ArF excimer laser exposure apparatus (numerical aperture: 0.55) is used, and in an example using an electron beam as an exposure light source, Hitachi, Ltd. Using an electron beam lithography apparatus HL700 (manufactured by Co., Ltd.) (acceleration voltage 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% 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 3 shows the evaluation results of each resist.

Example 26, 28 and 29 and Comparative Examples 5-6
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% tetramethylammonium hydroxide aqueous solution was used and developed by the paddle method at 23 ° C. for 1 minute, followed by washing with pure water and drying to form a resist pattern. Table 6 shows the evaluation results of each resist.

In Table 1-1, Table 1-2, and Table 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: N- (nonafluoro-n- Butanesulfonyloxy) bicyclo [2.2. 1] hept-5-ene-2,3-dicarboximide a-3: triphenylsulfonium nonafluoro-n-butanesulfonate a-4: triphenylsulfonium perfluoro-n-octanesulfonate a-5: 1- ( 4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate a-6: bis (cyclohexylsulfonyl) diazomethane

Alkali-soluble resin C-1: 4-hydroxystyrene / styrene copolymer (copolymerization molar ratio = 78: 22,
Mw = 3,100, Mw / Mn = 1.13)
Acid diffusion controller E-1: Tri-n-octylamine E-2: Triethanolamine E-3: 2-Phenylbenzimidazole E-4: 1,2-dimethylimidazole E-5: Nt-butoxycarbonyl 2-Phenylbenzimidazole
Crosslinker D-1: N, N, N, N-tetra (methoxymethyl) glycoluril
Other additive F-1: t-butoxycarbonylmethyl deoxycholate
Solvent S-1: Ethyl lactate S-3: Propylene glycol monomethyl ether acetate S-4: 2-heptanone S-5: Cyclohexanone S-6: γ-Butyrolactone

  From Table 3 and Table 6, the radiation sensitive resin composition of the Example which used the compound which has a structure (1) or a structure (2) as a radiation sensitive acid generator is the radiation sensitive resin composition of a comparative example, and In comparison, it is clear that both have good mask pattern dependency and good nanoedge roughness, so that they are excellent in smoothness, and have high resolution and high sensitivity.

It is a figure which shows the measurement result of the < ¹ > H-NMR analysis of the mixture of a compound (1-c) and a compound (1-c '). 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 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 cation 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 mass spectrometry of the anion part 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 anion part of an acid generator (A-5). It is a figure which shows the measurement result of the ¹ H-NMR analysis 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). It is a figure which shows the measurement result of the < ¹ > H-NMR analysis of an acid generator (A-7). It is a figure which shows the measurement result of the mass spectrometry of the anion part of an acid generator (A-7). It is a figure which shows the measurement result of the < ¹ > H-NMR analysis of an acid generator (A-8). It is a figure which shows the measurement result of the mass spectrometry of the anion part of an acid generator (A-8). It is a figure which shows the measurement result of the < ¹ > H-NMR analysis of the mixture of a compound (2-a) and a compound (2-a '). It is a figure which shows the measurement result of the ¹ H-NMR analysis of an acid generator (A-9). It is a figure which shows the measurement result of the mass spectrometry of the anion part of an acid generator (A-9). It is a figure which shows the measurement result of the ¹ H-NMR analysis of an acid generator (A-10). It is a figure which shows the measurement result of the mass spectrometry of an acid generator (A-10). It is a figure explaining the evaluation point of nano edge roughness.

Claims (6)

(A) a radiation-sensitive acid generator and (B) an alkali-insoluble or alkali-insoluble resin having an acid-dissociable group, the resin being alkali-soluble when the acid-dissociable group is dissociated And the component (A) comprises a compound having at least one structure represented by the following general formula (1) or the following general formula (2), and the component (B) is represented by the following general formula (42) Resin (B1) consisting only of a repeating unit and a repeating unit obtained by protecting a phenolic hydroxyl group in the repeating unit with an acid dissociable group, and a repeating unit represented by the following general formula (43) or the following general formula (44) A positive-type radiation-sensitive resin composition selected from the group of resins (B2) comprising only one or more types and a repeating unit represented by the following general formula (45).

[In the general formula (1), R ¹ represents a hydrogen atom or a monovalent substituent, p is an integer of 1 or more, and when R ² is present, R ¹ O— and R ² are included therein. In the presence of a plurality of R ¹ O— groups, at least two R ¹ O— may be bonded to each other via atoms contained in at least two R ^1. To form a ring.
In General Formula (1) and General Formula (2), Z ¹ and Z ² each independently represent a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, and Y ¹ is a single atom. A bond or a divalent group; R ² represents a monovalent or divalent substituent; q is an integer of 0 or more; and n is an integer of 0 to 5. ]

[In the general formula (42), R ¹⁷ represents a hydrogen atom or a monovalent organic group, a plurality of R ¹⁷ may be the same as or different from each other, and a and b are each an integer of 1 to 3. ]

[In General Formula (43), General Formula (44), and General Formula (45), R ¹⁸ , R ^20, and R ²¹ independently represent a hydrogen atom or a methyl group, and in General Formula (43), R ¹⁹ Are independently of each other a hydrogen atom, a hydroxyl group, a cyano group, or a —COOR ²³ group (where R ²³ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic group having 3 to 20 carbon atoms). Represents an alkyl group of the formula).
In the general formula (45), R ²² each independently represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof or a linear or branched alkyl group having 1 to 4 carbon atoms, and At least one of R ²² is the alicyclic hydrocarbon group or a derivative thereof, or any two R ²² are bonded to each other, and each having 2 to 4 carbon atoms together with the carbon atoms to which they are bonded. A valent alicyclic hydrocarbon group or a derivative thereof, and the remaining R ²² is a linear or branched alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon having 4 to 20 carbon atoms Represents a group or a derivative thereof. ] The component (A) is selected from the group consisting of compounds represented by the following general formula (3) or general formula (4) and compounds represented by the following general formula (7) or general formula (8). The positive radiation sensitive resin composition according to claim 1.

[In General formula (3), R < ¹ > and p are synonymous with R < ¹ > and p in the said General formula (1), respectively.
In General Formula (3) and General Formula (4), Z ¹ , Z ² , Y ¹ , R ² , q, and n are Z ¹ , Z ² , and Z in General Formula (1) and General Formula (2), respectively. It is synonymous with Y < ¹ >, R < ² >, q and n, and M ^<+> shows the iodonium cation represented by the sulfonium cation represented by the following general formula (5), or the following general formula (6).

{In the general formula (5), each R ³ is independently a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms. Or any two or more of R ³ are bonded to each other to form a ring together with the sulfur atom in the formula. }

{In General Formula (6), each R ⁴ is independently a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms. Or two R ^{4 's} are bonded to each other to form a ring together with the iodine atom in the formula. }

{In General formula (7), R < ¹ > and p are synonymous with R < ¹ > and p in the said General formula (1), respectively.
In the general formula (7) and the general formula (8), Z ¹ , Z ² , Y ¹ , R ² , q, and n are Z ¹ , Z ² , and Z in the general formula (1) and the general formula (2), respectively. Y ¹ , R ² , q and n are synonymous, and R ⁵ and R ⁶ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent organic group, or R ⁵ and R ⁶ are To form a ring together with the carbon atom to which they are bonded, and Y ² represents a single bond, a double bond or a divalent group. }] Y ¹ in the general formula (1) and the general formula (2) is a single bond, —O—, 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 or 1,4-phenylene group The positive-type radiation-sensitive resin composition according to claim 1 or 2, wherein (A) a radiation-sensitive acid generator, (C) an alkali-soluble resin, and (D) a compound capable of crosslinking the alkali-soluble resin in the presence of an acid, and (A) the component is represented by the following general formula (1) or A resin comprising a compound having one or more structures represented by the following general formula (2), wherein the component (C) comprises only one or more repeating units represented by the following general formulas (49) to (51) ( C1), and one or more of the repeating units represented by the following general formulas (49) to (51) and one of the repeating units in which the polymerizable unsaturated bond of the vinyl aromatic compound or (meth) acrylate is cleaved A negative radiation-sensitive resin composition selected from the group consisting of the above-mentioned resins (C2).

[In the general formula (1), R ¹ represents a hydrogen atom or a monovalent substituent, p is an integer of 1 or more, and when R ² is present, R ¹ O— and R ² are included therein. In the presence of a plurality of R ¹ O— groups, at least two R ¹ O— may be bonded to each other via atoms contained in at least two R ^1. To form a ring.
In General Formula (1) and General Formula (2), Z ¹ and Z ² each independently represent a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, and Y ¹ is a single atom. A bond or a divalent group; R ² represents a monovalent or divalent substituent; q is an integer of 0 or more; and n is an integer of 0 to 5. ]

[In General Formula (49) and General Formula (50), R ²⁵ and R ²⁷ each independently represent a hydrogen atom or a methyl group, R ²⁶ represents a hydroxyl group, a carboxyl group, —R ²⁸ COOH,
—OR ²⁸ COOH, —OCOR ²⁸ COOH, or —COOR ²⁸ COOH {provided that each R ²⁸ independently represents — (CH ₂ ) _c —, and c is an integer of 1 to 4. }. ] The component (A) is selected from the group consisting of compounds represented by the following general formula (3) or general formula (4) and compounds represented by the following general formula (7) or general formula (8). The negative radiation-sensitive resin composition according to claim 4.

[In General formula (3), R < ¹ > and p are synonymous with R < ¹ > and p in the said General formula (1), respectively.
In General Formula (3) and General Formula (4), Z ¹ , Z ² , Y ¹ , R ² , q, and n are Z ¹ , Z ² , and Z in General Formula (1) and General Formula (2), respectively. It is synonymous with Y < ¹ >, R < ² >, q and n, and M ^<+> shows the iodonium cation represented by the sulfonium cation represented by the following general formula (5), or the following general formula (6).

{In the general formula (5), each R ³ is independently a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms. Or any two or more of R ³ are bonded to each other to form a ring together with the sulfur atom in the formula. }

{In General Formula (6), each R ⁴ is independently a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms. Or two R ^{4 's} are bonded to each other to form a ring together with the iodine atom in the formula. }

{In General formula (7), R < ¹ > and p are synonymous with R < ¹ > and p in the said General formula (1), respectively.
In the general formula (7) and the general formula (8), Z ¹ , Z ² , Y ¹ , R ² , q, and n are Z ¹ , Z ² , and Z in the general formula (1) and the general formula (2), respectively. Y ¹ , R ² , q and n are synonymous, and R ⁵ and R ⁶ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent organic group, or R ⁵ and R ⁶ are To form a ring together with the carbon atom to which they are bonded, and Y ² represents a single bond, a double bond or a divalent group. }] Y ¹ in the general formula (1) and the general formula (2) is a single bond, —O—, 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 or 1,4-phenylene group The negative radiation sensitive resin composition of Claim 4 or Claim 5 which is.

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