JP5728916B2 - Method for producing sulfonamidoonium salt - Google Patents

Description

  The present invention relates to a microfabrication technique in a manufacturing process of a semiconductor element or the like, particularly to a sulfonamide onium salt useful as a photoacid generator for photolithography and a method for producing a sulfonamide alkali metal salt which is a precursor thereof.

  In recent years, with the high integration and high speed of LSI, the pattern rule has been miniaturized rapidly. The background is the development of chemically amplified resist materials that enable photolithography pattern miniaturization. This contains a radiation-sensitive acid generator (hereinafter referred to as “photoacid generator”) that forms an acid upon irradiation with radiation (hereinafter referred to as “exposure”), and the acid generated by exposure is used as a catalyst. It is a pattern forming material that forms a pattern by changing the solubility of the exposed portion in the developer by a reaction.

  Various studies have been made on photoacid generators used in such chemically amplified resist materials. Among them, photoacid generators having a sulfonamidoonium salt skeleton were developed (Patent Documents 1 and 2).

  Regarding a method for producing a sulfonamidoonium salt as a skeleton, a method in which trifluoromethanesulfonamide and 1-adamantanecarbonyl chloride are reacted in the presence of sodium carbonate to once convert the sodium salt of sulfonamide into an onium salt (Patent Document) 1) and a method in which sulfonamide is once converted to a sodium salt with sodium hydrogen carbonate and then ion-exchanged to an onium salt using an ion-exchange resin (Patent Document 2).

JP 2009-191055 A International Publication 2010/119910 Pamphlet

  In the method of Patent Document 1, although a reaction for forming a sulfonamide skeleton by an amidation reaction and a sodium chloride reaction for converting the obtained sulfonamide into a sodium salt are carried out by a single treatment, The salt yield is 65%, which is not always a satisfactory level. Further, in the method of Patent Document 2, the yield of the sodium chloride reaction for once converting the sulfonamide into a sodium salt is not described, but in the onium chloride reaction, an ion exchange resin that is complicated to handle is used. The yield of the onium chloride reaction based on sodium salt is as low as 16%.

  As is apparent from these, the method for producing a sulfonamidoonium salt via the sulfonamide sodium salt has a low yield of the sulfonamide sodium salt and cannot be said to be an industrial method for producing a sulfonamidoonium salt. .

  The inventors of the present invention have made extensive studies in order to solve the above-mentioned problems. As a result, by using sodium hydroxide when converting the sulfonamide to its sodium salt, the sulfonamide sodium salt can be obtained in high yield and high purity. As a result, the present invention was completed.

  According to the teachings of Patent Document 1 and Patent Document 2, a sodium salt of a weak acid such as sodium carbonate or sodium bicarbonate is suitable for obtaining a sodium salt of sulfonamide. However, when sodium sulfonamide was converted to sodium salt using these sodium salts, the yield was low due to the low reaction rate, and separation from unreacted sulfonamide was difficult, and a high-purity product could not be obtained. .

However, trifluoromethanesulfonamide having an easily decomposable sulfonamide bond (—NH—SO ₂ —) under basic conditions is chlorinated using sodium hydroxide, which is not a weak base, but a strong base. Surprisingly, it was found that no significant cleavage of the sulfonamide bond occurred, and when the reaction was carried out at a sufficiently low temperature, it was substantially free of impurities such as by-products, and sulfonamidoonium. It has been found that the salt can be obtained in high yield.

  That is, the present invention is as follows.

[Invention 1]
The following general formula (1)

Including a first step of reacting a sulfonamide represented by the formula (2) with an alkali metal hydroxide.

The manufacturing method of the sulfonamide alkali metal salt represented by these.

(In each formula, R ¹ has a polymerizable unsaturated group at the terminal having 2 or more carbon atoms which may have a substituent, or an alicyclic group having 5 or more carbon atoms or which may have a substituent. X is a divalent linking group, Y is a linear, branched or cyclic alkylene group or arylene group, Rf is a hydrocarbon group containing a fluorine atom, and M ⁺ is an alkali group. It is a metal ion.)
[Invention 2]
Invention 1 wherein the alkali metal hydroxide is sodium hydroxide.

[Invention 3]
Invention 1 or 2 in which the reaction in the first step is carried out in an organic solvent containing water.

[Invention 4]
Inventions 1 to 3 in which the reaction in the first step is performed at -10 to 40 ° C.

[Invention 5]
The sulfonamide alkali metal salt obtained in the inventions 1 to 4 is converted to a monovalent onium salt represented by the general formula (4) A ⁺ Z ⁻ (4)
Comprising a second step of exchanging onium salts by general formula (3)

The manufacturing method of the sulfonamido onium salt represented by these.

(In the formula, R ¹ is an alicyclic group having 5 or more carbon atoms which may have a substituent or a group having a polymerizable unsaturated group at the terminal having 2 or more carbon atoms which may have a substituent. X is a divalent linking group, Y is a linear, branched or cyclic alkylene group or an arylene group, Rf is a hydrocarbon group containing a fluorine atom, and Z ⁻ is a monovalent group. A ⁺ is a sulfonium cation represented by the following general formula (a) or an iodonium cation represented by the following general formula (b).

Wherein R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkenyl group or an oxoalkyl group, or a substituted or unsubstituted carbon group having 6 to 18 carbon atoms. Represents an aryl group, an aralkyl group or an aryloxoalkyl group, or any two or more of R ² , R ³ and R ⁴ may be bonded to each other to form a ring together with the sulfur atom in the formula .)

(Wherein R ⁵ and R ⁶ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkenyl group or an oxoalkyl group, or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, Represents an aralkyl group or an aryloxoalkyl group, or R ⁵ and R ⁶ may be bonded to each other to form a ring together with an iodine atom in the formula.)
[Invention 6]
Invention 5 in which the second step is carried out without isolating the sulfonamide alkali metal salt obtained in the first step.

  According to the production method of the present invention, a sulfonamide alkali metal salt can be obtained in a high yield, and if the obtained sulfonamide alkali metal salt is used, a high-purity sulfonamidoonium salt can be easily produced in a high yield. There is an effect that can be done.

  The present invention is a method for producing a sulfonamidoonium salt comprising a step of producing a sulfonamide alkali metal salt which is a first target product as the first step (alkali metal chlorination step), and further comprises a second step (onium). This is a method for producing a sulfonamidoonium salt comprising a step of producing a sulfonamidoonium salt as a chlorination step). A one-pot manufacturing method in which the second step is performed using the entire reactor contents including the reaction product obtained in the first step can also be performed.

  Each reaction step (alkali metal chlorination step, onium chlorination step) of the present invention can be carried out in a continuous method, a semi-continuous method or a batch method. It is simple and preferable to carry out in a batch reactor. Details thereof will be described below, but a range in which a person skilled in the art can easily adjust reaction conditions, operating conditions, and the like based on the description belongs to the scope of the present invention.

  The sulfonamide that is the starting material of the present invention will be described. The sulfonamide is represented by the following general formula (1).

[R ¹ is an alicyclic group having 5 or more carbon atoms which may have a substituent or a group having a polymerizable unsaturated group at an end having 2 or more carbon atoms which may have a substituent, X is a divalent linking group, Y is a linear, branched or cyclic alkylene group or an arylene group, and Rf is a hydrocarbon group containing a fluorine atom. ]
The alicyclic group of R ¹ may or may not have a substituent. Here, the “alicyclic group” means a monocyclic group or a polycyclic group having no aromaticity. Preferably carbon number is 5-30, More preferably, it is 5-15. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, an oxygen atom (= O), and the like. Is mentioned.

  The basic ring structure excluding the substituent of the alicyclic group is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but is preferably a hydrocarbon group. The “hydrocarbon group” may be either saturated or unsaturated, but is usually preferably saturated.

  Examples of the alicyclic group having 5 or more carbon atoms include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane. More specifically, one or more hydrogen atoms are removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Group.

Among them, R ¹ in the present invention is preferably a group obtained by removing one or more hydrogen atoms from polycycloalkane, and more preferably a group obtained by removing one or more hydrogen atoms from adamantane.

The “group having a polymerizable unsaturated group at the end” of R ¹ means a functional group having a double bond, a triple bond, or the like having an ability to form a polymer by polymerization. Moreover, carbon number becomes like this. Preferably it is 2-30, More preferably, it is 2-15.

The group having a polymerizable unsaturated group at the terminal of R ¹ is preferably a chain hydrocarbon group, and may or may not have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, an oxygen atom (= O), and the like. Is mentioned.

Specific examples of R ¹ include a vinyl group, 1-methylethenyl group, allyl group, 3-butenyl group, 1-methylallyl group, 2-methylallyl group, 4-pentenyl group, and 5-hexenyl group. be able to.

  In formula (1), Y is a linear, branched or cyclic alkylene group, or an arylene group.

  The linear or branched alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 5 carbon atoms.

Specific examples of the linear alkylene group include a methylene group [—CH ₂ —], an ethylene group [— (CH ₂ ) ₂ —], a trimethylene group [— (CH ₂ ) ₃ —], and a tetramethylene group. [— (CH ₂ ) ₄ —], pentamethylene group [— (CH ₂ ) ₅ —] and the like can be mentioned.

Specific examples of the branched alkylene group include —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ) ₂ —, —C (CH ₃ ) (CH ₂ ). _{CH 3) -, - C (} CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - alkyl groups such _{as; -CH (CH 3) CH 2} -, - CH ( _{CH 3) CH (CH 3)} -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH 3) 2 -CH 2 - alkyl ethylene such as Groups; alkyl trimethylene groups such as —CH (CH ₃ ) CH ₂ CH ₂ — and —CH ₂ CH (CH ₃ ) CH ₂ —; —CH (CH ₃ ) CH ₂ CH ₂ CH ₂ —, —CH ₂ CH _{(CH 3) CH 2 CH 2} - aralkyl, such as alkyl tetramethylene group such as Ruarukiren group, and the like. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

  The cyclic alkylene group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. Further, the “cyclic alkylene group” includes a group bonded to the terminal of the chain alkylene group described above or having a ring interposed in the middle of the chain alkylene group, in addition to the case where the ring skeleton is linked alone. .

  The cyclic alkylene group may be a polycyclic group or a monocyclic group. As the monocyclic group, a group in which two hydrogen atoms have been removed from a monocycloalkane having 3 to 6 carbon atoms is preferable, and examples of the monocycloalkane include cyclopentane and cyclohexane. As the polycyclic group, a group in which two hydrogen atoms are removed from a polycycloalkane having 7 to 12 carbon atoms is preferable. Specific examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, tetra And cyclododecane.

  Examples of the arylene group for Y include aromatic carbonization of monovalent aromatic hydrocarbon groups such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. A divalent aromatic hydrocarbon group obtained by further removing one hydrogen atom from the nucleus of hydrogen; benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group And an aromatic hydrocarbon group obtained by further removing one hydrogen atom from the nucleus of the aromatic hydrocarbon.

  Among these, Y in the present invention is preferably a linear or branched alkylene group having 1 to 5 carbon atoms, and more preferably a methylene group, an ethylene group, a trimethylene group or a tetramethylene group.

  In formula (1), X is a divalent linking group.

  As the divalent linking group for X, a divalent hydrocarbon group which may have a substituent (more preferably a divalent hydrocarbon group having a substituent), a divalent linking group containing a hetero atom Etc. are mentioned as suitable.

  The term “having a substituent” for the hydrocarbon group means that part or all of the hydrogen atoms in the hydrocarbon group are substituted with groups or atoms other than hydrogen atoms.

  The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity.

  The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

  More specifically, as the aliphatic hydrocarbon group in the hydrocarbon group of X, a linear, branched or cyclic aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, or the like Is mentioned. Specifically, a linear, branched or cyclic alkylene group mentioned for Y or a combination of a linear, branched or cyclic alkylene group mentioned for Y can be mentioned.

  The chain or cyclic aliphatic hydrocarbon group preferably has a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, an oxygen atom (= O) and the like.

  Specific examples of the aromatic hydrocarbon group in the hydrocarbon group for X include the arylene groups described above for Y. Further, in the case of X, an aromatic hydrocarbon group in which a part of carbon atoms constituting the ring of the divalent aromatic hydrocarbon group is substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom is also preferred. Can be mentioned.

  In the aromatic hydrocarbon group, part or all of the hydrogen atoms constituting the hydrocarbon group are preferably substituted with a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).

The hetero atom in the “divalent linking group containing a hetero atom” of X is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

Specific examples of the divalent linking group containing a hetero atom include —O—, —C (═O) —, —C (═O) —O—, and a carbonate bond (—O—C (═O) —. O-), -NH-, ^-NR04 ( ^R04 is an alkyl group)-, -NH-C (= O)-, = N- and the like. Moreover, the combination etc. of these "divalent coupling groups containing a hetero atom" and a bivalent hydrocarbon group are mentioned. Examples of the divalent hydrocarbon group include the “divalent hydrocarbon group which may have a substituent” as described above for X, and are linear, branched or aliphatic having a ring in the structure. A hydrocarbon group is preferred.

  X may or may not have an acid dissociable site in its structure.

  The “acid-dissociable site” refers to a site in the organic group that is dissociated by the action of an acid generated by exposure. When X has an acid dissociable part, it is preferable to have an acid dissociable part having a tertiary carbon atom.

  In the present invention, X is preferably a divalent linking group containing a hetero atom.

When X is a divalent linking group containing a hetero atom, preferred examples of the linking group include -O-, -C (= O) -O-, -C (= O) -NH-, -C ( = O)-, -OC (= O) -O-, general formula -A-O-, -O-A-O-,-[A-C (= O) -O] _m- or -A. A group represented by —O—C (═O) —, wherein A is a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m is 0 to 3 Is an integer. ] Etc. are mentioned.

In general formulas -A-O-, -O-A-O-,-[A-C (= O) -O] _m- , or -A-O-C (= O)-, A is a substituent. It is a divalent hydrocarbon group which may have. Examples of the divalent hydrocarbon group include those mentioned as the “divalent hydrocarbon group optionally having substituent (s)” described above for X.

  As A, a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group or an ethylene group is particularly preferable. .

In the group represented by the general formula-[A-C (= O) -O] _m- , m is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1. 1 is most preferred.

  The divalent linking group containing a hetero atom is preferably a linear group having an oxygen atom or a nitrogen atom as a hetero atom, for example, a group containing an ether bond, an ester bond, or an amide bond. ) -O- and -C (= O) -NH- are more preferred.

  In general formula (1), Rf is a hydrocarbon group containing a fluorine atom.

  Examples of the hydrocarbon group containing a fluorine atom of Rf include groups in which part or all of the hydrogen atoms constituting the hydrocarbon group are substituted with fluorine atoms. Here, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be saturated or unsaturated. It may be cyclic or cyclic, but is preferably a linear or branched aliphatic saturated hydrocarbon group (alkyl group).

  The linear alkyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms. preferable. Specifically, for example, a part or all of hydrogen atoms constituting a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. are fluorine atoms. And a group substituted by.

  The branched alkyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specifically, for example, a part or all of hydrogen atoms constituting 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, etc. Is a group substituted with a fluorine atom.

  Among these, Rf is preferably a group in which some or all of the hydrogen atoms constituting the linear alkyl group are substituted with fluorine atoms, and more preferably a linear perfluoroalkyl group. , A trifluoromethyl group, a pentafluoroethyl group, or a nonafluoropropyl group is more preferable.

  Specific examples of the sulfonamide represented by the general formula (1) are shown below.

  Next, the sulfonamide alkali metal salt obtained by the first step (alkali metal chlorination step) will be described. The sulfonamide alkali metal salt is represented by the following general formula (2).

In the general formula ^{(2), R 1, X} , Y, Rf is ^R 1, X, Y, the same definition as Rf in Formula (1). M ⁺ is an alkali metal ion. Specific examples include lithium ions, sodium ions, potassium ions, and the like. Sodium ions or lithium ions are more preferable, and sodium ions are particularly preferable.

The sulfonamide onium salt obtained by the second step (onium chloride step) will be described. The sulfonamidoonium salt is represented by the following general formula (3).

In Formula ^{(3), R 1, X} , Y, Rf is ^R 1, X, Y, the same definition as Rf in Formula (1). A ⁺ is a sulfonium cation represented by the following general formula (a) or an iodonium cation represented by the following general formula (b).

(Wherein R ² , R ³ and R ⁴ each independently represents an aryl group or an alkyl group, and any two of R ² , R ³ and R ⁴ are bonded to each other to form a sulfur atom in the formula) And at least one of R ² , R ³ and R ⁴ represents an aryl group.

(Wherein R ⁵ and R ⁶ each independently represents an aryl group or an alkyl group, and at least one of R ⁵ and R ⁶ may represent an aryl group.)
Hereinafter, the sulfonium cation represented by the general formula (a) and the iodonium cation represented by the general formula (b) will be described in detail.

<Sulfonium cation represented by general formula (a)>
In general formula (a), R ² , R ³ and R ⁴ each independently represents an aryl group or an alkyl group. In addition, any ^two of R ² , R ³ and R ⁴ in the general formula (a) may be bonded to each other to form a ring together with the sulfur atom in the formula.

Further, it is preferable that at least one of R ² , R ³ and R ⁴ is an aryl group. Of R ^{2, R 3} and ^{R 4,} more preferably 2 or more is an aryl ^group, and most preferably all the R 2, ^{R 3} and ^{R 4} are aryl groups.

The aryl group for R ² , R ³ and R ⁴ is not particularly limited, and is, for example, an aryl group having 6 to 20 carbon atoms, in which part or all of the hydrogen atoms are alkyl groups, It may or may not be substituted with an alkoxy group, a halogen atom, a hydroxyl group or the like.

  The aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at a low cost. Specific examples include a phenyl group and a naphthyl group.

  The alkyl group that may be substituted for the hydrogen atom of the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and is a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Is most preferred.

  As the alkoxy group that may be substituted for the hydrogen atom of the aryl group, an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, A tert-butoxy group is preferable, and a methoxy group and an ethoxy group are most preferable.

  The halogen atom that may be substituted with the hydrogen atom of the aryl group is preferably a fluorine atom.

The alkyl group of R ^2, R ³ and R ^4, is not particularly limited, for example, linear C1-10, branched or cyclic alkyl group, and the like. It is preferable that it is C1-C5 from the point which is excellent in resolution. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a nonyl group, and a decyl group. A methyl group is preferable because it is excellent in resolution and can be synthesized at low cost.

When any ^two of R ² , R ³ and R ⁴ in the general formula (a) are bonded to each other to form a ring together with the sulfur atom in the formula, a 3 to 10 membered ring including the sulfur atom is formed. It is preferable that a 5- to 7-membered ring is formed.

Formula (a) within the R ^2, R ³ and R ⁴ that put, if any two of forming a ring with the sulfur atom bonded to each other, the remaining one is an aryl group It is preferable. Examples of the aryl group include the same aryl groups as R ² , R ³ and R ⁴ .

  Preferable examples of the cation moiety represented by the general formula (a) include cation moieties represented by the following formulas (I-1-1) to (I-1-10). Among these, those having a triphenylmethane skeleton such as a cation moiety represented by formulas (I-1-1) to (I-1-9) are preferable.

In the following formulas (I-1-10) to (I-1-11), R ⁹ and R ¹⁰ are each independently a phenyl group, naphthyl group or carbon number 1 to 5 which may have a substituent. An alkyl group, an alkoxy group, and a hydroxyl group.

  u is an integer of 1 to 3, and 1 or 2 is most preferable.

Moreover, as A ^<+> , the organic cation represented by the following general formula (a-1) or (a-2) is also mentioned.

^Wherein, R 41 ^{to R 46} has the same meaning as the _{^{R 9 ~R 10, n 1 '}} ~n 5' are each independently represents an integer of 0 to 3, n _{6 'is} integer of 0 to 2 It is. ]
Wherein (a-1) or ^(a-2), when the sign n ₁ attached to ^R 41 ~R ⁴⁶ _{'~n 6'} is an integer of 2 or more, each of the plurality of ^R 41 ^{to R 46} are the same May be different.

n _{1 ′} is preferably 0 to 2, more preferably 0 or 1, and still more preferably 0.

n _{2 ′} and n _{3 ′} are preferably each independently 0 or 1, more preferably 0.

n _{4 ′} is preferably 0 to 2, and more preferably 0 or 1.

n _{5 ′} is preferably 0 or 1, and more preferably 0.

n _{6 ′} is preferably 0 or 1, more preferably 1.

<Iodonium cation represented by general formula (b)>
In general formula (b), R ^{5 to} R ⁶ each independently represents an aryl group or an alkyl group. Of R ^{5 to} R ⁶ , at least one is preferably an aryl group. More preferably, all of R ^{5 to} R ⁶ are aryl groups.

Examples of the aryl group of R ^{5 to} R ⁶ include the same aryl groups as R ² , R ^3, and R ⁴ .

Examples of the alkyl group for R ^{5 to} R ⁶ include the same alkyl groups as those for R ² , R ^3, and R ⁴ .

Among these, it is most preferable that all of R ^{5 to} R ⁶ are phenyl groups.

  Specific iodonium cations include bis (4-methylphenyl) iodonium, bis (4-ethylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (4- (1,1-dimethylpropyl) phenyl. ) Iodonium, (4-methoxyphenyl) phenyliodonium, (4-tert-butoxyphenyl) phenyliodonium, 4- (acryloyloxy) phenylphenyliodonium, 4- (methacryloyloxy) phenylphenyliodonium, and the like.

In the present invention, A ⁺ is preferably a sulfonium cation represented by the general formula (a), (a-1) or (a-2), and represented by the general formula (a) or (a-2). More preferred is the sulfonium cation.

Examples of the anion moiety of the sulfonamide represented by the general formula (1) and the sulfonamide alkali metal salt represented by the general formula (2) are specifically exemplified as the sulfonamide represented by the general formula (1). Illustrated is an ionized structure in which protons on nitrogen in the compound group are extracted.

[First step (alkali metal chloride step)]
In the first step (alkali metal chlorination step), the sulfonamide represented by the general formula (1) (sometimes referred to as “sulfonamide (1)” in the present specification) is reacted with an alkali metal hydroxide. And a step of obtaining a sulfonamide alkali metal salt represented by the general formula (2).

  In general, the reaction for converting an amide to an alkali metal salt of an amide (alkali metal chloride) is carried out in the presence of a base containing an alkali metal, but the alkali metal chloride according to the present invention uses an alkali metal hydroxide. Features.

In obtaining an alkali metal salt, by using mild conditions using a weakly basic alkali metal salt, cleavage of the sulfonamide moiety can be avoided, which is suitable for improving yield and selectivity. Was guessed. However, when alkali metal chloride according to the present invention is performed with alkali metal carbonate (NaCO ₃ ), hydrogen carbonate (NaHCO ₃ ) or the like in accordance with the disclosures of Patent Documents 1 and 2, the reactivity is low, and the raw material amide remains. I found out. On the other hand, it was found that the use of hydroxides did not cause cleavage of the amide bond, which was a concern, so that a high reaction rate was obtained and a sulfonamide alkali metal salt was produced with high selectivity. Furthermore, even if an ester group susceptible to alkali hydrolysis was present in the structure of the sulfonamide represented by the general formula (1) as a starting material, the ester group was not cleaved.

  Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and francium hydroxide, preferably lithium hydroxide, sodium hydroxide, and potassium hydroxide, Of these, sodium hydroxide is most preferred.

  The molar ratio of the alkali metal hydroxide to the sulfonamide (1) is usually 0.5 to 3.0, preferably 0.8 to 2.0, and more preferably 1.0 to 1.5. The reaction itself proceeds even at a molar ratio of 1.0 or less, but is not efficient because the yield decreases.

  This reaction is usually performed in the presence of water. The mass part of water with respect to 100 parts by mass of the sulfonamide (1) is usually 1 part by mass or more, preferably 50 parts by mass or more, and more preferably 100 parts by mass or more. The upper limit is not particularly related to the reaction, but if too much water is used, the efficiency decreases, so it is 10000 parts by mass or less, preferably 2000 parts by mass or less.

  Moreover, water and an organic solvent can be used together. Although there is no restriction | limiting in particular in the organic solvent used together, In order to improve the solubility with respect to the water of sulfonamide (1), it is preferable to use a water-soluble organic solvent. In the present specification, the “water-soluble organic solvent” refers to an organic solvent that is a hydrophilic polar solvent and has a theoretical value of a solubility parameter (SP value) of 9.9 or more. For example, organic solvents, such as acetonitrile, methanol, dimethylformamide, dimethyl sulfoxide, can be mentioned.

  The amount of the organic solvent used in this case is greatly influenced by the water solubility of the sulfonamide (1) to be used, but is 200 parts by mass or less and 100 parts by mass or less with respect to 100 parts by mass of the sulfonamide (1). Preferably, 50 parts by mass or less is more preferable. Although the ratio of an organic solvent and water is not specifically limited, It is 0-2000 mass parts with respect to 100 mass parts of water, and 0-500 mass parts is preferable. Since the use of an organic solvent causes an increase in production cost, it is not preferable to exceed the upper limit.

  The reaction temperature is usually −10 to 40 ° C., preferably 0 to 20 ° C., more preferably 0 to 10 ° C. If the temperature is higher than 40 ° C., the sulfonamide bond may be cleaved, and depending on the structure of the amide, side reactions such as polymerization of the polymerizable site and cleavage of the ester site may occur, which is not preferable. If it is less than -10 degreeC, there exists a possibility that a reaction liquid may solidify, and it is not preferable. The reaction time varies depending on the reaction conditions such as reaction temperature and substrate concentration, but is usually 10 minutes to 16 hours. Preferably, it is 30 minutes to 6 hours. Using an analytical instrument such as thin layer chromatography (TLC) or nuclear magnetic resonance apparatus (NMR), the end point of the reaction is preferably the end point of the sulfonamide (1) as a raw material.

  The first step can be performed using glass, stainless steel, fluororesin, or a container lined with these materials.

  The sulfonamide alkali metal salt represented by the general formula (2) thus obtained can be purified by methods such as extraction with an organic solvent and recrystallization.

  However, the sulfonamide alkali metal salt obtained in the first step is the most efficient method in terms of operability and sulfonamide onium salt yield to proceed to the onium chloride step without such purification. .

[Second step (onium chloride step)]
The 2nd process concerning the present invention is explained. In the second step, the sulfonamide alkali metal salt represented by the general formula (2) obtained in the first step is converted to the monovalent onium salt represented by the general formula (4) A ⁺ Z ⁻ (4).
Is used to obtain a sulfonamidoonium salt represented by the general formula (3) by exchanging an alkali metal ion and an onium ion with an onium salt. In the second step, the sulfonamide alkali metal salt is easily ion-exchanged, and cleavage or decomposition of the sulfonamide structure contained in the sulfonamide (1), the sulfonamide alkali metal salt, or the sulfonamide onium salt does not occur. A ⁺ in the general formula (4) has the same meaning as in the general formula (3). And Z ^- represents a monovalent anion. Specific examples of such anions include, for example, F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , HSO ₄ ⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , aliphatic Preferred examples include sulfonate anion, aromatic sulfonate anion, trifluoromethanesulfonate anion, fluorosulfonate anion, aliphatic carboxylate anion, aromatic carboxylate anion, fluorocarboxylate anion, and trifluoroacetate anion. Is Cl ⁻ , Br ⁻ , HSO ₄ ⁻ , BF ₄ ⁻ , an aliphatic sulfonate anion or the like, and more preferably Cl ⁻ , Br ⁻ or HSO ₄ ^— .

  The molar ratio of the monovalent onium salt represented by the general formula (4) to the sulfonamide alkali metal salt represented by the general formula (2) is usually 0.5 to 3.0, preferably 0.8. It is -2.0, More preferably, it is 1.0-1.5. The reaction itself proceeds even at a molar ratio of 0.5 or less, but it is not efficient because the yield decreases.

  This reaction is usually performed in a reaction solvent. As the reaction solvent, water or an organic solvent can be used. Examples of the organic solvent include lower alcohols (alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol, and isopropanol), tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, and the like. Is mentioned. Preferred are water, methanol, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide and the like, and particularly preferred is water.

The mass part with respect to 100 mass parts of sulfonamide sodium salt of a reaction solvent is 50-20000 weight part, and 100-10000 mass part is preferable. When using an organic solvent and water together,
Although the ratio of an organic solvent and water is not specifically limited, It is 0-2000 mass parts with respect to 100 mass parts of water, and 0-500 mass parts is preferable.

  The reaction temperature is usually 0 to 80 ° C., preferably 5 to 30 ° C., and the reaction time varies depending on the reaction conditions such as reaction temperature and substrate concentration, but is usually 10 minutes to 16 hours, preferably 30 minutes to Although it is 6 hours, using an analytical instrument such as thin layer chromatography (TLC) or nuclear magnetic resonance apparatus (NMR), the point of time when the raw material sulfonamide alkali metal salt is consumed may be the end point of the reaction. preferable.

  The second step can be performed using glass, stainless steel, fluororesin, or a container lined with these materials.

  The reaction solution (reactor contents) after the reaction is usually separated into an aqueous layer and an organic layer. The organic layer can be obtained and purified by washing with water, washing with an organic solvent, extraction or the like. Examples of the organic solvent used in the purification include esters such as ethyl acetate and n-butyl acetate; ethers such as diethyl ether and diisopropyl ether; alkyl halides such as methylene chloride and chloroform; An organic solvent is mentioned. In the present specification, the “organic solvent that is not mixed with water” refers to an organic solvent that is a hydrophobic nonpolar solvent and has a theoretical value of a solubility parameter (SP value) of 9.8 or less.

  Further, after extraction with an organic solvent, the organic solvent is distilled off, and the remaining sulfonamidoonium salt is purified by recrystallization, reprecipitation or the like, whereby a high-purity sulfonamidoonium salt can be obtained.

[One-pot manufacturing method]
In the production of the sulfonamidoonium salt represented by the general formula (3) of the present invention, the first step and the second step can be performed in one pot. “One pot” refers to performing the second step using the reaction liquid formed in the first step as it is. “As is” means that there is no substantial purification between the first step and the second step, and the two steps can be carried out in the same reactor or in different reactors. it can. Since the one-pot manufacturing method does not require purification between the first step and the second step, it is a simple, efficient and efficient method.

  In the one-pot manufacturing method, the first step and the second step may be performed in accordance with the detailed description of the first step and the second step, respectively, and the first step and the second step can be sequentially performed. .

  Although a specific embodiment is illustrated below, it is not restricted to this.

  The sulfonamide (1) is dissolved in an organic solvent that is not mixed with water. Examples of the organic solvent include esters such as ethyl acetate and n-butyl acetate; ethers such as diethyl ether and diisopropyl ether; and alkyl halides such as methylene chloride and chloroform.

  The mass part of the organic solvent with respect to 100 parts by mass of the sulfonamide (1) is usually 1 part by mass or more and 10,000 parts by mass or less, and preferably 100 parts by mass or more and 2000 parts by mass or less.

If an excessive amount of the organic solvent is used, the efficiency is deteriorated. Therefore, the amount is preferably 50 parts by mass or less, and more preferably 10 parts by mass or less.

  The solution in which the sulfonamide (1) is dissolved is mixed with a predetermined amount of alkali metal hydroxide described in the explanation of the first step and water separately or as an aqueous solution. The reaction is carried out at the predetermined temperature and time described in the first step.

  After a predetermined time has elapsed, a predetermined amount of a monovalent onium salt represented by the general formula (4) described in the explanation of the second step is added, and the reaction is carried out at a predetermined temperature and time. An organic solvent can be added at the start of the second step or as the reaction proceeds.

  After completion of the reaction, the target sulfonamidoonium salt is dissolved in an organic solvent that is not mixed with the initially added water, so a solution containing the target sulfonamidoonium salt can be obtained simply by performing a liquid separation operation with the aqueous layer. Can be obtained. Next, the organic solvent is distilled off, and the remaining sulfonamidoonium salt is purified by recrystallization, reprecipitation or the like, whereby a high purity sulfonamidoonium salt can be obtained.

  The sulfonamidoonium salt obtained by the method of the present invention can be used as an acid generator or a quencher for a chemically amplified resist composition in photolithography in the semiconductor industry. The acid generator is an alkali developer by which the acid generated by exposure to high energy rays such as ultraviolet rays and electron beams accelerates decomposition of acid detachment sites in the resist composition or crosslinks the cross-linking sites. It is used to form a resist pattern that is faithful to the exposed pattern shape by changing the solubility in the resist. When used as a quencher, the sulfonamidoonium salt according to the present invention captures the acid generated from the acid generator in the unexposed area in the same manner as a normal quencher and decomposes by exposure in the exposed area as a quencher. Thus, the acid catalysis in the unexposed and exposed areas can be adjusted without reducing the acid concentration.

  The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

The analysis of organic substances was performed with a nuclear magnetic resonance apparatus ( ¹⁹ F-NMR or ¹ H-NMR) other than those specified separately. Here, the chemical shift reference material of ¹ H-NMR is tetramethylsilane (TMS), and the chemical shift reference material of ¹⁹ F-NMR is trichlorofluoromethane (however, the peak of hexafluorobenzene is −162.2 ppm) ) The purity and yield were calculated based on the integral ratio with respect to the standard substance (1,3-bis (trifluoromethyl) benzene) using ¹⁹ F-NMR and expressed as “%”.

  [Synthesis Example 1] N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide

  In a glass flask equipped with a thermometer and a condenser, 100 g (0.52 mol) of trifluoromethanesulfonic acid amide ethanol, 108.6 g (0.54 mol) of 1-adamantanecarboxylic acid, p-toluenesulfonic acid (0.1 mol), and toluene 500 g was added and dehydration was performed under reflux using a Dean-Stark type dehydrator. After refluxing for 9 hours, about 9 ml of water could be removed. This reaction solution was dissolved in 500 g of ethyl acetate and washed successively with a saturated aqueous solution of sodium hydrogen carbonate, 1N hydrochloric acid and saturated brine. The organic phase was dried over sodium sulfate, the solvent was distilled off under reduced pressure, and then recrystallized in hexane to give 151 g of N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide (81% yield). 99% purity).

[Physical properties of N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide]
¹ H-NMR (measurement solvent: deuterated chloroform, reference material: tetramethylsilane); δ = 5.43-5.35 (brs, 1H), 4.20 (t, 2H, J = 5.2 Hz), 3 .53 (td, 2H, J = 5.2 Hz), 2.08-1.98 (brs, 3H), 1.91-1.87 (brs, 6H), 1.75-1.67 (brs, 6H).
¹⁹ F-NMR (measurement solvent: deuterated chloroform, reference material: trichlorofluoromethane); δ = −77.8 (s, 3F).
From the results of the above analysis, it was confirmed that the obtained compound was N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide shown above.

  Example 1 Synthesis of triphenylsulfonium N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide ((C) -1)

  In a 1 L glass reactor, 100 g (0.28 mol) of N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide obtained in Synthesis Example 1 and 400 mL of water were added. The mixture was charged, the internal temperature was maintained at 0 ° C., and 109 g of 11% sodium hydroxide aqueous solution (0.3 mol of sodium hydroxide) was slowly added dropwise with stirring, followed by stirring for 30 minutes. The reaction liquid suspended before dropping the aqueous sodium hydroxide solution became a uniform liquid when the addition of the aqueous sodium hydroxide solution was completed. Thereafter, water was distilled off to obtain 111 g of N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide sodium salt. At this time, purity was 90% and yield was 95%.

  Next, 100 g (purity 90%, 0.24 mol) of the obtained sodium salt, 200 mL of chloroform, and 86 g (0.25 mol) of triphenylsulfonium bromide were added to a 1 L glass reactor at a time at 25 to 32 ° C. After stirring for a period of time, the reaction solution was washed once with 300 mL of water and then separated, and the organic layer was concentrated under reduced pressure. The obtained yellow oil was dissolved in acetonitrile and recrystallized in diisopropyl ether to obtain 142 g of triphenylsulfonium N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide. At this time, the purity was 99% and the yield was 96%.

[Physical properties of triphenylsulfonium N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide]
¹ H-NMR (measurement solvent: heavy DMSO, reference material: tetramethylsilane); δ = 7.88-7.76 (m, 15H; Ph ₃ S ⁺ ), 3.85 (t, 2H), 3. 02 (t, 2H), 2.08-1.98 (brs, 3H), 1.91-1.87 (brs, 6H), 1.75-1.67 (brs, 6H).
¹⁹ F-NMR (measurement solvent: heavy DMSO, reference material: trichlorofluoromethane); δ = −75.5 (s, 3F).
From the results of the above analysis, it was confirmed that the obtained compound was triphenylsulfonium N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide represented by the above formula (C) -1. .

  [Example 2] Synthesis of triphenylsulfonium N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide ((C) -1)

  In a 3 L glass reactor, 240 g (0.63 mol) of N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide obtained in Synthesis Example 1 above, 800 mL of water, Chloroform 800 mL was charged, the internal temperature was maintained at 0 ° C., and 0.24 kg of 11% sodium hydroxide aqueous solution (0.68 mol of sodium hydroxide) was added dropwise with stirring, followed by stirring for 30 minutes. After stopping the stirring, it was confirmed that both layers separated into two layers were uniform and free from insoluble matter. Next, after adding 244 g (0.71 mol) of triphenylsulfonium bromide at a time and stirring at 23-30 ° C. for 15 hours, the reactor contents separated into two layers were separated, and the obtained organic layer was diluted with 800 mL of water. Washed and concentrated under reduced pressure. The obtained yellow oil was dissolved in acetonitrile and recrystallized in diisopropyl ether to obtain 360 g of triphenylsulfonium N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide. At this time, the purity was 99% and the yield was 87%.

[Example 3] Synthesis of triphenylsulfonium N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide In a 3 L glass reactor, N- [ 2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide 240 g (0.63 mol), water 800 mL and chloroform 800 mL were added, and 22% aqueous sodium hydroxide solution 0.12 kg (0.68 mol) at 30 to 32 ° C. ) Was added dropwise in 30 minutes, and stirring was continued for another 30 minutes. After stopping the stirring, it was confirmed that both layers separated into two layers were uniform and free from insoluble matter. Next, after adding 244 g (0.71 mol) of triphenylsulfonium bromide and stirring at 22-32 ° C. for 15 hours, the reactor contents separated into two layers were separated, and the obtained organic layer was once with 800 mL of water. Washed and concentrated under reduced pressure.

When analysis was performed using a ¹ H-NMR analyzer at this time, a total of 32% of components presumed to be cleaved from the sulfonamide or ester sites were detected.

  The obtained yellow oil was dissolved in acetonitrile and recrystallized in diisopropyl ether to obtain triphenylsulfonium N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide. Could not be crystallized. Accordingly, diisopropyl ether was distilled off to obtain 207 g of a crude product as a highly viscous liquid. At this time, the yield was 50% and the purity was 78%.

  [Example 4] Synthesis of triphenylsulfonium 2- (methacryloyloxy) ethyl trifluoromethanesulfonamide ((C) -B)

  To a 5 L glass reactor, 650 g (2.49 mol) of 2- (methacryloyloxy) ethyl trifluoromethanesulfonamide, 300 mL of water, and 200 mL of acetonitrile were added all at once, and the internal temperature was maintained at 0 ° C. by stirring. A 10% aqueous sodium hydroxide solution (1.11 kg, sodium hydroxide 2.75 mol) was slowly added dropwise, and stirring was continued for 1 hour. After adding 876 g (2.55 mol) of triphenylsulfonium bromide and 1.4 kg of chloroform at a time and stirring at 20-25 ° C. for 5 hours, the reactor contents separated into two layers were separated, and the obtained organic layer was separated. The extract was washed once with 800 mL of water and concentrated under reduced pressure. The obtained brown oil was dissolved in acetonitrile and recrystallized in diisopropyl ether to obtain 550 g of triphenylsulfonium 2- (methacryloyloxy) ethyl trifluoromethanesulfonamide. At this time, the purity was 99% and the yield was 42%.

[Physical properties of triphenylsulfonium 2- (methacryloyloxy) ethyl trifluoromethanesulfonamide]
¹ H-NMR (measurement solvent: heavy DMSO, reference material: tetramethylsilane); δ = 7.88-7.76 (m, 15H; Ph ₃ S ⁺ ), 6.00-5.89 (m, 1H ), 5.15-5.10 (m, 1H) , 3.96 (t, J = 6.59 Hz, 2H; CH 2), 3.13-3.09 (m, 2H; CH 2), 1.85 (s, 3H, CH ₃ ).
¹⁹ F-NMR (measurement solvent: heavy DMSO, reference material: trichlorofluoromethane); δ = −75.5 (s, 3F).
From the results of the above analysis, it was confirmed that the obtained compound was triphenylsulfonium 2- (methacryloyloxy) ethyl trifluoromethanesulfonamide represented by the above formula (C) -B.

[Example 5] Synthesis of compound (C) -2 To a reaction vessel, 3.91 g of N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide, 36 mL of water, and 180 mL of chloroform were added. While maintaining the temperature at 0 ° C., 4.4 g of 10% NaOH was added dropwise and stirred for 10 minutes. Thereto was added 5.42 g of PAG [A], and the mixture was stirred at room temperature for 1 hour, followed by liquid separation. The obtained organic layer was washed with 36 mL of water four times and concentrated under reduced pressure to give (C)- 6.7 g of 2 was obtained.

[Physical Properties of Compound (C) -2]
¹ H-NMR (DMSO, 400 MHz): δ (ppm) = 7.76-7.82 (m, 10H, ArH), 7.59 (s, 2H, ArH), 4.55 (s, 2H, CH _{2), 3.82-3.89 (t, 2H} , CH 2), 3.00-3.08 (t, 2H, CH 2), 2.29 (m, 6H, CH 3), 1.48 -1.93 (m, 25H, Cyclopentyl + Adamantan), 0.77-0.81 (t, 3H, CH 3).
¹⁹ F-NMR (DMSO, 376 MHz): δ (ppm) = − 75.5.
Example 6 Synthesis of Compound (C) -3 Compound (C) -3 was synthesized in the same manner as Compound (C) -2 using PAG [B].

[Physical properties of compound (C) -3]
¹ H-NMR (DMSO, 400 MHz): δ (ppm) = 8.28 (d, 2H, ArH), 8.12 (d, 1H, ArH), 7.88 (t, 1H, ArH), 7. 80 (d, 1H, ArH) , 7.62-7.74 (m, 5H, ArH), 3.82-3.89 (t, 2H, CH 2), 3.00-3.08 (t, _{2H, CH 2), 1.58-1.93 (} m, 15H, Adamantan), 1.27 (s, 9H, CH 3).
¹⁹ F-NMR (DMSO, 376 MHz): δ (ppm) = − 75.5.

[Comparative Example 1] Synthesis of triphenylsulfonium N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide In a 50 mL glass reactor, N- [2- (adamantan-1-ylcarbonyl) was added. Oxy) ethyl] trifluoromethanesulfonamide 3 g (0.009 mol), water 18 mL and chloroform 18 mL were added and stirred for 30 minutes. Thereafter, 3.1 g (0.009 mol) of triphenylsulfonium bromide was added and stirred at 21 to 28 ° C. for 15 hours at a time, followed by liquid separation. The obtained organic layer was washed 4 times with 20 mL of water and concentrated under reduced pressure. went. When acetone is added to the obtained yellow oily substance, a solid is precipitated, and the precipitate is triphenylsulfonium bromide, which is triphenylsulfonium N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide. Was not obtained.

[Comparative Example 2] Synthesis of N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide sodium salt In a 50 mL glass-made glass reactor, N obtained in [Synthesis Example 1] was used. -[2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide 3 g (9.0 mmol) and 20 mL of water were added all at once, the internal temperature was maintained at 0 ° C., and the bicarbonate was slowly stirred. Sodium (0.76 g) (NaHCO ₃ 9.0 mmol) was added, and stirring was performed while maintaining the internal temperature at 0 ° C. for 5 hours. Even when the stirring was stopped and the contents were allowed to stand, the content remained non-uniform and suspended, and water-soluble N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide sodium salt Almost no generation.

[Comparative Example 3] Synthesis of N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide sodium salt Following the reaction of Comparative Example 2, the reaction solution was stirred at room temperature for 10 hours. The liquid temperature at this time was about 23 ° C. The obtained reaction liquid was not uniform. Thereafter, water was distilled off to obtain 4.0 g of a white solid. ^{As a result} of analysis by ¹⁹ F-NMR, the ratio of the raw material N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide to the sodium salt was 9: 1.

  This white solid was dissolved in chloroform and recrystallized in diisopropyl ether, but N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide sodium salt did not crystallize.

[Comparative Example 4] Synthesis of triphenylsulfonium N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide In a 50 mL glass reactor, N-- obtained in [Synthesis Example 1] was added. 3 g (9.0 mmol) of [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide, 18 mL of water, 18 mL of chloroform, 0.76 g (9.0 mmol) of sodium bicarbonate were added, and the mixture was stirred at 23 ° C. for 30 minutes. Went. After adding 3.1 g (9.0 mmol) of triphenylsulfonium bromide and stirring at 19 to 24 ° C. for 15 hours, the reactor contents separated into two layers were separated, and the resulting organic layer was washed with 20 mL of water four times. Washed and concentrated under reduced pressure. The obtained yellow oil was analyzed by ¹⁹ F-NMR. As a result, raw materials N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide and triphenylsulfonium N- [2- ( The ratio of adamantane-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide was 8.5: 1.5.

  This yellow oil was dissolved in acetonitrile and recrystallized in diisopropyl ether, but triphenylsulfonium N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide did not crystallize.

[Comparative Example 5] Synthesis of triphenylsulfonium N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide In a 50 mL glass reactor, N- [ 2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide 3 g (0.009 mol), water 18 mL, chloroform 18 mL, potassium carbonate 1.23 g (0.009 mol) were added, and the mixture was stirred at 23 ° C. for 30 minutes. It was. After adding 3.1 g (0.009 mol) of triphenylsulfonium bromide and stirring at 19 to 24 ° C. for 15 hours, liquid separation was performed, and the obtained organic layer was washed with 20 mL of water four times and concentrated under reduced pressure. The obtained yellow oily substance was analyzed by ¹⁹ F-NMR. The ratio of the raw material N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide to the sodium salt was 4.5: 5. .5.

  This yellow oil was dissolved in acetonitrile and recrystallized in diisopropyl ether, but triphenylsulfonium N- [2- (adamantan-1-ylcarbonyloxy) ethyl] trifluoromethanesulfonamide did not crystallize.

[Comparative Example 6] Synthesis of triphenylsulfonium 2- (methacryloyloxy) ethyl trifluoromethanesulfonamide In a 25 mL glass reactor, 3.0 g of 2- (methacryloyloxy) ethyl trifluoromethanesulfonamide (11. 5 mmol), 6 mL of water, 1.5 g of acetonitrile, and 1.5 g (14.2 mmol) of sodium carbonate were added at 20 ° C., followed by stirring at 20-22 ° C. for 3 hours. After adding 4.1 g (11.2 mmol) of triphenylsulfonium bromide and 6 mL of chloroform and stirring at 18 to 26 ° C. for 15 hours, the reactor contents separated into two layers were separated, and the resulting organic layer was diluted with 6 mL of water. Washed once and concentrated under reduced pressure to give a brown oil. The obtained brown oily substance is a mixture of the raw material 2- (methacryloyloxy) ethyl trifluoromethanesulfonamide and the target triphenylsulfonium 2- (methacryloyloxy) ethyl trifluoromethanesulfonamide, It was 2.4 g. ^When analyzed by ¹⁹ F-NMR, the ratio of 2- (methacryloyloxy) ethyl trifluoromethanesulfonamide to triphenylsulfonium 2- (methacryloyloxy) ethyl trifluoromethanesulfonamide was 1: 2. . This was purified by recrystallization to obtain the desired triphenylsulfonium 2- (methacryloyloxy) ethyl trifluoromethanesulfonamide, but could not be crystallized.

[Reference Examples 1 to 5, Reference Comparative Example 1]
Each component shown in Table 1 was mixed and dissolved to prepare a positive resist composition.

  Each abbreviation in Table 1 has the following meaning. Moreover, the numerical value in [] is a compounding quantity (mass part).

(A) -1: the following polymer compound (A) -1.
(B) -1: The following compound (B) -1
(B) -2: The following compound (B) -2.
(C) -B: Compound (C) -B (produced in Example 4).
(C) -1: Compound (C) -1 (produced in Examples 1 and 2).
(C) -2: Compound (C) -2 (produced in Example 5).
(C) -3: Compound (C) -3 (produced in Example 6).
(D) -1: tri-n-octylamine.
(F) -1: The following polymer compound (F) -1.
(S) -1: PGMEA / PGME / cyclohexanone = 45/30/25 (mass ratio) mixed solvent.

[Mw = 9400, Mw / Mn = 1.65, the numerical value on the lower right of () indicates the copolymer composition ratio (molar ratio). ]

  Using the obtained positive resist composition, a resist pattern was formed according to the following procedure, and the following evaluations were performed.

[Formation of resist pattern]
An organic antireflection film composition “ARC95” (trade name, manufactured by Brewer Science Co., Ltd.) is applied onto a 12-inch silicon wafer using a spinner, and baked at 205 ° C. for 90 seconds on a hot plate and dried. Thereby, an organic antireflection film having a thickness of 90 nm was formed.

  Then, the resist compositions of Reference Examples 1 to 5 and Reference Comparative Example 1 were applied on the organic antireflection film using a spinner, and prebaked (PAB) on a hot plate at 120 ° C. for 60 seconds. ) A resist film having a film thickness of 100 nm was formed by performing treatment and drying.

  Next, using an ArF immersion exposure apparatus NSR-S609B (Nikon Corporation; Dipole (in / out: 0.78 / 0.97) w / POLANO; immersion medium: water), a mask pattern (6% halftone) Then, the resist film was selectively irradiated with an ArF excimer laser (193 nm).

  Then, PEB treatment was performed at 115 ° C. for 60 seconds, and further, alkali development treatment was carried out at 23 ° C. with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 10 seconds, and then water was added using pure water. Rinsing was performed for 30 seconds, and then shaken and dried.

Subsequently, post-baking was performed at 100 ° C. for 45 seconds.

  As a result, in each example, a 1: 1 line and space (LS) pattern having a line width of 50 nm was obtained.

The optimum exposure dose Eop (mJ / cm ² ; sensitivity) for forming the LS pattern was determined. The results are shown in Table 2.

[LWR (line width roughness) evaluation]
In an LS pattern having a line width of 50 nm and a pitch of 100 nm formed in the dew Eop, the space width is measured by a length measuring SEM (scanning electron microscope, acceleration voltage 800 V, trade name: S-9220, manufactured by Hitachi, Ltd.). 400 points were measured in the longitudinal direction, and a triple value (3s) of the standard deviation (s) was obtained from the result, and a value averaged for 3s at 400 points was calculated as a scale indicating LWR. The results are shown in Table 2.

  A smaller value of 3s means that the roughness of the line width is smaller, and an LS pattern having a more uniform width is obtained.

[Evaluation of pattern collapse]
The LS pattern was formed in the same manner as above except that the Eop was changed, and the line width immediately before the pattern collapsed was measured.

The smaller this value is, the better the resist pattern is less likely to fall (resistance to pattern fall).

[Evaluation of exposure margin (EL margin)]
In Eop, the exposure amount when the line of the LS pattern is formed within a range of ± 5% (47.5 nm to 52.5 nm) of the target dimension (line width 50 nm) is obtained, and the EL margin (unit: %). The results are shown in Table 2.

EL margin (%) = (| E1-E2 | / EOP) × 100
E1: Exposure amount (mJ / cm ² ) when an LS pattern having a space width of 47.5 nm was formed
E2: exposure amount (mJ / cm ² ) when an LS pattern having a space width of 52.5 nm was formed
Note that the larger the value of the EL margin, the smaller the change amount of the pattern size accompanying the change in the exposure amount.

[Pattern shape evaluation]
The cross-sectional shape of the pattern formed at the optimum exposure amount Eop at which the 50 nm 1: 1 LS pattern is formed is observed using a scanning electron microscope (trade name: S-4700, manufactured by Hitachi, Ltd.), and the shape is observed. Evaluation was made according to the following criteria. The results are shown in Table 2.
○: The rectangularity is high and good.
Δ: Top-round shape and low rectangularity.
X: T-top shape and low rectangularity.

  From the results in Table 2, the resist compositions of Reference Examples 1 to 5 have better lithography properties and shapes such as LWR and EL margin than the resist composition of Reference Comparative Example 1, and the pattern collapse is suppressed. It was confirmed that

Claims (8)

The following general formula (1)

Including a first step of reacting a sulfonamide represented by the formula (2) with an alkali metal hydroxide.

The manufacturing method of the sulfonamide alkali metal salt represented by these.
(In each formula, R ¹ has a polymerizable unsaturated group at the terminal having 2 or more carbon atoms which may have a substituent, or an alicyclic group having 5 or more carbon atoms or which may have a substituent. The substituent in R ¹ is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, or It is an oxygen atom (= O) X is a divalent linking group, and the divalent linking group is any group selected from the following (a) to (c).
(A) a linear, branched or cyclic aliphatic hydrocarbon group which may have a substituent [the substituent in the aliphatic hydrocarbon group is a fluorine atom or the number of carbon atoms substituted by a fluorine atom; 1 to 5 fluorinated alkyl groups, or an oxygen atom (= O)],
(B) an aromatic hydrocarbon group which may have a substituent [the substituent in the aromatic hydrocarbon group is an alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a carbon number substituted with a fluorine atom; 1 to 5 fluorinated alkyl groups, or an oxygen atom (= O). ],
(C) “—O—, —C (═O) —O—, —C (═O) —NH—, —C (═O) —, —O—C (═O) —O—, general formula Any group selected from —A—O—, —O—A—O—, — [A—C (═O) —O] _m —, and —A—O—C (═O) —. A has the same meaning as the “divalent linking group” defined in (a) or (b) above. m is an integer of 0-3. Y is a linear, branched or cyclic alkylene group or arylene group, Rf is a hydrocarbon group containing a fluorine atom, and M ⁺ is an alkali metal ion. ) The method for producing a sulfonamide alkali metal salt according to claim 1, wherein the alkali metal hydroxide is sodium hydroxide. The method for producing a sulfonamide alkali metal salt according to claim 1 or 2, wherein the reaction in the first step is carried out in an organic solvent containing water. The method for producing a sulfonamide alkali metal salt according to any one of claims 1 to 3, wherein the reaction in the first step is performed at -10 to 40 ° C. The monovalent onium salt A ^<+> Z ^{< - >} (4) represented by General formula (4) for the sulfonamide alkali metal salt obtained by the manufacturing method of any one of Claims 1-4.
Comprising a second step of exchanging onium salts by general formula (3)

The manufacturing method of the sulfonamido onium salt represented by these.
(In the formula, the meanings of R ¹ and X are the same as those in claim 1. Y is a linear, branched or cyclic alkylene group or arylene group, and Rf is a hydrocarbon group containing a fluorine atom.) Z ⁻ is a monovalent anion, and A ⁺ is a sulfonium cation represented by the following general formula (a) or an iodonium cation represented by the following general formula (b).

^(Wherein, R 2, ^{R 3} and ^{R 4} independently of one another, represent an alkyl group or a substituted or unsubstituted aryl group with carbon number from 6 to 20, from 1 to 1 0 carbon atoms. Substituted in the aryl group The group is an alkyl group, an alkoxy group, a halogen atom or a hydroxyl group, and any two or more of R ² , R ³ and R ⁴ are bonded to each other to form a ring together with the sulfur atom in the formula. May be.)

(Wherein, ^{R 5} and ^{R 6} independently of one another, substituents on. The aryl group represents an alkyl group or a substituted or unsubstituted aryl group with carbon number from 6 to 20, carbon number 1-1 0, An alkyl group, an alkoxy group, a halogen atom or a hydroxyl group, and R ⁵ and R ⁶ may be bonded to each other to form a ring together with the iodine atom in the formula.) The method for producing a sulfonamidoonium salt according to claim 5, wherein the second step is carried out without isolating the sulfonamide alkali metal salt obtained in the first step. The production method according to claim 1, wherein R ¹ is an adamantyl group, X is “—C (═O) —O—”, and Rf is a trifluoromethyl group . The production method according to claim 1, wherein R ¹ is a methacryloyl group, X is “—C (═O) —O—”, and Rf is a trifluoromethyl group .