JP2011093868A - Method for producing sulfonium salt containing cyclic structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new method for producing a sulfonium salt, which has a few number of processes and produces a sulfonium salt by a simple operation. <P>SOLUTION: The method for producing a sulfonium salt represented by general formula (7) is provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a sulfonium salt useful for a photoacid generator used in the fields of paints, coating agents, photocurable adhesives, semiconductor photolithography and the like.

  Photoacid generators are used in the fields of paints, coating agents, photo-curing adhesives and the like because they can generate an acid by light irradiation and cationically polymerize an epoxy monomer, an oxetane monomer, and the like. In the field of semiconductor photolithography, a chemically amplified resist that becomes soluble in an alkali developer by removing a protecting group that has insolubilized the resist resin by the catalytic action of an acid generated from a photoacid generator upon exposure. Is used.

The molecular structure of the photoacid generator is composed of a cation moiety that absorbs irradiation light and an anion moiety that is a source of acid generation. Representative examples of the photoacid generator include onium salts such as sulfonium salts and iodonium salts. The sulfonium salt has better storage stability than the iodonium salt, and the sulfonium salt having various structures having an absorption wavelength on the longer wavelength side has been developed. As the anion site of the sulfonium salt, SbF ₆ ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ^{− and the} like are used, but Sb is a deleterious substance. Since they are poisonous, onium salts containing these metal elements have safety problems and their use is limited. In the field of semiconductor photolithography, an anion site containing a metal element (for example, SbF ₆ ⁻ and AsF ₆ ⁻ ), an anion site containing a phosphorus element (for example PF ₆ ⁻ ), an anion site containing a boron element (for example, BF ₄ ^−). And B (C ₆ F ₅ ) ₄ ⁻ ) and the like cannot be used for chemically amplified resist applications. This is because such an element becomes an impurity and greatly affects transistor performance (see, for example, Non-Patent Document 1).

からなる環状構造をもつスルホニウム塩が挙げられる。 Examples of the photoacid generator that solves the above problem include a sulfonium salt in which a cation moiety is composed of arylsulfonium and an anion moiety is composed of a fluorine-containing sulfonimidate.
Aryl sulfonium such as triphenylsulfonium is used as the cation moiety of the sulfonium salt. However, these arylsulfonium have a light absorption wavelength of only up to about 320 nm, and the wavelength of 350 nm or more by LED lamps or i-line steppers. In the case of curing with this light, the sensitivity is remarkably lowered.
As a photoacid generator for solving the above problem, for example, the cation moiety has the following structure (8):

A sulfonium salt having a cyclic structure consisting of

スキーム１中、Ｍ’はアルカリ金属を表し、Ｒｆ’’及びＲｆ’’’はフッ素残基を表す。｝に示すように以下の２つの工程から合成される（例えば、特許文献４を参照）：
第１工程：環状スルホキシド化合物とアリール化合物から、酸と脱水剤の存在下スルホン酸スルホニウムを合成する。
第２工程：スルホン酸スルホニウムとスルホンイミド塩とを反応させて、スルホニウム塩を合成する。 The sulfonium salt having the above cyclic structure (8) has the following scheme 1:

In Scheme 1, M ′ represents an alkali metal, and Rf ″ and Rf ′ ″ represent a fluorine residue. } Is synthesized from the following two steps (see, for example, Patent Document 4):
First step: Sulfonium sulfonate is synthesized from a cyclic sulfoxide compound and an aryl compound in the presence of an acid and a dehydrating agent.
Second step: A sulfonium salt is reacted with a sulfonimide salt to synthesize a sulfonium salt.

  However, in the production method described above, two steps are required until a sulfonium salt is obtained from the sulfoxide compound, and in each step, a complicated processing operation after completion of the reaction is required. In addition, trace amounts of fluorine-substituted sulfonate ions may remain as impurities, and when the photoacid generator obtained by the above method is used for the polymerization of epoxy compounds or oxetane compounds, the determination of fluorine-substituted sulfonate ions. There is a possibility that the polymerization reaction is inhibited by the nuclei and the polymerization activity is lowered.

  As described above, since the conventional method for producing a sulfonium salt involves complicated operations and there is a possibility of residual impurities, it is possible to produce a sulfonium salt with a small number of steps and a small amount of impurities by a simple operation. Development of such a method was strongly desired.

JP 2008-89777 A JP-T-2001-512714 JP 2005-275153 A JP 2007-114719 A JP 2008-222657 A JP 2001-288193 A

2. Supervised by Mitsuru Ueda, edited by Radtech Study Group, “Latest Trends in UV / EB Curing Technology”, Chapter 2 Material Development Trends. Photopolymerization initiator CMC Publishing (2006) Journal of The Electrochemical Society Vol. 151, A1363 (2004) Journal of Fluorine Chemistry Vol. 125, p. 243 (2004) Inorganic Chemisty 23 3720 (1984) Inorganic Chemisty 32, 5007 (1993) Journal of Fluorine Chemistry 125 243 (2004)

  In view of the above problems, the problem to be solved by the present invention is to provide a novel method for producing a sulfonium salt in which the number of steps is small and a sulfonium salt can be produced by a simple operation.

  The present inventors diligently studied a method for producing a sulfonium salt from a cyclic sulfoxide compound, and as a result of repeated experiments, the cyclic sulfoxide compound, the aromatic compound, and the sulfonimide are brought into contact and mixed in the presence of a dehydrating agent. As a result, it was found that a sulfonium salt can be produced with high yield in one step, and the present invention has been completed. That is, the present invention is as follows.

｛式中、Ｘは、単結合、カルボニル基、アルキレン基、スルホニル基、カルボニルオキシ基、カルボニルアミノ基、スルホニルアミド基、エーテル基、チオエーテル基又はジスルフィド基であり、ｍは、０〜４の整数であり、ｎは、０〜４の整数であり、Ｒ¹及びＲ²は、各々独立に、水素原子、水酸基、ハロゲン原子、シアノ基、ニトロ基、カルボキシル基、アルコキシ基、アルキル基、又は下記一般式（２）：

（式中、Ｒ³は、ハロゲン原子、炭素数１〜８個のアルキル基、炭素数１〜８個のアルコキシ基、フェノキシ基、炭素数１〜８個のアルキルチオ基又はフェニルチオ基であり、そしてｐは、０〜５の整数である。）で表されるアリール基である。｝で表されるスルホキシド化合物（Ａ）と、下記一般式（３）：

｛式中、Ｒ⁴は、ハロゲン原子、炭素数１〜８個のアルキル基、炭素数１〜８個のアルコキシ基、フェノキシ基、炭素数１〜８個のアルキルチオ基又はフェニルチオ基であり、そしてｑは、０〜５の整数である。｝又は下記一般式（４）：

｛式中、Ｒ⁵、及びＲ⁶は、各々独立に、水素原子、ハロゲン原子、水酸基、炭素数１〜８個のアルキル基、炭素数１〜８個のアルコキシ基又は炭素数１〜８個のアルキルチオ基であり、そしてｒ、及びｓは、各々独立に、１〜３の整数である。｝で表される芳香族化合物（Ｂ）と、下記一般式（５）：

｛式中、Ｒｆ、及びＲｆ’は、各々独立に、Ｆ、Ｃ_６Ｆ_５、若しくはＣ_ａＦ_{２ａ＋１−ｂ}Ｈ _ｂ（ここで、ａは、１〜８の整数であり、そしてｂは、０又は１である。）である。｝又は下記一般式（６）：

｛式中、ｎは、１〜５の整数である。｝で表されるスルホンイミド（Ｃ）とを、脱水剤の存在下、接触・混合させる工程を含む、下記一般式（７）：

｛式中、Ｒ^１、及びＲ^２は、上記一般式（１）において定義したものと同じであり、Ａｒは、上記一般式（３）又は上記一般式（４）で表される芳香族基であり、そしてＲｆ、及びＲｆ’は、上記一般式（５）において定義したものと同じである。｝で表されるスルホニウム塩の製造方法。 [1] The following general formula (1):

{In the formula, X is a single bond, a carbonyl group, an alkylene group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether group, a thioether group, or a disulfide group, and m is an integer of 0 to 4. N is an integer of 0 to 4, and R ¹ and R ² are each independently a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a nitro group, a carboxyl group, an alkoxy group, an alkyl group, or General formula (2):

(Wherein R ³ is a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenoxy group, an alkylthio group having 1 to 8 carbon atoms, or a phenylthio group, and p is an integer of 0 to 5). } And a sulfoxide compound (A) represented by the following general formula (3):

{Wherein R ⁴ is a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenoxy group, an alkylthio group having 1 to 8 carbon atoms, or a phenylthio group, and q is an integer of 0-5. } Or the following general formula (4):

{In the formula, R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. And r and s are each independently an integer of 1 to 3. } And the following general formula (5):

{Wherein Rf and Rf ′ are each independently F, C ₆ F ₅ , or C _a F _{2a + 1-b} H _b, where a is an integer from 1 to 8 and b is 0 or 1). } Or the following general formula (6):

{Wherein n is an integer of 1 to 5. The following general formula (7) including the step of contacting and mixing the sulfonimide (C) represented by the following formula:

{In the formula, R ¹ and R ² are the same as defined in the general formula (1), and Ar is an aromatic group represented by the general formula (3) or the general formula (4). Rf and Rf ′ are the same as those defined in the general formula (5). } The manufacturing method of the sulfonium salt represented by these.

  [2] The production method according to [1], wherein the dehydrating agent is phosphorus pentoxide.

  [3] A method of using the sulfonium salt obtained by the production method according to [1] or [2] as a photoacid generator.

  According to the present invention, a sulfonium salt can be produced with high yield from a cyclic sulfoxide compound in one step.

｛式中、Ｘは、単結合、カルボニル基、アルキレン基、スルホニル基、カルボニルオキシ基、カルボニルアミノ基、スルホニルアミド基、エーテル基、チオエーテル基又はジスルフィド基であり、ｍは、０〜４の整数であり、ｎは、０〜４の整数であり、Ｒ¹及びＲ²は、各々独立に、水素原子、水酸基、ハロゲン原子、シアノ基、ニトロ基、カルボキシル基、アルコキシ基、アルキル基、又は下記一般式（２）：

（式中、Ｒ³は、ハロゲン原子、炭素数１〜８個のアルキル基、炭素数１〜８個のアルコキシ基、フェノキシ基、炭素数１〜８個のアルキルチオ基又はフェニルチオ基であり、そしてｐは、０〜５の整数である。）で表されるアリール基である。｝で表されるスルホキシド化合物（Ａ）と、下記一般式（３）：

｛式中、Ｒ⁴は、ハロゲン原子、炭素数１〜８個のアルキル基、炭素数１〜８個のアルコキシ基、フェノキシ基、炭素数１〜８個のアルキルチオ基又はフェニルチオ基であり、そしてｑは、０〜５の整数である。｝又は下記一般式（４）：

｛式中、Ｒ⁵、及びＲ⁶は、各々独立に、水素原子、ハロゲン原子、水酸基、炭素数１〜８個のアルキル基、炭素数１〜８個のアルコキシ基又は炭素数１〜８個のアルキルチオ基であり、そしてｒ、及びｓは、各々独立に、１〜３の整数である。｝で表される芳香族化合物（Ｂ）と、下記一般式（５）：

｛式中、Ｒｆ、及びＲｆ’は、各々独立に、Ｆ、Ｃ_６Ｆ_５、若しくはＣ_ａＦ_{２ａ＋１−ｂ}Ｈ _ｂ（ここで、ａは、１〜８の整数であり、そしてｂは、０又は１である。）である。｝又は下記一般式（６）：

｛式中、ｎは、１〜５の整数である。｝で表されるスルホンイミド（Ｃ）とを、脱水剤の存在下、接触・混合させる工程を含む、下記一般式（７）：

｛式中、Ｒ^１、及びＲ^２は、上記一般式（１）において定義したものと同じであり、Ａｒは、上記一般式（３）又は上記一般式（４）で表される芳香族基であり、そしてＲｆ、及びＲｆ’は、上記一般式（５）において定義したものと同じである。｝で表されるスルホニウム塩の製造方法を提供する。 The present invention will be described in detail below.
The present invention provides the following general formula (1):

{In the formula, X is a single bond, a carbonyl group, an alkylene group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether group, a thioether group, or a disulfide group, and m is an integer of 0 to 4. N is an integer of 0 to 4, and R ¹ and R ² are each independently a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a nitro group, a carboxyl group, an alkoxy group, an alkyl group, or General formula (2):

(Wherein R ³ is a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenoxy group, an alkylthio group having 1 to 8 carbon atoms, or a phenylthio group, and p is an integer of 0 to 5). } And a sulfoxide compound (A) represented by the following general formula (3):

{Wherein R ⁴ is a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenoxy group, an alkylthio group having 1 to 8 carbon atoms, or a phenylthio group, and q is an integer of 0-5. } Or the following general formula (4):

{In the formula, R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. And r and s are each independently an integer of 1 to 3. } And the following general formula (5):

{Wherein Rf and Rf ′ are each independently F, C ₆ F ₅ , or C _a F _{2a + 1-b} H _b, where a is an integer from 1 to 8 and b is 0 or 1). } Or the following general formula (6):

{Wherein n is an integer of 1 to 5. The following general formula (7) including the step of contacting and mixing the sulfonimide (C) represented by the following formula:

{In the formula, R ¹ and R ² are the same as defined in the general formula (1), and Ar is an aromatic group represented by the general formula (3) or the general formula (4). Rf and Rf ′ are the same as those defined in the general formula (5). } The manufacturing method of the sulfonium salt represented by this is provided.

に示すように、上記一般式（７）で表されるスルホニウム塩を１工程で収率良く製造でき、フッ素置換スルホン酸イオン等の不純物の残存量を低く抑えることができる。 According to the method of the present invention, the following scheme 2:

As shown in the above, the sulfonium salt represented by the general formula (7) can be produced in a single step with good yield, and the residual amount of impurities such as fluorine-substituted sulfonate ions can be kept low.

Sulfoxide compound (A)
The sulfoxide compound (A) used in the present invention is a cyclic sulfoxide compound represented by the above general formula (1). X in the general formula (1) is a single bond, a carbonyl group, an alkylene group, a sulfonyl group, a carbonyloxy group from the viewpoint of the stability of the photoacid generator and the solubility of the photoacid generator in the solvent or monomer. , A carbonylamino group, a sulfonylamide group, an ether group, a thioether group, or a disulfide group. From the viewpoint of the stability of the photoacid generator and the solubility of the photoacid generator in a solvent or monomer, m is 0-4. N is an integer of 0 to 4, and R ¹ and R ² are each independently a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a nitro group, a carboxyl group, an alkoxy group, an alkyl group, Or a substituted or unsubstituted aryl group represented by the general formula (2).

In the general formula (2), R ³ represents a substituent. In view of stability of the photoacid generator, longer wavelength of light absorption, and decomposability at the time of exposure, in general formula (2), each R ³ is independently a halogen atom or 1 to 8 carbon atoms. An alkyl group, an alkoxy group having 1 to 8 carbon atoms, a phenoxy group, an alkylthio group having 1 to 8 carbon atoms, or a phenylthio group, and p is an integer of 0 to 5.

  In the general formula (1), X is preferably a single bond, a carbonyl group, a sulfonyl group, because of the availability of the sulfoxide compound represented by the general formula (1) and the handling property during synthesis. An ether group, a thioether group, a disulfide group, or an alkylene group having 1 to 4 carbon atoms, more preferably a single bond, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 2 carbon atoms, and particularly preferably a single bond. A bond, a carbonyl group, a sulfonyl group, or an alkylene group having 1 carbon atom;

Preferred examples of the structure of the sulfoxide compound (A) represented by the general formula (1) having X include the following:
・ X is a single bond

-X is a carbonyl group

-X is a sulfonyl group

・ X is an ether group

・ X is a thioether group

-X is a disulfide group

-X is an alkylene group having 1 to 4 carbon atoms

From the viewpoints of availability of the sulfoxide compound represented by the general formula (1) and handling properties at the time of synthesis, in the general formula (1), R ¹ and R ² are preferably each independently hydrogen. An atom, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group represented by the above general formula (2) {in the formula, each R ³ independently represents a halogen atom, 1 carbon atom It is -4 alkyl groups, a C1-C4 alkoxy group, a phenoxy group, a C1-C4 alkylthio group, or a phenylthio group, and p is 0-5. }.

R ¹ and R ² are more preferably each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted aryl group represented by the above general formula (2) {wherein R ³ is each independently a fluorine atom, a chlorine atom, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, a phenoxy group, an alkylthio group having 1 to 2 carbon atoms, or a phenylthio group. Yes, and p is 0-5. }.

R ¹ and R ² are particularly preferably each independently a methyl group, an ethyl group, a propyl group, an isopropyl group, or a substituted or unsubstituted aryl group represented by the general formula (2) ³ is each independently a chlorine atom, a methyl group or a methoxy group, and p is 0-5. }.

  When p in the general formula (2) is 0, the aryl group represented by the general formula (2) is an unsubstituted aryl group, and when p is 1 to 5, the aryl group is represented by the general formula (2). The aryl group is a substituted aryl group. p is preferably 0 to 3 and more preferably 0 to 2 from the viewpoints of stability of the photoacid generator, longer wavelength of light absorption, and decomposability upon exposure.

Preferable specific examples of R ¹ and R ^{2 in} the general formula (1) include those having the following structures:
・ Hydrogen atom -H
・ Hydroxyl group -OH
· Carbon 1-8C alkyl radical _{-CH 3, -CH 2 CH 3,} -CH 2 CH 2 CH 3, -CH (CH 3) 2,
_{-CH 2 CH 2 CH 2 CH 3} , -CH 2 CH (CH 3) 2, -C (CH 3) 3,
_{- (CH 2) 4 CH 3} , - (CH 2) 5 CH 3, - (CH 2) 6 CH 3,
_{- (CH 2) 7 CH 3} ,

・ P is 0

.Having halogen atoms as R ³

.R ³ having an alkyl group having 1 to 8 carbon atoms

.R ³ having an alkoxy group having 1 to 8 carbon atoms

.R ³ having a phenoxy group

.R ³ having an alkylthio group having 1 to 8 carbon atoms

.R ³ having a phenylthio group

が挙げられる。 Preferred examples of the sulfoxide compound (A) used in the present invention include the following compounds:

Is mentioned.

Aromatic compound (B)
The aromatic compound (B) used in the present invention is an aromatic compound represented by the general formula (3) or the general formula (4).
In the general formula (3), R ⁴ represents a substituent. From the viewpoint of stability of the photoacid generator, longer wavelength of light absorption, and decomposability during exposure, in general formula (3), R ⁴ is a halogen atom, an alkyl group having 1 to 8 carbon atoms, An alkoxy group having 1 to 8 carbon atoms, a phenoxy group, an alkylthio group having 1 to 8 carbon atoms or a phenylthio group, and q is an integer of 0 to 5;

R ⁴ is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a carbon number for reasons such as availability of the aromatic compound represented by the general formula (3) and handling properties at the time of synthesis. 1 to 4 alkoxy groups, a phenoxy group, an alkylthio group having 1 to 4 carbon atoms, or a phenylthio group, and q is an integer of 0 to 5, more preferably R ⁴ is a fluorine atom, A chlorine atom, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, a phenoxy group, an alkylthio group having 1 to 2 carbon atoms or a phenylthio group, and q is 0 to 5 More preferably, R ⁴ is a chlorine atom, a methyl group, a methoxy group, a phenoxy group, a methylthio group or a phenylthio group, and q is an integer of 0 to 5.

Specific examples of the aromatic compound represented by the general formula (3) include those having the following structures.
.Q is 0

.Having a halogen atom as R ⁴

.R ⁴ having an alkyl group having 1 to 8 carbon atoms

.R ⁴ having an alkoxy group having 1 to 8 carbon atoms

As · R ⁴ having a phenoxy group

.R ⁴ having an alkylthio group having 1 to 8 carbon atoms

.Having a phenylthio group as R ⁴

In the general formula (4), R ⁵ and R ⁶ are each independently a hydrogen atom or a halogen atom from the viewpoints of stability of the photoacid generator, longer wavelength of light absorption, and decomposability during exposure. , A hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkylthio group having 1 to 8 carbon atoms, and r and s are each independently an integer of 1 to 3 It is.

From the viewpoints of availability of the aromatic compound represented by the general formula (4) and handling properties at the time of synthesis, preferably R ⁵ and R ⁶ are each independently a halogen atom, a hydroxyl group, or a carbon number of 1 -4 alkyl groups, alkoxy groups having 1 to 4 carbon atoms or alkylthio groups having 1 to 4 carbon atoms, and r and s are each independently an integer of 1 to 3, more preferably. R ⁵ and R ⁶ are each independently a fluorine atom, a chlorine atom, a hydroxyl group, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or an alkylthio group having 1 to 2 carbon atoms. And r and s are each independently an integer of 1 to 3, particularly preferably R ⁵ and R ⁶ are each independently a chlorine atom, a hydroxyl group, a methyl group, a methoxy group or a methylthio group. And r and s are each independently an integer of 1 to 3. That.

Specific examples of the aromatic compound represented by the general formula (4) include those having the following structures:

｛式中、ｎは、１〜５の整数である。｝
で表される構造をもつ。 Sulfonimide (C)
Rf and Rf ′ of the sulfonimide (C) represented by the general formula (5) used in the present invention are each independently F, C ₆ F ₅ or C _a F _{2a + 1-b} H _b (wherein , A is an integer from 1 to 8 and b is 0 or 1).
Alternatively, the sulfonimide (C) has the following general formula (6):

{Wherein n is an integer of 1 to 5. }
It has a structure represented by

Specific examples of the sulfonimide (C) represented by the general formula (5) include the following:
HN (SO ₂ F) ₂
HN (SO ₂ CF ₃ ) SO ₂ F
HN (SO ₂ CF ₃ ) ₂
HN (SO ₂ CF ₂ CF ₃ ) SO ₂ F
HN (SO ₂ CF ₂ CF ₃ ) SO ₂ CF ₃
HN (SO ₂ CF ₂ CF ₃ ) ₂
HN [SO ₂ (CF ₂ ) ₂ CF ₃ ] SO ₂ F
HN [SO ₂ (CF ₂ ) ₂ CF ₃ ] SO ₂ CF ₃
HN [SO ₂ (CF ₂ ) ₂ CF ₃ ] SO ₂ CF ₂ CF ₃
HN [SO ₂ (CF ₂ ) ₂ CF ₃ ] ₂

HN [SO ₂ (CF ₂ ) ₃ CF ₃ ] SO ₂ F
HN [SO ₂ (CF ₂ ) ₃ CF ₃ ] SO ₂ CF ₃
HN [SO ₂ (CF ₂ ) ₃ CF ₃ ] SO ₂ CF ₂ CF ₃
HN [SO ₂ (CF ₂ ) ₃ CF ₃ ] SO ₂ (CF ₂ ) ₂ CF ₃
HN [SO ₂ (CF ₂ ) ₃ CF ₃ ] ₂
HN [SO ₂ (CF ₂ ) ₄ CF ₃ ] SO ₂ F
HN [SO ₂ (CF ₂ ) ₄ CF ₃ ] SO ₂ CF ₃
HN [SO ₂ (CF ₂ ) ₄ CF ₃ ] SO ₂ CF ₂ CF ₃
HN [SO ₂ (CF ₂ ) ₄ CF ₃ ] SO ₂ (CF ₂ ) ₂ CF ₃
HN [SO ₂ (CF ₂ ) ₄ CF ₃ ] SO ₂ (CF ₂ ) ₃ CF ₃
HN [SO ₂ (CF ₂ ) ₄ CF ₃ ] ₂

HN [SO ₂ (CF ₂ ) ₅ CF ₃ ] SO ₂ F
HN [SO ₂ (CF ₂ ) ₅ CF ₃ ] SO ₂ CF ₃
HN [SO ₂ (CF ₂ ) ₅ CF ₃ ] SO ₂ CF ₂ CF ₃
HN [SO ₂ (CF ₂ ) ₅ CF ₃ ] SO ₂ (CF ₂ ) ₂ CF ₃
HN [SO ₂ (CF ₂ ) ₅ CF ₃ ] SO ₂ (CF ₂ ) ₃ CF ₃
HN [SO ₂ (CF ₂ ) ₅ CF ₃ ] SO ₂ (CF ₂ ) ₄ CF ₃
HN [SO ₂ (CF ₂ ) ₅ CF ₃ ] ₂
HN [SO ₂ (CF ₂ ) ₆ CF ₃ ] SO ₂ F
HN [SO ₂ (CF ₂ ) ₆ CF ₃ ] SO ₂ CF ₃
HN [SO ₂ (CF ₂ ) ₆ CF ₃ ] SO ₂ CF ₂ CF ₃
HN [SO ₂ (CF ₂ ) ₆ CF ₃ ] SO ₂ (CF ₂ ) ₂ CF ₃
HN [SO ₂ (CF ₂ ) ₆ CF ₃ ] SO ₂ (CF ₂ ) ₃ CF ₃
HN [SO ₂ (CF ₂ ) ₆ CF ₃ ] SO ₂ (CF ₂ ) ₄ CF ₃
HN [SO ₂ (CF ₂ ) ₆ CF ₃ ] SO ₂ (CF ₂ ) ₅ CF ₃
HN [SO ₂ (CF ₂ ) ₆ CF ₃ ] ₂

HN [SO ₂ (CF ₂ ) ₇ CF ₃ ] SO ₂ F
HN [SO ₂ (CF ₂ ) ₇ CF ₃ ] SO ₂ CF ₃
HN [SO ₂ (CF ₂ ) ₇ CF ₃ ] SO ₂ CF ₂ CF ₃
HN [SO ₂ (CF ₂ ) ₇ CF ₃ ] SO ₂ (CF ₂ ) ₂ CF ₃
HN [SO ₂ (CF ₂ ) ₇ CF ₃ ] SO ₂ (CF ₂ ) ₃ CF ₃
HN [SO ₂ (CF ₂ ) ₇ CF ₃ ] SO ₂ (CF ₂ ) ₄ CF ₃
HN [SO ₂ (CF ₂ ) ₇ CF ₃ ] SO ₂ (CF ₂ ) ₅ CF ₃
HN [SO ₂ (CF ₂ ) ₇ CF ₃ ] SO ₂ (CF ₂ ) ₆ CF ₃
HN [SO ₂ (CF ₂ ) ₇ CF ₃ ] ₂
HN (SO ₂ CF ₂ CF ₂ H) SO ₂ F
HN (SO ₂ CF ₂ CF ₂ H) SO ₂ CF ₃
HN (SO ₂ CF ₂ CF ₂ H) SO ₂ CF ₂ H
HN (SO ₂ CF ₂ CF ₂ H) SO ₂ CF ₂ CF ₃
HN (SO ₂ CF ₂ CF ₂ H) ₂

HN (SO ₂ CF ₂ CF ₂ H) SO ₂ CFHCF _{3
HN (SO 2 CF 2 CF 2} H) SO 2 (CF 2) 2 CF 3
HN (SO ₂ CF ₂ CF ₂ H) SO ₂ (CF ₂ ) ₃ CF ₃
HN (SO ₂ CF ₂ CF ₂ H) SO ₂ (CF ₂ ) ₄ CF _{3
HN (SO 2 CF 2 CF 2} H) SO 2 (CF 2) 5 CF 3
HN (SO ₂ CF ₂ CF ₂ H) SO ₂ (CF ₂ ) ₆ CF ₃
HN (SO ₂ CF ₂ CF ₂ H) SO ₂ (CF ₂ ) ₇ CF ₃
HN (SO ₂ CFHCF ₃ ) SO ₂ F
HN (SO ₂ CFHCF ₃ ) SO ₂ CF ₃
HN (SO ₂ CFHCF ₃ ) SO ₂ CF ₂ H
HN (SO ₂ CFHCF ₃ ) SO ₂ CF ₂ CF ₃
HN (SO ₂ CFHCF ₃ ) SO ₂ CF ₂ CF ₂ H
HN (SO ₂ CFHCF ₃ ) ₂

HN (SO ₂ CFHCF ₃ ) SO ₂ (CF ₂ ) ₂ CF ₃
HN (SO ₂ CFHCF ₃ ) SO ₂ (CF ₂ ) ₃ CF ₃
HN (SO ₂ CFHCF ₃ ) SO ₂ (CF ₂ ) ₄ CF ₃
HN (SO ₂ CFHCF ₃ ) SO ₂ (CF ₂ ) ₅ CF ₃
HN (SO ₂ CFHCF ₃ ) SO ₂ (CF ₂ ) ₆ CF ₃
HN (SO ₂ CFHCF ₃ ) SO ₂ (CF ₂ ) ₇ CF ₃

が例示される。

Is exemplified.

As described later, the general formula (5) is synthesized using a sulfonyl halide as a starting material. From the viewpoints of availability of the sulfonyl halide, handling at the time of sulfonimide synthesis, and the like, the general formula (5) , Rf and Rf ′ are preferably each independently F, C ₆ F ₅ or C _a F _{2a + 1-b} H _b , wherein a is an integer from 1 to 6 and b is 0 Or more preferably Rf and Rf ′ are each independently F, C ₆ F ₅ or C _a F _{2a + 1-b} H _b (wherein a is 1 to 4). And b is 0 or 1. More preferably, Rf and Rf ′ are each independently F, C ₆ F ₅ or C _a F _{2a + 1-b} H _b (formula In which a is an integer from 1 to 4 and b is 0). , And in the general formula (6), n is preferably an integer of 1 to 4, more preferably an integer of 2 to 4, more preferably 2-3 integer.

In addition, as a manufacturing method of the sulfonimide salt which is a precursor of sulfonimide (C) represented by the said General formula (5), the following (1)-(4) is known, for example:
(1) A method of reacting perfluoroalkylsulfonyl fluoride with an alkali metal salt of a trimethylsilyl group-containing perfluoroalkylsulfonamide (for example, see Non-Patent Documents 4 to 5)
RfSO ₂ F + Rf'SO ₂ N (SiMe ₃ ) Na → RfSO ₂ N (Na) SO ₂ Rf '+ Me ₃ SiF

(2) A method of reacting perfluoroalkylsulfonyl halide and perfluoroalkylsulfonamide in the presence of an alkali metal fluoride (for example, see Patent Document 6)
RfSO ₂ X + Rf'SO ₂ NH ₂ + 4MF → RfSO ₂ N (M) SO ₂ Rf '+ 2MFHF + MX

(3) A method of reacting a fluorinated alkylsulfonyl halide and a fluorinated alkylsulfonamide in the presence of a carbonate (see, for example, Patent Document 5)
RfSO ₂ X + Rf'SO ₂ NH ₂ + M ₂ CO ₃ → RfSO ₂ N (M) SO ₂ Rf '+ MX + CO ₂ + H ₂ O

(4) A method of reacting perfluoroalkyldisulfonyl halide with ammonia (for example, see Non-Patent Document 6)

The manufacturing method of the sulfonimide salt which is a precursor of the sulfonimide (C) represented by the general formula (5) is not particularly limited.
After converting the sulfonimide salt obtained by these production methods into a sulfonimide using, for example, concentrated sulfuric acid or a cation exchange membrane, a high-purity sulfonimide can be obtained by distillation operation or the like.

In the general formula (7), R ¹ and R ² are the same as those defined in the general formula (1), and Ar is represented by the general formula (3) or the general formula (4). An aromatic group obtained by removing one atom of hydrogen from the aromatic compound (B) is represented, and Rf and Rf ′ are the same as those defined in the general formula (5).
Preferable compound examples of the sulfonium salt represented by the general formula (7) produced by the production method of the present invention include the compounds produced in Examples 1 to 4.

  As shown in Scheme 2 above, the method for producing a sulfonium salt of the present invention utilizes a dehydration condensation reaction. Therefore, when water exists in the reaction system, the dehydration condensation reaction is delayed, and the yield of the sulfonium salt represented by the general formula (7) is lowered. A dehydrating agent is necessary to efficiently remove water generated by the reaction. Examples of the dehydrating agent include inorganic compounds such as phosphorus pentoxide, sodium sulfate, and magnesium sulfate, and organic compounds such as acetic anhydride, trifluoroacetic anhydride, propionic anhydride, and phthalic anhydride. From the viewpoint of goodness, a more preferable dehydrating agent is phosphorus pentoxide, sodium sulfate, magnesium sulfate, acetic anhydride or trifluoroacetic anhydride, and particularly preferably phosphorus pentoxide. These dehydrating agents may be used alone or in combination of two or more.

  The amount of the aromatic compound (B) and the dehydrating agent used is preferably 0.95 mol to 10 mol, more preferably 0.98 mol to 5 mol, relative to 1 mol of the sulfoxide compound (A). Mole to 2 mol is more preferable. The amount of the aromatic compound (B) used relative to 1 mol of the sulfoxide compound (A) is preferably 0.95 mol or more from the viewpoint of avoiding deterioration of isolation due to the excess sulfoxide salt remaining. From the viewpoint of avoiding deterioration of isolation due to a large excess of aromatic compound remaining, it is preferably 10 mol or less. The amount of the dehydrating agent used per 1 mol of the sulfoxide compound (A) is preferably 0.95 mol or more from the viewpoint of surely dehydrating the generated water, while a large excess of the dehydrating agent remains in the system. From the viewpoint of avoiding deterioration of handleability due to the above, it is preferably 10 mol or less.

  The amount of the sulfonimide (C) to be used is preferably 0.95 mol to 10 mol, more preferably 0.98 mol to 5 mol, further preferably 1 with respect to 1 mol of the sulfoxide compound (A). Mol to 2 mol. The amount of the sulfonimide (C) used relative to 1 mol of the sulfoxide compound (A) is preferably 0.95 mol or more from the viewpoint of avoiding deterioration of isolation due to a large excess of the sulfoxide compound remaining, From the viewpoint of avoiding deterioration in handling properties due to the remaining of a large excess of sulfonimide, the amount is preferably 10 mol or less.

  The dehydration condensation reaction in the method for producing a sulfonium salt of the present invention can be performed in the presence of a reaction solvent. The reaction solvent to be used may be a solvent inert to the reactant. Specific examples of the reaction solvent include ether solvents such as chloroform, dichloromethane, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether, and nitriles such as acetonitrile, propionitrile, and butyronitrile. System solvents, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane and the like. These solvents can be used alone or in admixture of two or more.

  In the dehydration condensation reaction, the reaction temperature is usually −20 ° C. to 100 ° C., preferably −10 ° C. to 80 ° C., more preferably 0 ° C. to 50 ° C., further preferably 10 ° C. to 30 ° C. The reaction time is usually 0.01 to 60 hours, preferably 0.1 to 48 hours, more preferably 0.2 to 36 hours, still more preferably 0.5 to 24 hours. is there.

  After completion of the reaction, for example, the solvent in the reaction mixture is distilled off under reduced pressure, and the residue is added with an organic solvent such as dichloromethane, chloroform, ethyl acetate and water, and separated into an organic layer and an aqueous layer. The operation of extracting with fresh organic solvent is repeated 2-3 times. When the organic solvent is distilled off under reduced pressure from a mixture of the separated organic layer and the organic solvent used for extraction, the sulfonium salt represented by the general formula (7) can be obtained. The obtained sulfonium salt may be purified by a conventionally known purification method such as crystallization or column chromatography.

  As shown in Scheme 1 above, when producing a sulfonium salt in which the cation moiety is an arylsulfonium having a cyclic structure and the anion moiety is a fluorine-containing sulfonimidate, the conventional method obtains the sulfonium salt from the sulfoxide compound. This required at least two steps. On the other hand, as shown in Scheme 2 described above, according to the method for producing a sulfonium salt of the present invention, it is possible to obtain a sulfonium salt from a sulfoxide compound in a single step with a good yield. It turns out that it is useful.

  The sulfonium salt obtained by the production method of the present invention can be used as a photoacid generator for advancing the polymerization reaction of various polymerizable monomers. Examples of the polymerizable monomer include an epoxy compound, an oxetane compound, and a vinyl ether compound. When the polymerizable monomer is an epoxy compound, an oxetane compound, a vinyl ether compound or the like, the effect that the curing reaction proceeds even with light having a wavelength of 350 nm or more obtained by using the sulfonium salt according to the present invention is remarkable.

Hereinafter, the present invention will be specifically described, but the present invention is not limited to the following examples.
The following analytical methods were used in the following synthesis examples and examples.
(1) Molecular structure analysis and measurement apparatus by ¹ H NMR and ¹⁹ F NMR: JNM-GSX400G type nuclear magnetic resonance apparatus (manufactured by JEOL Ltd.)
Solvent: deuterated chloroform,
Reference materials: tetramethylsilane ( ¹ H NMR), Freon-11 (CFCl ₃ ) ( ¹⁹ F NMR)
(2) MALDI-TOF / MS structural analysis measurement device: AXIMA CFR plus (manufactured by Shimadzu Corporation)
Laser: Nitrogen laser (337 nm)
Detector type: Reflectron mode ion detection: Positive ion, Negative ion
Integration count: 500 times Matrix: Disranol chloroform solution

Synthesis Example 1 Synthesis of Diethylthioxanthone Oxide (O-1) In a 200 mL 3-neck flask, 2,4-diethylthioxanthen-9-one (16.1 g, 60.0 mmol) and trifluoroacetic acid (50 mL) ) And cooled to 0 ° C. A solution prepared by dissolving 30% aqueous hydrogen peroxide (6.87 mL, 60.6 mmol) in trifluoroacetic acid (13.7 mL) was dropped into a three-necked flask. After completion of dropping, the mixture was stirred at 0 ° C. for 30 minutes and further stirred at room temperature for 1 hour. Water and chloroform were added to the reaction mixture, the chloroform layer was separated, and the aqueous layer was extracted twice with chloroform. The chloroform layer and chloroform used for the extraction operation were mixed, and the mixture was washed with an aqueous sodium bicarbonate solution. The washed chloroform solution was dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain O-1 (16.90 g) (yield 99%). The molecular structure analysis results of O-1 were as follows:
¹ H NMR: 1.29-1.36 ppm (m, 3H), 1.38-1.45 ppm (m, 3H), 2.73-2.80 ppm (m, 2H), 3.20-3.35 ppm (M, 2H), 7.42-8.39 ppm (m, 6H)

Synthesis Example 2 Synthesis of Isopropylthioxanthone Oxide (O-2) In Synthesis Example 1, instead of 2,4-diethylthioxanthen-9-one, 2-isopropylthioxanthen-9-one (15.26 g, Except for using 60.0 mmol), the same operation as in Synthesis Example 1 was performed to obtain O-2 (15.73 g) (yield 97%). The molecular structure analysis results of O-2 were as follows:
¹ H NMR: 1.34 ppm (m, 6H), 3.04 to 3.14 ppm (m, 1H), 8.03 to 8.38 ppm (m, 7H)

１００ｍＬの３口フラスコに、Ｏ−１（８５３ｍｇ、３ｍｍｏｌ）、トルエン（４１５ｍｇ、４．５ｍｍｏｌ）、クロロホルム（１０ｍＬ）、及び五酸化リン（４２６ｍｇ、３ｍｍｏｌ）を加え、０℃に冷却した。トリフルオロメタンスルホンイミド（１．６８７ｇ、６ｍｍｏｌ）をクロロホルム（１０ｍＬ）に溶解させた溶液を、３口フラスコの中へ滴下した。滴下終了後、さらに室温で２３時間攪拌した。反応混合物に水を加えてクロロホルム層を分液し、水層はクロロホルムで２回抽出操作を行った。上記クロロホルム層と、該抽出操作に用いたクロロホルムとを混合し、この混合液を炭酸水素ナトリウム水溶液で洗浄した。洗浄したクロロホルム溶液を硫酸ナトリウムで乾燥後、溶媒を減圧留去してＰ−１（１．３６２ｇ）を得た（収率７１％）。Ｐ−１の分子構造解析結果は以下の通りであった：
¹Ｈ ＮＭＲ：１．５２-１．５４ｐｐｍ（ｍ，３Ｈ）、１．７４−１．８５（ｍ，６Ｈ）、３．２２−３．２８（ｍ，２Ｈ）、３．６２−３．６４（ｍ，２Ｈ）、７．８４−８．９５ｐｐｍ（ｍ，１０Ｈ）
¹⁹Ｆ ＮＭＲ：−７８．３７ｐｐｍ（ｓ，６Ｆ）
ＭＡＬＤＩ−ＴＯＦ／ＭＳ：３５９．１［Ｍ^＋］、２７９．６［Ｍ^―］ [Example 1] Synthesis of (P-1) having the following structure:

To a 100 mL 3-neck flask, O-1 (853 mg, 3 mmol), toluene (415 mg, 4.5 mmol), chloroform (10 mL), and phosphorus pentoxide (426 mg, 3 mmol) were added and cooled to 0 ° C. A solution of trifluoromethanesulfonimide (1.687 g, 6 mmol) dissolved in chloroform (10 mL) was dropped into a three-necked flask. After completion of dropping, the mixture was further stirred at room temperature for 23 hours. Water was added to the reaction mixture to separate the chloroform layer, and the aqueous layer was extracted twice with chloroform. The chloroform layer and chloroform used for the extraction operation were mixed, and the mixture was washed with an aqueous sodium bicarbonate solution. The washed chloroform solution was dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain P-1 (1.362 g) (yield 71%). The results of molecular structure analysis of P-1 were as follows:
¹ H NMR: 1.52-1.54 ppm (m, 3H), 1.74-1.85 (m, 6H), 3.22-3.28 (m, 2H), 3.62-3.64 (M, 2H), 7.84-8.95 ppm (m, 10H)
¹⁹ F NMR: −78.37 ppm (s, 6F)
MALDI-TOF / MS: 359.1 [M ⁺ ], 279.6 [M ⁻ ]

実施例１において、トリフルオロメタンスルホンイミドに代えて、ＨＮ（ＳＯ₂Ｃ₂Ｆ₅）₂（２．２８７ｇ、６ｍｍｏｌ）を用いた以外は、実施例１と同様の操作を行い、Ｐ−２（１．９３９ｇ）を得た（収率８７％）。Ｐ−２の分子構造解析結果は以下の通りであった：
¹Ｈ ＮＭＲ：１．５２−１．５４ｐｐｍ（ｍ，３Ｈ）、１．７３−１．８５（ｍ，６Ｈ）、３．２１−３．２８（ｍ，２Ｈ）、３．６２−３．６５（ｍ，２Ｈ）、８．１４−８．７８ｐｐｍ（ｍ，１０Ｈ）
¹⁹Ｆ ＮＭＲ：−１１７．８７（ｓ，４Ｆ）、−７８．５４ｐｐｍ（ｓ，６Ｆ） [Example 2] Synthesis of (P-2) having the following structure:

In Example 1, in place of trifluoromethane sulfonimide, except for using _{HN (SO 2 C 2 F 5} ) 2 (2.287g, 6mmol) performs the same operation as in Example 1, P-2 ( 1.939 g) was obtained (yield 87%). The results of molecular structure analysis of P-2 were as follows:
¹ H NMR: 1.52-1.54 ppm (m, 3H), 1.73-1.85 (m, 6H), 3.21-3.28 (m, 2H), 3.62-3.65 (M, 2H), 8.14-8.78 ppm (m, 10H)
¹⁹ F NMR: −117.87 (s, 4F), −78.54 ppm (s, 6F)

実施例１において、Ｏ−１に代えて、Ｏ−２（８１１ｍｇ、３ｍｍｏｌ）を用いた以外は、実施例１と同様の操作を行い、Ｐ−３（１．６５２ｇ）を得た（収率８８％）。Ｐ−３の分子構造解析結果は以下の通りであった：
¹Ｈ ＮＭＲ：１．２９-１．３７ｐｐｍ（ｍ，９Ｈ）、３．０５−３．１０ｐｐｍ（ｍ，１Ｈ）、７．１６−８．５４ｐｐｍ（ｍ，１１Ｈ）
¹⁹Ｆ ＮＭＲ：−７８．６５ｐｐｍ（ｓ，６Ｆ）
ＭＡＬＤＩ−ＴＯＦ／ＭＳ：３４５．１［Ｍ^＋］、２７９．６［Ｍ^―］ [Example 3] Synthesis of (P-3) having the following structure:

In Example 1, it replaced with O-1 and except having used O-2 (811 mg, 3 mmol), operation similar to Example 1 was performed and P-3 (1.652g) was obtained (yield) 88%). The results of molecular structure analysis of P-3 were as follows:
¹ H NMR: 1.29-1.37 ppm (m, 9H), 3.05-3.10 ppm (m, 1H), 7.16-8.54 ppm (m, 11H)
¹⁹ F NMR: −78.65 ppm (s, 6F)
MALDI-TOF / MS: 345.1 [M ⁺ ], 279.6 [M ⁻ ]

実施例１において、Ｏ−１に代えて、Ｏ−２（８１１ｍｇ、３ｍｍｏｌ）を用い、トリフルオロメタンスルホンイミドに代えて、ＨＮ（ＳＯ₂Ｃ₂Ｆ₅）₂（２．２８７ｇ、６ｍｍｏｌ）を用いた以外は実施例１と同様の操作を行い、Ｐ−４（１．７６３ｇ）を得た（収率８１％）。Ｐ−４の分子構造解析結果は以下の通りであった:
¹Ｈ ＮＭＲ：１．２９-１．３７ｐｐｍ（ｍ，９Ｈ）、３．０５−３．１０ｐｐｍ（ｍ，１Ｈ）、７．１６−８．５４ｐｐｍ（ｍ，１１Ｈ）
¹⁹Ｆ ＮＭＲ：−１１７．８７（ｓ，４Ｆ）、−７８．５４ｐｐｍ（ｓ，６Ｆ） [Example 4] Synthesis of (P-4) having the following structure:

In Example 1, O-2 (811 mg, 3 mmol) was used instead of O-1, and HN (SO ₂ C ₂ F ₅ ) ₂ (2.287 g, 6 mmol) was used instead of trifluoromethanesulfonimide. Except that, P-4 (1.763 g) was obtained in the same manner as in Example 1 (yield 81%). The molecular structure analysis result of P-4 was as follows:
¹ H NMR: 1.29-1.37 ppm (m, 9H), 3.05-3.10 ppm (m, 1H), 7.16-8.54 ppm (m, 11H)
¹⁹ F NMR: −117.87 (s, 4F), −78.54 ppm (s, 6F)

  The present invention is a novel method for producing a sulfonium salt, which can produce a sulfonium salt by a simple operation with a small number of steps, and the sulfonium salt obtained by the method comprises a paint, a coating agent, and a photocuring agent. It can be used as a photoacid generator in various applications such as mold adhesives and semiconductor photolithography.

Claims (3)

The following general formula (1):

{In the formula, X is a single bond, a carbonyl group, an alkylene group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether group, a thioether group, or a disulfide group, and m is an integer of 0 to 4. N is an integer of 0 to 4, and R ¹ and R ² are each independently a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a nitro group, a carboxyl group, an alkoxy group, an alkyl group, or General formula (2):

(Wherein R ³ is a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenoxy group, an alkylthio group having 1 to 8 carbon atoms, or a phenylthio group, and p is an integer of 0 to 5). } And a sulfoxide compound (A) represented by the following general formula (3):

{Wherein R ⁴ is a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenoxy group, an alkylthio group having 1 to 8 carbon atoms, or a phenylthio group, and q is an integer of 0-5. } Or the following general formula (4):

{In the formula, R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. And r and s are each independently an integer of 1 to 3. } And the following general formula (5):

{Wherein Rf and Rf ′ are each independently F, C ₆ F ₅ , or C _a F _{2a + 1-b} H _b, where a is an integer from 1 to 8 and b is 0 or 1). } Or the following general formula (6):

{Wherein n is an integer of 1 to 5. The following general formula (7) including the step of contacting and mixing the sulfonimide (C) represented by the following formula:

{In the formula, R ¹ and R ² are the same as defined in the general formula (1), and Ar is an aromatic group represented by the general formula (3) or the general formula (4). Rf and Rf ′ are the same as those defined in the general formula (5). } The manufacturing method of the sulfonium salt represented by these.   The production method according to claim 1, wherein the dehydrating agent is phosphorus pentoxide.   A method of using the sulfonium salt obtained by the production method according to claim 1 or 2 as a photoacid generator.