JP5703701B2 - Salt and resist composition for acid generator - Google Patents

Description

  The present invention relates to a salt for an acid generator and a resist composition.

A resist composition used for fine processing of a semiconductor using a lithography technique contains an acid generator.
Patent Document 1 describes a salt represented by the following formula as an acid generator.

JP 2007-161707 A

  Conventional salt for an acid generator may not always satisfy the resolution of a pattern obtained from a resist composition containing the salt.

［式（Ｉ）中、
Ｑ^１及びＱ^２は、互いに独立に、フッ素原子又はＣ_１-６ペルフルオロアルキル基を表す。
Ｌ^１及びＬ^２は、それぞれ独立に、Ｃ_１-１７アルキレン基を表し、該アルキレン基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
環Ｗ^１は、Ｃ_３-３６飽和炭化水素環を表す。
Ｒ^２は、Ｃ_１-６アルキル基又はＣ_１-６アルコキシ基を表す。
ｓは、０〜２の整数を表す。ｓが２である場合、複数のＲ^２は同じであっても異なっていてもよい。
環Ｗ^２は、Ｃ_３-３６飽和炭化水素環を表す。
Ｒ^４は、ヒドロキシル基、Ｃ_１-６ヒドロキシアルキル基又はＣ_１-６ヒドロキシアルコキシ基を表し、該ヒドロキシアルキル基及び該ヒドロキシアルコキシに含まれる水素原子はハロゲン原子で置換されていてもよい。
ｖは、１〜３の整数を表す。ｖが２又は３である場合、複数のＲ^４は同じであっても異なっていてもよい。
Ｒ^５は、Ｃ_１-６アルキル基又はＣ_１-６アルコキシ基を表す。
ｗは、０〜２の整数を表す。ｗが２である場合、複数のＲ^５は同じであっても異なっていてもよい。
Ｚ^＋は、有機対イオンを表す。］ The present invention includes the following inventions.
[1] A salt represented by the formula (I).

[In the formula (I),
Q ¹ and Q ² each independently represent a fluorine atom or a C _1-6 perfluoroalkyl group.
L ¹ and L ² each independently represent a C _1-17 alkylene group, and —CH ₂ — contained in the alkylene group may be replaced by —O— or —CO—.
Ring W ¹ represents a C _3-36 saturated hydrocarbon ring.
R ² represents a C _1-6 alkyl group or a C _1-6 alkoxy group.
s represents the integer of 0-2. When s is 2, the plurality of R ² may be the same or different.
Ring W ² represents a C _3-36 saturated hydrocarbon ring.
R ⁴ represents a hydroxyl group, a C _1-6 hydroxyalkyl group or a C _1-6 hydroxyalkoxy group, and a hydrogen atom contained in the hydroxyalkyl group and the hydroxyalkoxy may be substituted with a halogen atom.
v represents an integer of 1 to 3. When v is 2 or 3, the plurality of R ⁴ may be the same or different.
R ⁵ represents a C _1-6 alkyl group or a C _1-6 alkoxy group.
w represents an integer of 0 to 2. When w is 2, the plurality of R ⁵ may be the same or different.
Z ⁺ represents an organic counter ion. ]

［式（Ｉ１）中、
Ｑ^１、Ｑ^２、Ｌ^１、Ｌ^２、環Ｗ^１、Ｒ^２、ｓ、環Ｗ^２、Ｒ^４、ｖ、Ｒ^５、ｗ及びＺ^＋は、前記と同じ意味を表す。
Ｒ^１は、水素原子又はＣ_１-６アルキル基を表すか、環Ｗ^１に含まれる炭素原子と互いに結合して環を形成する。］ [2] The salt according to [1], wherein the salt represented by the formula (I) is a salt represented by the formula (I1).

[In the formula (I1),
Q ¹ , Q ² , L ¹ , L ² , ring W ¹ , R ² , s, ring W ² , R ⁴ , v, R ⁵ , w and Z ⁺ represent the same meaning as described above.
R ¹ represents a hydrogen atom or a C _1-6 alkyl group, or is bonded to a carbon atom contained in the ring W ¹ to form a ring. ]

[3] L ¹ is ^* —CO—OL ³ —, ^* —CO—O—L ⁴ —O—, —L ⁵ —O—CO— or ^* —CO—O—L ⁶ —CO—O. -(L ³ represents a single bond or a C _1-6 alkylene group, L ⁴ , L ⁵ and L ⁶ each independently represent a C _1-6 alkylene group, and * represents —C (Q ¹ ) ( Q ² )-represents a bond to-.) The salt according to [1] or [2].

[4] L ² is ^* -OL ⁷ -CO-O-, ^* -OL ⁸ -CO-OL ⁹ -O-, ^* -CO-OL ¹⁰ -CO-O-, ^* —O—CO—L ¹¹ —O— or ^* —O—L ¹² —O— (L ^{7 to} L ¹² each independently represents a C _1-6 alkylene group, and * represents a bond to ring W ^1. The salt according to any one of [1] to [3].

[5] The salt according to any one of [1] to [4], wherein Ring W ¹ is an adamantane ring.

[6] The salt according to any one of [1] to [5], wherein ring W ² is an adamantane ring.

[7] The salt according to any one of [1] to [6], wherein Z ⁺ is a triarylsulfonium cation.

[8] An acid generator containing the salt according to any one of [1] to [7].

[9] The acid generator according to [8] and a resin, wherein the resin has an acid labile group and is insoluble or hardly soluble in an alkaline aqueous solution, and is dissolved in an alkaline aqueous solution by the action of an acid. Resist composition which is resin which can be done.

[10] The resist composition according to [9], further containing a basic compound.

[11] (1) A step of applying the resist composition according to [9] or [10] on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer using an exposure machine;
(4) A step of heating the composition layer after exposure,
(5) a step of developing the heated composition layer using a developing device;
A method for producing a resist pattern including:

  According to the salt of the present invention, a pattern having excellent resolution can be obtained from a resist composition containing the salt.

［式（Ｉ）中、
Ｑ^１及びＱ^２は、互いに独立に、フッ素原子又はＣ_１-６ペルフルオロアルキル基を表す。
Ｌ^１及びＬ^２は、それぞれ独立に、Ｃ_１-１７アルキレン基を表し、該アルキレン基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
環Ｗ^１は、Ｃ_３-３６飽和炭化水素環を表す。
Ｒ^２は、Ｃ_１-６アルキル基又はＣ_１-６アルコキシ基を表す。
ｓは、０〜２の整数を表す。ｓが２である場合、複数のＲ^２は同じであっても異なっていてもよい。
環Ｗ^２は、Ｃ_３-３６飽和炭化水素環を表す。
Ｒ^４は、ヒドロキシル基、Ｃ_１-６ヒドロキシアルキル基又はＣ_１-６ヒドロキシアルコキシ基を表し、該ヒドロキシアルキル基及び該ヒドロキシアルコキシに含まれる水素原子はハロゲン原子で置換されていてもよい。
ｖは、１〜３の整数を表す。ｖが２又は３である場合、複数のＲ^４は同じであっても異なっていてもよい。
Ｒ^５は、Ｃ_１-６アルキル基又はＣ_１-６アルコキシ基を表す。
ｗは、０〜２の整数を表す。ｗが２である場合、複数のＲ^５は同じであっても異なっていてもよい。
Ｚ^＋は、有機対イオンを表す。］ <Salt represented by formula (I)>
The salt of the present invention is represented by the formula (I).
In this specification, “C _ab ” means “carbon number ab”.

[In the formula (I),
Q ¹ and Q ² each independently represent a fluorine atom or a C _1-6 perfluoroalkyl group.
L ¹ and L ² each independently represent a C _1-17 alkylene group, and —CH ₂ — contained in the alkylene group may be replaced by —O— or —CO—.
Ring W ¹ represents a C _3-36 saturated hydrocarbon ring.
R ² represents a C _1-6 alkyl group or a C _1-6 alkoxy group.
s represents the integer of 0-2. When s is 2, the plurality of R ² may be the same or different.
Ring W ² represents a C _3-36 saturated hydrocarbon ring.
R ⁴ represents a hydroxyl group, a C _1-6 hydroxyalkyl group or a C _1-6 hydroxyalkoxy group, and a hydrogen atom contained in the hydroxyalkyl group and the hydroxyalkoxy may be substituted with a halogen atom.
v represents an integer of 1 to 3. When v is 2 or 3, the plurality of R ⁴ may be the same or different.
R ⁵ represents a C _1-6 alkyl group or a C _1-6 alkoxy group.
w represents an integer of 0 to 2. When w is 2, the plurality of R ⁵ may be the same or different.
Z ⁺ represents an organic counter ion. ]

In the present specification, “C _ab ” means “the number of carbon atoms is ab”.
Q ¹ and Q ² each independently represents a fluorine atom or a C _1-6 perfluoroalkyl group. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. . Q ¹ and Q ² are each independently preferably a perfluoromethyl group or a fluorine atom, more preferably a fluorine atom.

L ¹ represents ^* —CO—O—L ³ —, ^* —CO—O—L ⁴ —O—, —L ⁵ —O—CO— or ^* —CO—O—L ⁶ —CO—O— (L ³ represents a single bond or a C _1-6 alkylene group, L ⁴ , L ⁵ and L ⁶ each independently represent a C _1-6 alkylene group, and * represents —C (Q ¹ ) (Q ² ). -Represents a bond with-).
L ¹ is more preferably ^* —CO—O—L ³ —, ^* —CO—O—L ⁴ —O—, and ^* —CO—O—L ⁶ —CO—O—, and ^* —CO—O—. ^* -CO—O—CH ₂ —, ^* —CO—O—C ₂ H ₅ —O— or ^* —CO—O—CH ₂ —CO—O— is more preferable, and ^* —CO—O— is particularly preferable. preferable.

L ² is ^* -OL ⁷ -CO-O-, ^* -OL ⁸ -CO-OL ⁹ -O-, ^* -CO-OL ¹⁰ -CO-O-, ^* -O —CO—L ¹¹ —O— or ^* —O—L ¹² —O— (L ^{7 to} L ¹² each independently represents a C _1-6 alkylene group, and * represents a bond to ring W ^1. .).
L ² is more preferably ^* —O—L ⁷ —CO—O— or ^* —CO—O—L ¹⁰ —CO—O—, ^* —O—CH ₂ —CO—O— or ^* —CO—. O—CH ₂ —CO—O— is particularly preferred.

［式（Ｉ１）中、
Ｑ^１、Ｑ^２、Ｌ^１、Ｌ^２、環Ｗ^１、Ｒ^２、ｓ、環Ｗ^２、Ｒ^４、ｖ、Ｒ^５、ｗ及びＺ^＋は、前記と同じ意味を表す。
Ｒ^１は、水素原子又はＣ_１-６アルキル基を表すか、環Ｗ^１に含まれる炭素原子と互いに結合して環を形成する。］ The salt represented by the formula (I) is preferably a salt represented by the formula (I1).

[In the formula (I1),
Q ¹ , Q ² , L ¹ , L ² , ring W ¹ , R ² , s, ring W ² , R ⁴ , v, R ⁵ , w and Z ⁺ represent the same meaning as described above.
R ¹ represents a hydrogen atom or a C _1-6 alkyl group, or is bonded to a carbon atom contained in the ring W ¹ to form a ring. ]

［式（Ｉ−Ａ）中、Ｒ^１、Ｒ^２、環Ｗ^１及びｓは上記と同じ意味を表す。＊は、Ｌ^１との結合手を表す。］ The group represented by the formula (IA) will be described.

[In formula (IA), R ¹ , R ² , ring W ¹ and s represent the same meaning as described above. * Represents a bond to ^{L 1.} ]

The saturated hydrocarbon ring in the ring W ¹ refers to a ring composed of only carbon and hydrogen that does not contain an unsaturated bond. Examples of the saturated hydrocarbon ring include a cyclohexane ring and an adamantane ring, and an adamantane ring is preferable.

Among groups represented by the formula (IA), examples of the group in which R ¹ is a C _1-6 alkyl group include groups represented by the following.

Of the groups represented by the formula (IA), examples of the group in which R ¹ is a hydrogen atom include the groups represented by the following.

式（Ｉ−Ａ)で表される基としては、式（Ｉ−Ａａ）で表される基が好ましい。 Of the groups represented by formula (IA), examples of the group in which R ¹ is bonded to the carbon atom contained in ring W ¹ to form a ring include the groups represented by the following.

The group represented by the formula (IA) is preferably a group represented by the formula (I-Aa).

［式（Ｉ−Ｂ）中、Ｒ^４、ｖ、Ｒ^５、ｗ及び環Ｗ^２は上記と同じ意味を表す。
＊は、Ｌ^２との結合手を表す。］ The group represented by the formula (IB) will be described.

[In the formula (IB), R ⁴ , v, R ⁵ , w and ring W ² represent the same meaning as described above.
* Represents a bond to ^{L 2.} ]

The saturated hydrocarbon ring in the ring W ² refers to a ring composed of only carbon and hydrogen that does not contain an unsaturated bond. Examples of the saturated hydrocarbon ring include a cyclohexane ring and an adamantane ring, and an adamantane ring is preferable.

Specific examples of the group represented by the formula (IB) include the following groups.

R ⁴ represents a hydroxy group, a C _1-6 hydroxyalkyl group or a C _1-6 hydroxyalkoxy group, and a hydrogen atom contained in the hydroxyalkyl group and the hydroxyalkoxy may be substituted with a halogen atom.
The C _1-6 hydroxyalkyl group, a hydrogen atom contained in the C _1-6 alkyl groups described above include groups substituted with a hydroxy group.
The C _1-6 hydroxyalkoxy group, a hydrogen atom contained in the C _1-6 alkoxy group described above include groups substituted with a hydroxy group.

Specific examples of R ⁴ include the following groups.

Examples of the substituent that the ring W ¹ and the ring W ² may have include a C _1-6 alkyl group and a C _1-6 alkoxy group.
Examples of the C _1-6 alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, and the like. A C _1-4 alkyl group is preferred, a C _1-2 alkyl group is more preferred, and a methyl group is particularly preferred.
Examples of the C _1-6 alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, and an n-hexoxy group. A C _1-4 alkoxy group is preferable, a C _1-2 alkoxy group is more preferable, and a methoxy group is particularly preferable.

Examples of the salt represented by the formula (I) include the following salts.

Examples of Z ⁺ include onium cations such as sulfonium cations, iodonium cations, ammonium cations, benzothiazolium cations, and phosphonium cations. Among these, a sulfonium cation and an iodonium cation are preferable, and an arylsulfonium cation is more preferable.

Z ⁺ is preferably represented by any one of formulas (b2-1) to (b2-4).

In formula (b2-1), R ^{b4 to} R ^b6 each independently represent a C _1-30 alkyl group, a C _3-36 saturated cyclic hydrocarbon group, or a C _6-18 aromatic hydrocarbon group. The alkyl group may be substituted with a hydroxy group, a C _1-12 alkoxy group or a C _6-18 aromatic hydrocarbon group, and the saturated cyclic hydrocarbon group includes a halogen atom, a C _2-4 acyl group, Alternatively, the aromatic hydrocarbon group may be substituted with a glycidyloxy group, and the aromatic hydrocarbon group is a halogen atom, a hydroxy group, a C _1-36 alkyl group, a C _3-36 saturated cyclic hydrocarbon group or a C _1-12 alkoxy group. May be substituted.

In formula (b2-2), R ^b7 and R ^b8 each independently represent a hydroxy group, a C _1-12 alkyl group or a C _1-12 alkoxy group, and m2 and n2 each independently represent 0 to 5 Represents an integer.

In formula (b2-3), R ^b9 and R ^b10 each independently represent a C _1-36 alkyl group or a C _3-36 saturated cyclic hydrocarbon group. R ^b11 represents a hydrogen atom, a C _1-36 alkyl group, a C _3-36 saturated cyclic hydrocarbon group or a C _6-18 aromatic hydrocarbon group. R ^b9 to R number of carbon atoms in the alkyl group ^b11 is preferably from 1 to 12 carbon atoms in the saturated cyclic hydrocarbon group is preferably 3 to 36, more preferably 4 to 12. R ^b12 represents a C _1-12 alkyl group, a C _3-18 saturated cyclic hydrocarbon group, or a C _6-18 aromatic hydrocarbon group. The aromatic hydrocarbon group may be substituted with a C _1-12 alkyl group, a C _1-12 alkoxy group, a C _3-18 saturated cyclic hydrocarbon group, or an alkylcarbonyloxy group. R ^b9 and R ^b10 , and R ^b11 and R ^b12 may be independently bonded to each other to form a 3- to 12-membered ring (preferably a 3- to 7-membered ring), In these rings, —CH ₂ — may be replaced by —O—, —S—, or —CO—.

In formula (b2-4), R ^{b13 to} R ^b18 each independently represent a hydroxy group, a C _1-12 alkyl group, or a C _1-12 alkoxy group. L ^b11 represents -S- or -O-. o2, p2, s2, and t2 each independently represent an integer of 0 to 5, q2 and r2 each independently represent an integer of 0 to 4, and u2 represents 0 or 1. When any of o2 to t2 is 2, any of the plurality of R ^{b13 to} R ^b18 may be the same as or different from each other.

Next, substituents included in the formulas (b2-1) to (b2-4) will be described. Examples of the alkyl group, saturated cyclic hydrocarbon group and aromatic hydrocarbon group include those described above. Preferred alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, and 2-ethylhexyl. . Preferred saturated cyclic hydrocarbon groups are cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclodecyl group, 2-alkyl-2-adamantyl group, 1- (1-adamantyl) -1-alkyl group, And an isobornyl group. Preferred aromatic hydrocarbon groups are phenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-tert-butylphenyl group, 4-cyclohexylphenyl group, 4-methoxyphenyl group, biphenylyl group, naphthyl group. It is. Examples of the alkyl group (aralkyl group) whose substituent is an aromatic hydrocarbon group include a benzyl group. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, n-hexoxy, heptoxy, octoxy Group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like. Examples of the ring formed by R ^b9 and R ^b10 include a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium ring. ^Examples of the ring formed by R ^b11 and R ^b12 include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

  Among the cations (b2-1) to (b2-4), the cation (b2-1) is preferable, the cation represented by the formula (b2-1-1) is more preferable, and the triphenylsulfonium cation (formula (b2) In (1-1), v2 = w2 = x2 = 0) is more preferable.

In formula (b2-1-1), R ^{b19 to} R ^b21 each independently represent a halogen atom, a hydroxy group, a C _1-36 alkyl group, a C _3-36 saturated cyclic hydrocarbon group or a C _1-12 alkoxy group. R ^b19 and R ^b20 may be combined to form a ring. The alkyl group preferably has 1 to 12 carbon atoms, and the saturated cyclic hydrocarbon group preferably has 4 to 36 carbon atoms. The alkyl group may be substituted with a hydroxy group, a C _1-12 alkoxy group or a C _6-18 aromatic hydrocarbon group, and the saturated cyclic hydrocarbon group includes a halogen atom, a C _2-4 acyl group, Alternatively, it may be substituted with a glycidyloxy group. v2 to x2 each independently represents an integer of 0 to 5 (preferably 0 or 1). When any one of v2 to x2 is 2 or more, any one of the plurality of R ^{b19 to} R ^b21 may be the same as or different from each other.

R ^{b19 to} R ^b21 in formula (b2-1-1) are preferably each independently a halogen atom (more preferably a fluorine atom), a hydroxy group, a C _1-12 alkyl group, or a C _1-12 alkoxy. And v2 to x2 each independently represents an integer of 0 to 5 (preferably 0 or 1).

  Specific examples of the cation (b2-1-1) include the following.

  Specific examples of the cation (b2-2) include the following.

  Specific examples of the cation (b2-3) include the following.

  Specific examples of the cation (b2-4) include the following.

Examples of the salt represented by the formula (I) include the following salts.

A method for producing the salt represented by the formula (I) will be described.
For example, the manufacturing method of the salt represented by Formula (b1) is shown below.

［Ｘ^１は、ハロゲン原子を表す。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられ、塩素原子が好ましい。］ A compound represented by the formula (b1-c) can be obtained by reacting a compound represented by the formula (b1-a) with a compound represented by the formula (b1-b) under a basic catalyst. it can. Examples of the solvent include tetrahydrofuran. Examples of the base catalyst include pyridine.

[X ¹ represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable. ]

The compound represented by the formula (b1-e) can be obtained by reacting the compound represented by the formula (b1-c) with the compound represented by the formula (b1-d) in the presence of a catalyst. Examples of the solvent include dimethylformamide. Examples of the catalyst include potassium carbonate and potassium iodide.

The salt represented by the formula (b1-f) can be synthesized by the method described in JP-A-2008-127367.
The salt represented by the formula (b1) can be obtained by reacting the compound represented by the formula (b1-e) with the salt represented by the formula (b1-f) under a catalyst. Examples of the solvent include monochlorobenzene. Examples of the catalyst include sulfuric acid.

A method for producing the salt represented by the formula (b2) is shown below.

［Ｘ^３は、それぞれ独立に、ハロゲン原子を表す。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられ、臭素原子が好ましい。］ A compound represented by the formula (b2-b) can be obtained by reacting a compound represented by the formula (b2-a) with a compound represented by the formula (b1-e) under a basic catalyst. it can. Examples of the solvent include tetrahydrofuran. Examples of the base catalyst include pyridine.

[X ³ each independently represents a halogen atom. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, A bromine atom is preferable. ]

The salt represented by the formula (b1-f) can be synthesized by the method described in JP-A-2008-127367.
The salt represented by the formula (b2) can be obtained by reacting the compound represented by the formula (b2-b) with the salt represented by the formula (b1-f) in the presence of a catalyst. Examples of the solvent include monochlorobenzene. Examples of the catalyst include sulfuric acid.

A method for producing the salt represented by the formula (b3) is shown below.

式（ｂ３−ａ）で表される化合物と式（ｂ１−ｂ）で表される化合物を塩基性触媒下で、反応させることにより、式（ｂ３−ｂ）で表される化合物を得ることができる。溶媒としては、テトラヒドロフラン等が挙げられる。塩基触媒としては、ピリジン等が挙げられる。

A compound represented by the formula (b3-a) can be obtained by reacting a compound represented by the formula (b1-a) with a compound represented by the formula (b2-a) under a basic catalyst. it can. Examples of the solvent include tetrahydrofuran. Examples of the base catalyst include pyridine.

A compound represented by formula (b3-b) can be obtained by reacting a compound represented by formula (b3-a) with a compound represented by formula (b1-b) under a basic catalyst. it can. Examples of the solvent include tetrahydrofuran. Examples of the base catalyst include pyridine.

The compound represented by the formula (b3-c) can be obtained by reacting the compound represented by the formula (b3-b) with the compound represented by the formula (b1-d) in the presence of a catalyst. Examples of the solvent include dimethylformamide. Examples of the catalyst include potassium carbonate and potassium iodide.

The salt represented by the formula (b1-f) can be synthesized by the method described in JP-A-2008-127367.
The salt represented by the formula (b3) can be obtained by reacting the compound represented by the formula (b3-c) with the salt represented by the formula (b1-f) under a catalyst. Examples of the solvent include monochlorobenzene. Examples of the catalyst include sulfuric acid.

A method for producing the salt represented by the formula (b4) is shown below.

［Ｘ^１及びＸ^２は、それぞれ独立に、ハロゲン原子を表す。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられ、塩素原子が好ましい。］ A compound represented by the formula (b4-c) can be obtained by reacting a compound represented by the formula (b4-a) with a compound represented by the formula (b4-b) under a basic catalyst. it can. Examples of the solvent include tetrahydrofuran. Examples of the base catalyst include pyridine.

[X ¹ and X ² each independently represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable. ]

The compound represented by the formula (b4-e) can be obtained by reacting the compound represented by the formula (b4-c) with the compound represented by the formula (b4-d) in the presence of a catalyst. Examples of the solvent include dimethylformamide. Examples of the catalyst include potassium carbonate and potassium iodide.

The compound represented by the formula (b4-f) can be obtained by reducing the compound represented by the formula (b4-e) under a catalyst. Examples of the solvent include acetonitrile. Examples of the catalyst include sodium borohydride.

The salt represented by the formula (b4) can be obtained by reacting the salt represented by the formula (b4-g) with the compound represented by the formula (b4-f) in the presence of an acid catalyst.
The salt represented by the formula (b4-g) can be synthesized, for example, by the method described in JP2008-13551A. Examples of the solvent include monochlorobenzene. Examples of the catalyst include sulfuric acid.

  The acid generator of the present invention contains a salt represented by the formula (I). When used as an acid generator, the salt represented by the formula (I) may be used alone or in combination of two or more. The acid generator of the present invention further includes a known salt other than the salt represented by the formula (I), a salt composed of a cation and a known anion contained in the salt represented by the formula (I), and a formula You may use together with the salt which consists of an anion contained in the salt represented by (I), and a well-known cation.

  As an acid generator (B) used together, what is represented by a formula (B1-1)-a formula (B1-17) is mentioned, for example. Among them, acid generators (B1-1), (B1-2), (B1-6), (B1-11), (B1-12), (B1-13) and (B1-14) containing a triphenylsulfonium cation ) Is preferred.

The content of the salt represented by formula (I) is preferably 10 parts by mass or more (more preferably 30 parts by mass or more), preferably 90 parts by mass or less (more preferably) with respect to 100 parts by mass of the total amount of the acid generator. Is 70 parts by mass or less).
The content of the acid generator is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 40 parts by mass or less (more preferably 35 parts by mass or less) with respect to 100 parts by mass of the resin (A). It is.

<Resin (hereinafter sometimes referred to as “resin (A)”)>
Resin (A) is a resin that becomes alkali-soluble by the action of an acid. A resin that becomes alkali-soluble by the action of an acid can be produced by polymerizing a monomer having an acid-labile group (hereinafter sometimes referred to as “monomer having an acid-labile group (a1)”), It becomes alkali-soluble by the action of acid. The phrase “becomes soluble in an alkali by the action of an acid” means “being insoluble or hardly soluble in an alkaline aqueous solution before contact with an acid, but soluble in an alkaline aqueous solution after contact with an acid”. . As the monomer (a1) having an acid labile group, one type may be used alone, or two or more types may be used in combination.

<Monomer (a1) having an acid labile group>
The “acid-labile group” means a group that cleaves a leaving group upon contact with an acid to form a hydrophilic group (for example, a hydroxy group or a carboxy group). Examples of the acid labile group include a group represented by the formula (1). Hereinafter, the group represented by the formula (1) may be referred to as “acid-labile group (1)”.

In formula (1), R ^{a1 to} R ^a3 each independently represents an alkyl group or a saturated cyclic hydrocarbon group, or R ^a1 and R ^a2 are bonded to each other to form a ring. * Represents a bond.

Examples of the acid labile group (1) include a 1,1-dialkylalkoxycarbonyl group (in the group (1), R ^{a1 to} R ^a3 are alkyl groups, preferably a tert-butoxycarbonyl group), 2 -Alkyl-2-adamantyloxycarbonyl group (in formula (1), wherein R ^a1 , R ^a2 and a carbon atom form an adamantyl group, and R ^a3 is an alkyl group), and 1- (1-adamantyl)- 1-alkylalkoxycarbonyl groups (in the formula (1), R ^a1 and R ^a2 are alkyl groups and R ^a3 is an adamantyl group) and the like.

The monomer (a1) having an acid labile group is preferably a monomer having an acid labile group (1) and a carbon-carbon double bond, more preferably an acid labile group (1). (Meth) acrylic monomer having In the present specification, "(meth) acrylic monomer" means "CH ₂ = CH-CO-" or _{"CH 2 = C (CH 3)} -CO- " at least one monomer having the structure To do. Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.

Among the (meth) acrylic monomers having the acid labile group (1), those having a C _5-20 saturated cyclic hydrocarbon group are preferred. If a resin obtained by polymerizing the monomer (a1) having a bulky structure such as a saturated cyclic hydrocarbon group is used, the resolution of the resist can be improved. The saturated cyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic saturated cyclic hydrocarbon group include a cycloalkyl group (for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group). Examples of the polycyclic saturated cyclic hydrocarbon group include a group obtained by hydrogenating a condensed aromatic hydrocarbon group (for example, a hydronaphthyl group), a bridged cyclic hydrocarbon group (for example, an adamantyl group, a norbornyl group), and the like. . In addition, a bridged ring (for example, a norbornane ring) and a single ring (for example, a cycloheptane ring or a cyclohexane ring) or a polycyclic (for example, a decahydronaphthalene ring) in a condensed form, such that a bridged ring is condensed. The group having the above shape is also included in the saturated cyclic hydrocarbon group.

  Among the (meth) acrylic monomers having the acid labile group (1) and the saturated cyclic hydrocarbon group, the acid labile group represented by the formula (a1-1) or the formula (a1-2) Monomers having are preferred. These may be used alone or in combination of two or more.

Wherein (a1-1) and the formula (a1-2), L ^a1 and L ^a2 each ^{independently,} * -O- or _{^{* -O- (CH 2) k1 -CO}} -O- and represents and * It represents a bond with —CO—, and k1 represents an integer of 1 to 7. R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group. R ^a6 and R ^a7 each independently represent a C _1-8 alkyl group or a C _3-10 saturated cyclic hydrocarbon group, m1 represents an integer of 0-14, and n1 represents an integer of 0-10. . The chemical formula in this specification includes stereoisomers.

L ^a1 and L ^a2 are preferably ^* —O— or ^* —O— (CH ₂ ) _f1 —CO—O— (wherein f1 is an integer of 1 to 4), more preferably ^* —. O-.

R ^a4 and R ^a5 are preferably methyl groups. The carbon number of the alkyl group of R ^a6 and R ^a7 is preferably 6 or less, and the carbon number of the saturated cyclic hydrocarbon group is preferably 8 or less, more preferably 6 or less. Examples of the alkyl group for R ^a6 and R ^a7 include a methyl group, an ethyl group, a 1-methylethyl group (isopropyl group), a 1,1-dimethylethyl group (tert-butyl group), a 2,2-dimethylethyl group, Propyl group, 1-methylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-propylbutyl group, pentyl group, Examples include 1-methylpentyl group, hexyl group, 1,4-dimethylhexyl group, heptyl group, 1-methylheptyl group, octyl group and the like. Examples of the saturated cyclic hydrocarbon group for R ^a6 and R ^a7 include a cycloheptyl group, a methylcycloheptyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a norbornyl group, and a methylnorbornyl group.

  m1 is preferably an integer of 0 to 3, more preferably 0 or 1. n1 is 0, preferably an integer of 0 to 3, more preferably 0 or 1. k1 is preferably an integer of 1 to 4, more preferably 1.

  Examples of the monomer (a1-1) having an adamantyl group include the following, among which 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, and 2-Isopropyl-2-adamantyl (meth) acrylate is preferred, and the methacrylate form is more preferred.

  Examples of the monomer (a1-2) having a cyclohexyl group include the following, among which 1-ethyl-1-cyclohexyl (meth) acrylate is preferable, and 1-ethyl-1-cyclohexyl methacrylate is more preferable. preferable.

  The content of the structural unit derived from the monomer represented by the formula (a1-1) or the formula (a1-2) in the resin is usually 10 to 95 mol%, preferably 15 to 90, in all units of the resin. It is mol%, More preferably, it is 20-85 mol%.

  Examples of the monomer having an acid labile group (1) and a carbon-carbon double bond include a monomer having a norbornene ring represented by the formula (a1-3). Since the resin having a structural unit derived from the monomer (a1-3) having an acid labile group has a bulky structure, the resolution of the resist can be improved. Furthermore, the monomer (a1-3) having an acid labile group can improve the resistance to dry etching of a resist by introducing a rigid norbornane ring into the main chain of the resin.

In formula (a1-3), R ^a9 represents a hydrogen atom, a C _1-3 alkyl group, a carboxy group, a cyano group, or an alkoxycarbonyl group (—COOR ^a13) optionally having a substituent (for example, a hydroxy group). R ^a13 represents a C _1-8 alkyl group or a C _3-8 saturated cyclic hydrocarbon group, and the hydrogen atom of the alkyl group and the saturated cyclic hydrocarbon group may be substituted with a hydroxy group In the alkyl group and the saturated cyclic hydrocarbon group, —CH ₂ — may be replaced by —O— or —CO—. R ^{a10 to} R ^a12 each independently represents a C _1-12 alkyl group or a C _3-12 saturated cyclic hydrocarbon group, or R ^a10 and R ^a11 are bonded to each other to form a ring, and the alkyl group and A hydrogen atom of the saturated cyclic hydrocarbon group may be substituted with a hydroxy group or the like, and —CH ₂ — of the alkyl group and the saturated cyclic hydrocarbon group may be replaced with —O— or —CO—. .

Examples of the alkyl group which may have a substituent for R ^a9 include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a 2-hydroxyethyl group. ^Examples of R ^a13 include a methyl group, an ethyl group, a propyl group, a 2-oxo-oxolan-3-yl group, and a 2-oxo-oxolan-4-yl group.

Examples of R ^{a10 to} R ^a12 include a methyl group, an ethyl group, a cyclohexyl group, a methylcyclohexyl group, a hydroxycyclohexyl group, an oxocyclohexyl group, and an adamantyl group. Examples of the saturated cyclic hydrocarbon group formed by R ^a10 , R ^a11 and the carbon to which they are bonded include a cyclohexyl group and an adamantyl group.

  Examples of the monomer (a1-3) having a norbornene ring include, for example, 5-norbornene-2-carboxylic acid-tert-butyl, 5-norbornene-2-carboxylic acid 1-cyclohexyl-1-methylethyl, 5-norbornene-2 -1-methylcyclohexyl carboxylate, 2-methyl-2-adamantyl 5-norbornene-2-carboxylate, 2-ethyl-2-adamantyl 5-norbornene-2-carboxylate, 5-norbornene-2-carboxylic acid 1- (4-methylcyclohexyl) -1-methylethyl, 5-norbornene-2-carboxylic acid 1- (4-hydroxycyclohexyl) -1-methylethyl, 5-norbornene-2-carboxylic acid 1-methyl-1- (4 -Oxocyclohexyl) ethyl, 5-norbornene-2-carboxylic acid 1- (1-adap Pentyl) -1-methylethyl and the like.

  The content of the structural unit derived from the monomer represented by the formula (a1-3) in the resin is usually 10 to 95 mol%, preferably 15 to 90 mol%, more preferably in all units of the resin. Is 20 to 85 mol%.

［式（ａ１−４）中、Ｒ¹⁰は、水素原子、ハロゲン原子又はハロゲン原子を有してもよいＣ_1-6アルキル基を表す。
Ｒ¹¹は、それぞれ独立に、ハロゲン原子、ヒドロキシ基、Ｃ_1-6アルキル基、Ｃ_1-6アルコキシ基、Ｃ_2-4アシル基、Ｃ_2-4アシルオキシ基、アクリロイル基又はメタクリロイル基を表す。
ｌ^ａは０〜４の整数を表す。ｌ^ａが２以上の整数である場合、複数のＲ¹¹は同一の種類の基であっても異なる種類の基であってもよい。
Ｒ¹²及びＲ¹³はそれぞれ独立に、水素原子又はＣ_1-12炭化水素基を表す。
Ｘ^ａ２は、単結合又は置換基を有していてもよいＣ_1-17飽和炭化水素基を表し、該飽和炭化水素基に含まれる−ＣＨ_２−は−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ_２−又は−Ｎ（Ｒ^ｃ）−で置き換わっていてもよい。Ｒ^ｃは、水素原子又はＣ_1-6アルキル基を表す。
Ｙ^ａ３は、Ｃ_1-12アルキル基、Ｃ_3-18飽和環状炭化水素基又はＣ_6-18芳香族炭化水素基であり、該アルキル基、飽和環状炭化水素基及び芳香族炭化水素基は、置換基を有していてもよい。］ Examples of the monomer having the acid labile group (1) and the carbon-carbon double bond include a monomer (a1-4) represented by the formula (a1-4).

[In formula (a1-4), R ¹⁰ represents a hydrogen atom, a halogen atom or a C _1-6 alkyl group which may have a halogen atom.
R ¹¹ each independently represents a halogen atom, a hydroxy group, a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _2-4 acyl group, a C _2-4 acyloxy group, an acryloyl group or a methacryloyl group.
l ^a represents an integer of 0 to 4; If l ^a is an integer of 2 or more, plural R ¹¹ may be the same kind a group even if different types of groups.
R ¹² and R ¹³ each independently represents a hydrogen atom or a C _1-12 hydrocarbon group.
X ^a2 represents a C _1-17 saturated hydrocarbon group which may have a single bond or a substituent, and —CH ₂ — contained in the saturated hydrocarbon group represents —CO—, —O—, —S. -, - SO ₂ - or -N ^{(R c)} - may be replaced by. R ^c represents a hydrogen atom or a C _1-6 alkyl group.
Y ^a3 is a C _1-12 alkyl group, a C _3-18 saturated cyclic hydrocarbon group or a C _6-18 aromatic hydrocarbon group, and the alkyl group, saturated cyclic hydrocarbon group and aromatic hydrocarbon group are: It may have a substituent. ]

Ｃ_6-18芳香族炭化水素基としては、例えば、フェニル基、ナフチル基、アントニル基、ｐ−メチルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、ｐ−アダマンチルフェニル基等が挙げられる。 Examples of the C _1-6 alkyl group which may have a halogen atom include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, A perfluoropentyl group, a perfluorohexyl group, etc. are mentioned. Q ¹ and Q ² are each independently preferably a perfluoromethyl group or a fluorine atom, more preferably a fluorine atom.
Examples of the C _1-6 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. A C _1-4 alkyl group is preferred, a C _1-2 alkyl group is more preferred, and a methyl group is particularly preferred.
Examples of the C _1-6 alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, and an n-hexoxy group. A C _1-4 alkoxy group is preferable, a C _1-2 alkoxy group is more preferable, and a methoxy group is particularly preferable.
Examples of the C _2-4 acyl group include acetyl, propionyl, butyryl and the like.
Examples of the C _2-4 acyloxy group include acetyloxy, propionyloxy, butyryloxy and the like.
Examples of the C _1-12 hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, Examples include 2-ethylhexyl group, cyclohexyl group, adamantyl group, 2-alkyl-2-adamantyl group, 1- (1-adamantyl) -1-alkyl group, isobornyl group and the like.
Examples of the C _1-12 alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, Examples include heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like.
Examples of the C _3-18 saturated cyclic hydrocarbon group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, 1-adamantyl group, 2 -Adamantyl group, isobornyl group, group shown below, etc. are mentioned.

Examples of the C _6-18 aromatic hydrocarbon group include a phenyl group, a naphthyl group, an antonyl group, a p-methylphenyl group, a p-tert-butylphenyl group, and a p-adamantylphenyl group.

  As a monomer (a1-4), the following monomers are mentioned, for example.

  The content of the structural unit derived from the monomer represented by the formula (a1-4) in the resin is usually 10 to 95 mol%, preferably 15 to 90 mol%, more preferably in all units of the resin. Is 20 to 85 mol%.

The resin (A) is preferably a co-polymerization of a monomer (a1) having an acid labile group and a monomer having no acid labile group (hereinafter sometimes referred to as “acid stable monomer”). It is a coalescence. An acid stable monomer may be used individually by 1 type, and may use 2 or more types together.
When the resin (A) is a copolymer of a monomer (a1) having an acid labile group and an acid stable monomer, the structural units derived from the monomer (a1) having an acid labile group are all Preferably it is 10-80 mol% with respect to 100 mol% of structural units, More preferably, it is 20-60 mol%. Further, the structural unit derived from the monomer having an adamantyl group (particularly the monomer (a1-1) having an acid labile group) is added in an amount of 15 mol with respect to 100 mol% of the monomer (a1) having an acid labile group. % Or more is preferable. When the ratio of the monomer having an adamantyl group is increased, the dry etching resistance of the resist is improved.

  As the acid stable monomer, those having a hydroxy group or a lactone ring are preferred. Derived from an acid stable monomer having a hydroxy group (hereinafter referred to as “acid stable monomer having a hydroxy group (a2)”) or an acid stable monomer having a lactone ring (hereinafter referred to as “acid stable monomer having a lactone ring (a3)”) If a resin having a structural unit to be used is used, the resolution of the resist and the adhesion to the substrate can be improved.

<Acid-stable monomer having a hydroxy group (a2)>
When the resist composition is used for KrF excimer laser exposure (248 nm), high energy beam exposure such as electron beam or EUV light, the acid-stable monomer (a2) having a hydroxy group has an acid having a phenolic hydroxyl group which is a hydroxystyrene. It is preferable to use a stable monomer (a2-0). When using short wavelength ArF excimer laser exposure (193 nm) or the like, an acid stable monomer having a hydroxyadamantyl group represented by formula (a2-1) should be used as the acid stable monomer having a hydroxy group (a2). Is preferred. The acid-stable monomer (a2) having a hydroxy group may be used alone or in combination of two or more.

  Examples of the monomer (a2-0) having a phenolic hydroxyl group include styrene monomers such as p- or m-hydroxystyrene represented by the formula (a2-0).

［式（ａ２−０）中、
Ｒ^８は、水素原子、ハロゲン原子又はハロゲン原子を有してもよいＣ_1-6アルキル基を表す。
Ｒ^９は、ハロゲン原子、ヒドロキシ基、Ｃ_1-6アルキル基、Ｃ_1-6アルコキシ基、Ｃ_2-4アシル基、Ｃ_2-4アシルオキシ基、アクリロイル基又はメタクリロイル基を表す。
ｍａは０〜４の整数を表す。ｍａが２以上の整数である場合、複数のＲ^９は同一の種類の基であっても異なる種類の基であってもよい。］

[In the formula (a2-0),
R ⁸ represents a hydrogen atom, a halogen atom or a C _1-6 alkyl group which may have a halogen atom.
R ⁹ represents a halogen atom, a hydroxy group, a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _2-4 acyl group, a C _2-4 acyloxy group, an acryloyl group or a methacryloyl group.
ma represents an integer of 0 to 4. When ma is an integer of 2 or more, the plurality of R ⁹ may be the same type of group or different types of groups. ]

Examples of the C _1-6 alkyl group which may have a halogen atom include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, A perfluoropentyl group, a perfluorohexyl group, etc. are mentioned. Q ¹ and Q ² are each independently preferably a perfluoromethyl group or a fluorine atom, more preferably a fluorine atom.
Examples of the C _1-6 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. A C _1-4 alkyl group is preferred, a C _1-2 alkyl group is more preferred, and a methyl group is particularly preferred.
Examples of the C _1-6 alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, and an n-hexoxy group. A C _1-4 alkoxy group is preferable, a C _1-2 alkoxy group is more preferable, and a methoxy group is particularly preferable.
Examples of the C _2-4 acyl group include acetyl, propionyl, butyryl and the like.
Examples of the C _2-4 acyloxy group include acetyloxy, propionyloxy, butyryloxy and the like.

When obtaining a copolymer resin having a structural unit derived from a monomer having such a phenolic hydroxyl group, the corresponding (meth) acrylic acid ester monomer, acetoxystyrene, and styrene are radically polymerized and then deacetylated with an acid. Can be obtained.
Examples of the monomer having a phenolic hydroxyl group include the following monomers.

  Of the above monomers, 4-hydroxystyrene or 4-hydroxy-α-methylstyrene is particularly preferred.

  The content of the structural unit derived from the monomer represented by the formula (a2-0) in the resin is usually from 5 to 90 mol%, preferably from 10 to 85 mol%, more preferably in all units of the resin. Is 15 to 80 mol%.

  Examples of the acid stable monomer having a hydroxyadamantyl group include a monomer represented by the formula (a2-1).

Wherein (a2-1), L ^{a3 is,} * -O- or _{^{* -O- (CH 2) k2 -CO}} -O- the stands, * represents a binding position to -CO-, k2 is 1 An integer of 7 is represented. R ^a14 represents a hydrogen atom or a methyl group. R ^a15 and R ^a16 each independently represent a hydrogen atom, a methyl group or a hydroxy group. o1 represents an integer of 0 to 10.

L ^a3 is ^{preferably, * -O-, * -O- (CH} 2) f1 -CO-O- and is (wherein f1 is an integer from 1 to 4), more preferably ^* -O- in is there. R ^a14 is preferably a methyl group. R ^a15 is preferably a hydrogen atom. R ^a16 is preferably a hydrogen atom or a hydroxy group. o1 is preferably an integer of 0 to 3, more preferably 0 or 1.

  Examples of the acid-stable monomer (a2-1) having a hydroxyadamantyl group include the following. Among these, 3-hydroxy-1-adamantyl (meth) acrylate, 3,5-dihydroxy-1-adamantyl ( 1- (3,5-dihydroxy-1-adamantyloxycarbonyl) methyl (meth) acrylate and (meth) acrylate are preferred, and 3-hydroxy-1-adamantyl (meth) acrylate and 3,5-dihydroxy-1-adamantyl ( (Meth) acrylate is more preferable, and 3-hydroxy-1-adamantyl methacrylate and 3,5-dihydroxy-1-adamantyl methacrylate are more preferable.

  The content of the structural unit derived from the monomer represented by the formula (a2-1) in the resin is usually from 3 to 45 mol%, preferably from 5 to 40 mol%, more preferably in all units of the resin. Is 5 to 35 mol%.

<Acid-stable monomer having a lactone ring (a3)>
The lactone ring possessed by the acid-stable monomer (a3) may be a monocycle such as a β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, and may be a monocyclic lactone ring and another ring. A condensed ring may be used. Among these lactone rings, a γ-butyrolactone ring and a condensed ring of a γ-butyrolactone ring and another ring are preferable.

  The acid stable monomer (a3) having a lactone ring is preferably represented by the formula (a3-1), the formula (a3-2) or the formula (a3-3). These 1 type may be used independently and may use 2 or more types together.

In formulas (a3-1) to (a3-3), L ^{a4 to} L ^a6 each independently represent ^* —O— or ^* —O— (CH ₂ ) _k3 —CO—O—, and * represents It represents a bond with —CO—, and k3 represents an integer of 1 to 7. R ^{a18 to} R ^a20 each independently represents a hydrogen atom or a methyl group. R ^a21 represents a C _1-4 alkyl group, and p1 represents an integer of 0 to 5. R ^a22 and R ^a23 each independently represent a carboxy group, a cyano group or a C _1-4 alkyl group, and q1 and r1 each independently represent an integer of 0 to 3. When p1, q1 or r1 is 2 or more, a plurality of R ^a21 , R ^a22 or R ^a23 may be the same as or different from each other.

Examples of L ^{a4 to} L ^a6 include those described for L ^a3 . L ^{a4 to} L ^a6 are each independently preferably ^* —O— or ^* —O— (CH ₂ ) _d1 —CO—O— (wherein d1 is an integer of 1 to 4), ^* -O- is preferable. R ^{a18 to} R ^a20 are preferably methyl groups. R ^a21 is preferably a methyl group. R ^a22 and R ^a23 are each independently preferably a carboxy group, a cyano group or a methyl group. p1 to r1 are each independently preferably 0 to 2, more preferably 0 or 1.

  Examples of the acid stable monomer (a3-1) having a γ-butyrolactone ring include the following.

  As the acid stable monomer (a3-1) having a γ-butyrolactone ring, an acid labile monomer can also be exemplified. For example, the following are mentioned.

  Examples of the acid stable monomer (a3-2) having a condensed ring of γ-butyrolactone ring and norbornane ring include the following.

  As the acid stable monomer (a3-2) having a condensed ring of γ-butyrolactone ring and norbornane ring, an acid labile monomer can be exemplified. For example, the following are mentioned.

  Examples of the acid stable monomer (a3-3) having a condensed ring of γ-butyrolactone ring and cyclohexane ring include the following.

  An acid labile monomer can also be exemplified as the monomer (a3-3) having a condensed ring of γ-butyrolactone ring and cyclohexane ring. For example, the following are mentioned.

Among acid-stable monomers (a3) having a lactone ring, (meth) acrylic acid (5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl, (meth) acrylic Acid tetrahydro-2-oxo-3-furyl, 2- (5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yloxy) -2-oxoethyl (meth) acrylate Are preferred, and those in the form of methacrylate are more preferred.

  Content of the structural unit derived from the monomer represented by Formula (a3-1), Formula (a3-2) or Formula (a3-3) in the resin is usually 5 to 70 mol% in all units of the resin. Yes, preferably 10 to 65 mol%, more preferably 10 to 60 mol%.

<Other acid stable monomers (a4)>
Examples of the other acid stable monomer (a4) include maleic anhydride represented by formula (a4-1), itaconic anhydride represented by formula (a4-2), and formula (a4-3). And acid-stable monomers having a norbornene ring.

In formula (a4-3), R ^a25 and R ^a26 each independently represent a hydrogen atom, a C _1-3 alkyl group ^optionally having a substituent (for example, a hydroxy group), a cyano group, a carboxy group, or Represents an alkoxycarbonyl group (—COOR ^a27 ), or R ^a25 and R ^a26 combine with each other to form —CO—O—CO—, and R ^a27 represents a C _1-36 alkyl group or a C _3-36 saturated cyclic group. Represents a hydrocarbon group, and —CH ₂ — in the alkyl group and saturated cyclic hydrocarbon group may be replaced by —O— or —CO—. However, those in which —COOR ^a27 is an acid labile group are excluded (that is, R ^a27 does not include those in which a tertiary carbon atom is bonded to —O—).

^Examples of the alkyl group which may have a substituent for R ^a25 and R ^a26 include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a 2-hydroxyethyl group. Carbon number of the alkyl group of R ^a27 is preferably 1-8, more preferably 1-6, and carbon number of the saturated cyclic hydrocarbon group is preferably 4-36, more preferably 4-12. ^Examples of R ^a27 include a methyl group, an ethyl group, a propyl group, a 2-oxo-oxolan-3-yl group, and a 2-oxo-oxolan-4-yl group.

  Examples of the acid-stable monomer (a4-3) having a norbornene ring include 2-norbornene, 2-hydroxy-5-norbornene, 5-norbornene-2-carboxylic acid, methyl 5-norbornene-2-carboxylate, and 5-norbornene. Examples include 2-hydroxy-1-ethyl-2-carboxylate, 5-norbornene-2-methanol, 5-norbornene-2,3-dicarboxylic acid anhydride, and the like.

  Content of the structural unit derived from the monomer represented by Formula (a4-1), Formula (a4-2), or Formula (a4-3) in the resin is usually 2 to 40 mol% in all units of the resin. Yes, preferably 3-30 mol%, more preferably 5-20 mol%.

  A preferred resin (A) is a copolymer obtained by polymerizing at least a monomer (a1) having an acid labile group, an acid stable monomer (a2) having a hydroxy group, and / or an acid stable monomer (a3) having a lactone ring. It is a polymer. In this preferred copolymer, the monomer (a1) having an acid labile group is more preferably at least one of a monomer (a1-1) having an adamantyl group and a monomer (a1-2) having a cyclohexyl group. A species (more preferably a monomer (a1-1) having an adamantyl group), and an acid stable monomer (a2) having a hydroxy group, preferably an acid stable monomer (a2-1) having a hydroxyadamantyl group, and a lactone The acid-stable monomer (a3) having a ring is more preferably an acid-stable monomer (a3-1) having a γ-butyrolactone ring and an acid-stable monomer (a3-2) having a condensed ring of a γ-butyrolactone ring and a norbornane ring At least one of the following. Resin (A) can be manufactured by a well-known polymerization method (for example, radical polymerization method).

  The weight average molecular weight of the resin (A) is preferably 2,500 or more (more preferably 3,000 or more) and 50,000 or less (more preferably 30,000 or less).

  It is preferable that content of resin (A) is 80 mass% or more in solid content of a composition. In the present specification, the “solid content in the composition” means the total of the composition components excluding the solvent (E). The solid content in the composition and the content of the resin (A) relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

<Basic compound (hereinafter sometimes referred to as “basic compound (C)”)>
The resist composition of the present invention contains a basic compound (C). The content of the basic compound (C) is preferably about 0.01 to 1% by mass based on the solid content of the resist composition.

  The basic compound (C) is preferably a basic nitrogen-containing organic compound (for example, an amine) and an ammonium salt. The amine may be an aliphatic amine or an aromatic amine. As the aliphatic amine, any of primary amine, secondary amine and tertiary amine can be used. The aromatic amine may be any of an amino group bonded to an aromatic ring such as aniline and a heteroaromatic amine such as pyridine. Preferable basic compound (C) includes an aromatic amine represented by the formula (C2), particularly an aniline represented by the formula (C2-1).

In the formula (C2), Ar ^c1 represents an aromatic hydrocarbon group. R ^c5 and R ^c6 each independently represent a hydrogen atom, a C _1-6 alkyl group, a C _5-10 saturated cyclic hydrocarbon group (preferably a cycloalkyl group) or a C _6-10 aromatic hydrocarbon group. However, the hydrogen atom of the alkyl group, the saturated cyclic hydrocarbon group or the aromatic hydrocarbon group may be substituted with a hydroxy group, an amino group, or a C _1-6 alkoxy group. _It may be substituted with a _1-4 alkyl group.

In formula (C2-1), R ^c5 and R ^c6 are the same as described above. R ^c7 represents a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _5-10 saturated cyclic hydrocarbon group (preferably a cycloalkyl group) or a C _6-10 aromatic hydrocarbon group. However, the hydrogen atom of an alkyl group, an alkoxy group, a saturated cyclic hydrocarbon group and an aromatic hydrocarbon group may have the substituent described in the formula (C2). m3 represents an integer of 0 to 3. When m3 is 2 or more, the plurality of R ^c7 may be the same as or different from each other.

  Examples of the aromatic amine (C2) include 1-naphthylamine and 2-naphthylamine. Examples of aniline (C2-1) include aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine and the like. Of these, diisopropylaniline (particularly 2,6-diisopropylaniline) is preferable.

  Moreover, as a basic compound (C), the compound represented by Formula (C3)-Formula (C11) is mentioned.

R ^c8 in formula (C3) represents any of the groups described for R ^c7 in formula (C2). R ^c9 , R ^c10 , R ^{c11 to} R ^c14 , R ^{c16 to} R ^c19 and R ^c22 bonded to the nitrogen atom in formula (C3) to formula (C8) are each independently R ^{c5 in} formula (C2) and It represents one of the groups described for R ^c6 . R ^c20 , R ^c21 and R ^{c23 to} R ^c28 bonded to the aromatic ring in formula (C7) to formula (C11) are each independently any one of the groups described for R ^c7 in formula (C2-1). Represent. O3 to u3 in Formula (C7) and Formula (C9) to Formula (C11) each independently represents an integer of 0 to 3. When any of o3 to u3 is 2 or more, any of the plurality of R ^{c20 to} R ^c28 may be the same as or different from each other.

R ^c15 in formula (C6) represents a C _1-6 alkyl group, a C _3-6 saturated cyclic hydrocarbon group, or a C _2-6 alkanoyl group, and n3 represents an integer of 0-8. When n3 is 2 or more, the plurality of R ^c15 may be the same as or different from each other.

L ^c1 and L ^{c2 in} formula (C7) and formula (C10) are each independently a divalent C _1-6 alkylene group, —CO—, —C (═NH) —, —C (═NR ^c3 ). -, -S-, -SS-, or a combination thereof is represented. R ^c3 represents a C _1-4 alkyl group.

  Examples of the compound (C3) include hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, Tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctyl Amine, methyl dinonyl amine, methyl didecyl amine, ethyl dibutyl amine, ethyl dipentyl amine, ethyl di Silamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine ethylenediamine, tetramethylenediamine, hexamethylene Examples include diamine, 4,4′-diamino-1,2-diphenylethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, and the like.

  Examples of the compound (C4) include piperazine. Examples of the compound (C5) include morpholine. Examples of the compound (C6) include piperidine and hindered amine compounds having a piperidine skeleton described in JP-A No. 11-52575. Examples of the compound (C7) include 2,2′-methylenebisaniline.

  Examples of the compound (C8) include imidazole and 4-methylimidazole. Examples of the compound (C9) include pyridine and 4-methylpyridine. Examples of the compound (C10) include 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,2-di (2-pyridyl) ethene, and 1,2-di. (4-pyridyl) ethene, 1,3-di (4-pyridyl) propane, 1,2-di (4-pyridyloxy) ethane, di (2-pyridyl) ketone, 4,4′-dipyridyl sulfide, 4, 4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine and the like can be mentioned. Examples of the compound (C11) include bipyridine.

  As ammonium salts, tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3- (trifluoromethyl) phenyltrimethyl Ammonium hydroxide, tetra-n-butylammonium salicylate, choline and the like can be mentioned.

<Solvent (sometimes referred to as "solvent (E)")
The resist composition of the present invention may contain the solvent (E) in an amount of 90% by mass or more in the composition. The resist composition of the present invention containing the solvent (E) is suitable for producing a thin film resist. The content of the solvent (E) is 90% by mass or more (preferably 92% by mass or more, more preferably 94% by mass or more) and 99.9% by mass or less (preferably 99% by mass or less) in the composition. The content of the solvent (E) can be measured by a known analysis means such as liquid chromatography or gas chromatography.

  Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethyl lactate, butyl acetate, amyl acetate and And esters such as ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; A solvent (E) may be used individually by 1 type, and may use 2 or more types together.

<Other components (hereinafter sometimes referred to as “other components (F)”)>
The resist composition of this invention may contain the other component (F) as needed. Component (F) is not particularly limited, and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, and the like can be used.

<Method for producing resist pattern>
The method for producing a resist pattern of the present invention comprises:
(1) The process of apply | coating the resist composition of this invention mentioned above on a board | substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer using an exposure machine;
(4) A step of heating the composition layer after exposure,
(5) The process which develops the composition layer after a heating using a image development apparatus is included.

  Application of the resist composition onto the substrate can be performed by a commonly used apparatus such as a spin coater.

The composition after application | coating is dried and the solvent contained in a composition is removed. The removal of the solvent is performed, for example, by evaporating the solvent using a heating device such as a hot plate or by using a decompression device to form a composition layer from which the solvent has been removed. As for the temperature in this case, about 50-200 degreeC is illustrated, for example. The pressure is exemplified by about 1 to 1.0 × 10 ⁵ Pa.

The obtained composition layer is exposed using an exposure machine. At this time, exposure is usually performed through a mask corresponding to a required pattern. The exposure light source emits ultraviolet laser light such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ laser (wavelength 157 nm), solid-state laser light source (YAG or semiconductor laser, etc.) Various types of laser beam can be used, such as those that convert the wavelength of the laser beam from) to radiate a harmonic laser beam in the far ultraviolet region or the vacuum ultraviolet region.

The composition layer after the exposure is subjected to heat treatment for promoting the deprotection group reaction. As heating temperature, it is about 50-200 degreeC normally, Preferably it is about 70-150 degreeC.
The heated composition layer is usually developed using an alkali developer using a developing device.
The alkaline developer used here may be various alkaline aqueous solutions used in this field. Examples thereof include an aqueous solution of tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline).
After development, it is preferable to rinse with ultrapure water to remove water remaining on the substrate and the pattern.

<Application>
The composition of the present invention is useful for a photoresist composition, particularly a chemically amplified photoresist composition, and is used for fine processing of semiconductors, manufacture of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes. It can be suitably used for a wide range of applications. In particular, it can be used as a chemically amplified photoresist composition suitable for excimer laser lithography such as ArF and KrF, ArF immersion exposure lithography, EB exposure lithography, and EUV exposure lithography. In addition to immersion exposure, it can also be used for dry exposure. Furthermore, it can be used for double imaging and is industrially useful.

Hereinafter, the present invention will be described in detail by way of examples.
In Examples and Comparative Examples, “%” and “part” representing content and use amount are based on mass unless otherwise specified.
The weight average molecular weight is a value obtained by gel permeation chromatography (HLC-8120GPC, manufactured by Tosoh Corporation, three columns are “TSKgel Multipore HXL-M”, and the solvent is tetrahydrofuran) using polystyrene as a standard product.
Column: TSKgel Multipore H _XL -M x 3 + guardcolumn (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

Example 1: Synthesis of a salt represented by the formula (B1)

After adding 250 parts of 1,3-adamantanediol and 2000 parts of tetrahydrofuran and stirring at room temperature, 142 parts of pyridine was added and the temperature was raised to 40 ° C. Further, a mixed solution of 254 parts of chloroacetyl chloride and 500 parts of tetrahydrofuran was added dropwise over 80 minutes. After dropping, the mixture was stirred at 40 ° C. for 8 hours, and the temperature was lowered to 5 ° C. 1000 parts of ion-exchanged water cooled to 5 ° C. was added and stirred, and the aqueous layer was recovered by liquid separation. 600 parts of ethyl acetate was added to the recovered aqueous layer, and the organic layer was recovered by liquid separation. To the recovered organic layer, 600 parts of a 10% potassium carbonate aqueous solution at 5 ° C. is added and washed, and after separating and recovering the organic layer, 600 parts of ion-exchanged water is further added to the recovered organic layer. The organic layer was recovered by washing with water and liquid separation. This washing operation was repeated 3 times. The collected organic layer was concentrated and then fractionated in a column under the following conditions to obtain 75 parts of the compound represented by the formula (B1-a).
Developing medium; silica gel 60-200 mesh; manufactured by Merck developing solvent: n-heptane / ethyl acetate = 1/1 (volume ratio)

式（Ｂ１−ｂ）で表される化合物（商品名：ＨＡＤＭ、出光製）２６．４４部、ジオキサン８０．００部を仕込み、２３℃で攪拌下、水酸化ナトリウム４．４０部をイオン交換水８０．００部に溶解した水溶液を３０分かけて滴下し、９０℃で３６時間攪拌した。反応マスを冷却し、イオン交換水４００．００部、酢酸エチル５００．０部及び塩化ナトリウム２００．０部を添加し、攪拌し、分液を行った。得られた有機層に３Ｎ塩酸塩化ナトリウム４００．０部を添加し、攪拌し、分液を行った。得られた有機層にイオン交換水４００．００部を添加し、攪拌し、分液を行った。この水洗を３回行った。回収された有機層を濃縮後、以下の条件でカラム分取することにより、式（Ｂ１−ｃ）で表される化合物７．８９部を得た。
展開媒体；シリカゲル６０−２００メッシュ；メルク社製
展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１（容量比）

A compound represented by the formula (B1-b) (trade name: HADM, manufactured by Idemitsu Co., Ltd.), 26.44 parts, dioxane (80.00 parts) were charged, and stirred at 23 ° C., sodium hydroxide (4.40 parts) was ion-exchanged water. An aqueous solution dissolved in 80.00 parts was dropped over 30 minutes and stirred at 90 ° C. for 36 hours. The reaction mass was cooled, 400.00 parts of ion-exchanged water, 500.0 parts of ethyl acetate and 200.0 parts of sodium chloride were added, stirred, and separated. To the obtained organic layer, 400.0 parts of 3N sodium chloride hydrochloride was added, stirred, and separated. To the obtained organic layer, 400.00 parts of ion exchanged water was added, stirred, and separated. This washing with water was performed three times. The collected organic layer was concentrated and then fractionated on a column under the following conditions to obtain 7.89 parts of a compound represented by the formula (B1-c).
Developing medium; silica gel 60-200 mesh; manufactured by Merck developing solvent: n-heptane / ethyl acetate = 1/1 (volume ratio)

4.88 parts of a compound represented by the formula (B1-a) and 25.00 parts of N, N′-dimethylformamide were charged and stirred at 23 ° C. for 30 minutes. To the obtained mixture, 1.66 parts of potassium carbonate and 0.84 part of potassium iodide were charged and stirred at 50 ° C. for 1 hour. The obtained mixture was cooled to 40 ° C., and a solution obtained by dissolving 3.93 parts of the compound represented by the formula (B1-c) in 25.00 parts of N, N′-dimethylformamide was added dropwise over 1 hour. And stirred at 75 ° C. for 5 hours. The obtained mixture was cooled to 23 ° C., 60.00 parts of chloroform and 60.00 parts of 1N hydrochloric acid were added, and the mixture was stirred and separated. The collected organic layer was repeatedly washed with 60.00 parts of ion-exchanged water until the aqueous layer became neutral. After the collected organic layer was concentrated, 2.54 parts of a compound represented by the formula (B1-d) was obtained by fractionating the column under the following conditions.
Developing medium; silica gel 60-200 mesh; made by Merck developing solvent: ethyl acetate

  A salt represented by the formula (B1-e) was synthesized by the method described in Example 1 of JP2008-127367A. After 2.19 parts of a salt represented by the formula (B1-e), 50.00 parts of monochlorobenzene and 2.43 parts of a compound represented by the formula (B1-d) were stirred and stirred at 23 ° C. for 30 minutes, 0.20 parts of sulfuric acid and 10.00 parts of molecular sieve (trade name: Molecular Sieve 4A, manufactured by Wako Pure Chemical Industries, Ltd.) were charged, followed by reflux dehydration at 130 ° C. for 3 hours. After concentrating the obtained reaction product, 100 parts of chloroform and 50 parts of ion-exchanged water were added, followed by stirring and liquid separation. Water washing was performed 3 times. The obtained organic layer was charged with 1.00 part of activated carbon, stirred at 23 ° C. for 30 minutes, and then filtered. After the filtrate was concentrated, 20 parts of acetonitrile was added to the resulting concentrate to dissolve it, concentrated, 20 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 20 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in chloroform and concentrated to obtain 0.62 part of a salt represented by the formula (B1) as an oily substance.

MS (ESI (+) Spectrum): M ⁺ 263.1
MS (ESI (-) Spectrum): M ^- 561.2

Example 2: Synthesis of a salt represented by the formula (B2)

  First, 25.31 parts of the compound represented by the formula (B2-a) and 200.00 parts of tetrahydrofuran were charged, stirred at room temperature, and after confirming the dissolution of the compound represented by the formula (B2-a), 14.27 parts of pyridine. Was heated to 40 ° C. Further, a mixed solution of 25.47 parts of chloroacetyl chloride and 50 parts of tetrahydrofuran was added dropwise over 1 hour. After dropping, the mixture was stirred at 40 ° C. for 8 hours, and the temperature was lowered to 5 ° C. 100.00 parts of ion-exchanged water cooled to 5 ° C. was added and stirred, and the aqueous layer was recovered by liquid separation. 65.00 parts of ethyl acetate was added to the recovered aqueous layer, and the organic layer was recovered by liquid separation. The recovered organic layer was washed by adding 65.00 parts of a 10% aqueous potassium carbonate solution at 5 ° C. and separated to recover the organic layer, and then the ion-exchanged water 65. 00 parts were added and washed with water, followed by liquid separation to recover the organic layer. This washing operation was repeated 3 times. The collected organic layer is concentrated, and then fractionated by a column (silica gel 60-200 mesh; developing solvent: ethyl acetate, manufactured by Merck & Co., Inc.) to give compound 22 represented by formula (B2-b). 24 parts were obtained.

  7.50 parts of the compound represented by the formula (B2-c) and 37.50 parts of N, N′-dimethylformamide were charged and stirred at 23 ° C. for 30 minutes. To the obtained mixture, 3.20 parts of potassium carbonate and 0.96 part of potassium iodide were charged and stirred at 50 ° C. for 1 hour. A solution prepared by dissolving 8.50 parts of the compound represented by the formula (B2-b) in 16.87 parts of N, N′-dimethylformamide was added dropwise to the obtained mixture over 1 hour, and the mixture was stirred at 50 ° C. for 5 hours. Stir. The obtained mixture was cooled to 23 ° C., 150 parts of ethyl acetate and 75 parts of ion-exchanged water were added, and the mixture was stirred and separated. The collected organic layer was repeatedly washed with 75 parts of ion-exchanged water until the aqueous layer became neutral. After the collected organic layer is concentrated, the compound (B2-d) represented by the formula (B2-d) is separated by separating the column (silica gel 60-200 mesh; developing solvent: ethyl acetate) under the following conditions. 29 parts were obtained.

  7.54 parts of a compound represented by the formula (B2-d) and 37.50 parts of acetonitrile were charged, stirred at 23 ° C. for 30 minutes, and then cooled to 5 ° C. To the obtained mixture, 0.36 part of sodium borohydride and 5.32 parts of ion-exchanged water were added and stirred at 5 ° C. for 3 hours. To the obtained mixture, 25 parts of ion-exchanged water and 50 parts of ethyl acetate were added, stirred and separated. The collected organic layer was repeatedly washed with 25 parts of ion-exchanged water until the aqueous layer became neutral. After the collected organic layer is concentrated, the compound represented by the formula (B2-e) is obtained by fractionating a column (silica gel 60-200 mesh; developing solvent: ethyl acetate) by the following conditions. 33 parts were obtained.

A salt represented by the formula (B2-f) was synthesized by the method described in JP-A-2008-127367.
After 2.19 parts of a salt represented by the formula (B2-f), 50.00 parts of monochlorobenzene and 2.43 parts of a compound represented by the formula (B2-e) were charged and stirred at 23 ° C. for 30 minutes, 0.20 parts of sulfuric acid and 10.00 parts of molecular sieve (trade name: Molecular Sieve 4A, manufactured by Wako Pure Chemical Industries, Ltd.) were charged, followed by reflux dehydration at 130 ° C. for 3 hours. After concentrating the obtained reaction product, 100 parts of chloroform and 50 parts of ion-exchanged water were added, followed by stirring and liquid separation. Water washing was performed 5 times. The obtained organic layer was charged with 1.00 parts of activated carbon, stirred at 23 ° C. for 30 minutes, and filtered. After the filtrate was concentrated, 25 parts of acetonitrile was added to the resulting concentrate to dissolve it, concentrated, 25 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 25 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in chloroform and concentrated, and the resulting concentrate was fractionated in a column (Merck silica gel 60-200 mesh developing solvent: chloroform / methanol = 5/1) to obtain the formula (B2). 1.48 parts of the represented salt were obtained.

MS (ESI (+) Spectrum): M ⁺ 263.1
MS (ESI (-) Spectrum): M ^- 561.2

リチウムアルミニウムハイドライド１０．４部、無水テトラヒドロフラン１２０部を仕込み２３℃で３０分間攪拌した。次いで、式（Ｂ３−ａ）で表される塩６２．２部を無水ＴＨＦ９００部に溶かした溶液を氷冷下で滴下し、２３℃で５時間攪拌した。反応マスに酢酸エチル５０．０部、６Ｎ塩酸５０．００部を添加、攪拌後、分液を行った。有機層を濃縮後、カラム（メルク シリカゲル６０−２００メッシュ 展開溶媒：クロロホルム／メタノール＝５／１）分取することにより、式（Ｂ３−ｂ）で表される塩を８４．７部（純度６０％）を得た。
式（Ｂ３−ｃ）で表される化合物３．５１部、無水ＴＨＦ７５部を仕込み２３℃で３０分間攪拌した。次いで、カルボニルジイミダゾール２．８９部、無水ＴＨＦ５０部の混合溶液を２３℃で滴下し、２３℃で４時間攪拌した。得られた反応液を、式（Ｂ３−ｂ）で表される塩６．０４部（純度６０％）、無水ＴＨＦ５０部の混合液中に５４〜６０℃で、２５分間で滴下し、６５℃で１８時間加熱し、冷却後、ろ過した。得られたろ液を濃縮し、濃縮物をカラム（メルク シリカゲル６０−２００メッシュ 展開溶媒：クロロホルム／メタノール＝５／１）分取することにより、式（Ｂ３−ｄ）で表される塩２．９９部を得た。

式（Ｂ３−ｄ）で表される塩１．０部、クロロホルム３０部を仕込み２３℃で３０分間攪拌した。次いで、式（Ｂ３−ｅ）で表される塩０．８３部を２３℃で１２時間攪拌した後、分液を行った。有機層にイオン交換水１０部を添加、分液水洗を行った。この操作を３回行った。得られた有機層に活性炭１．００部を仕込み、２３℃で３０分間攪拌した後、ろ過した。ろ液を濃縮した後、得られた濃縮物に、アセトニトリル２０部を添加して溶解し、濃縮し、酢酸エチル２０部を加えて攪拌し、上澄液を除去した。得られた残渣にｔｅｒｔ−ブチルメチルエーテル２０部を加えて攪拌し、上澄液を除去した。得られた残渣をクロロホルムに溶解し、濃縮した後、得られた濃縮物をカラム（メルク シリカゲル６０−２００メッシュ 展開溶媒：クロロホルム／メタノール＝５／１）分取することにより、式（Ｂ３−ｆ）で表される塩０．６９部を得た。

式（Ｂ３−ｆ）で表される塩０．６９部及びＮ，Ｎ’−ジメチルホルムアミド１０．００部を仕込み、２３℃で３０分間攪拌した。得られた混合物に、炭酸カリウム０．０９部及びヨウ化カリウム０．０５部を仕込み、５０℃で１時間攪拌した。得られた混合物を、４０℃まで冷却し、式（Ｂ２−ｂ）で表される化合物０．２８部をＮ，Ｎ’−ジメチルホルムアミド５．００部に溶解した溶液を１時間かけて滴下し、７５℃で３時間攪拌した。得られた混合物を、２３℃まで冷却し、クロロホルム３０．００部及び１Ｎ塩酸１０．００部を加えて攪拌し、分離した。回収された有機層をイオン交換水１０．００部で水層が中性になるまで水洗を繰り返した。回収された有機層を濃縮した後、得られた濃縮物をカラム（メルク シリカゲル６０−２００メッシュ 展開溶媒：クロロホルム／メタノール＝５／１）分取することにより、式（Ｂ３）で表される塩０．１２部を得た。 Example 3: Synthesis of a salt represented by the formula (B3)

10.4 parts of lithium aluminum hydride and 120 parts of anhydrous tetrahydrofuran were charged and stirred at 23 ° C. for 30 minutes. Next, a solution obtained by dissolving 62.2 parts of the salt represented by the formula (B3-a) in 900 parts of anhydrous THF was added dropwise under ice cooling, and the mixture was stirred at 23 ° C. for 5 hours. To the reaction mass, 50.0 parts of ethyl acetate and 50.00 parts of 6N hydrochloric acid were added, followed by liquid separation. After concentrating the organic layer, by separating the column (Merck silica gel 60-200 mesh developing solvent: chloroform / methanol = 5/1), 84.7 parts (purity 60) of the salt represented by the formula (B3-b) was obtained. %).
3.51 parts of a compound represented by the formula (B3-c) and 75 parts of anhydrous THF were charged and stirred at 23 ° C. for 30 minutes. Next, a mixed solution of 2.89 parts of carbonyldiimidazole and 50 parts of anhydrous THF was added dropwise at 23 ° C., and the mixture was stirred at 23 ° C. for 4 hours. The obtained reaction solution was dropped in a mixed solution of 6.04 parts (purity 60%) of the salt represented by the formula (B3-b) and 50 parts of anhydrous THF at 25 to 60 ° C. over 25 minutes, and 65 ° C. For 18 hours, cooled and filtered. The obtained filtrate is concentrated, and the concentrate is fractionated in a column (Merck silica gel 60-200 mesh developing solvent: chloroform / methanol = 5/1) to obtain a salt 2.99 represented by the formula (B3-d). Got a part.

1.0 part of the salt represented by the formula (B3-d) and 30 parts of chloroform were charged and stirred at 23 ° C. for 30 minutes. Next, 0.83 parts of the salt represented by the formula (B3-e) was stirred at 23 ° C. for 12 hours, and then separated. 10 parts of ion-exchanged water was added to the organic layer, followed by liquid separation washing. This operation was performed three times. The obtained organic layer was charged with 1.00 part of activated carbon, stirred at 23 ° C. for 30 minutes, and then filtered. After the filtrate was concentrated, 20 parts of acetonitrile was added to the resulting concentrate to dissolve it, concentrated, 20 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 20 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in chloroform and concentrated, and the resulting concentrate was fractionated in a column (Merck silica gel 60-200 mesh developing solvent: chloroform / methanol = 5/1) to obtain the formula (B3-f ) Was obtained.

0.69 parts of a salt represented by the formula (B3-f) and 10.00 parts of N, N′-dimethylformamide were charged and stirred at 23 ° C. for 30 minutes. To the obtained mixture, 0.09 part of potassium carbonate and 0.05 part of potassium iodide were charged and stirred at 50 ° C. for 1 hour. The obtained mixture was cooled to 40 ° C., and a solution prepared by dissolving 0.28 parts of the compound represented by the formula (B2-b) in 5.00 parts of N, N′-dimethylformamide was added dropwise over 1 hour. , And stirred at 75 ° C. for 3 hours. The obtained mixture was cooled to 23 ° C., 30.00 parts of chloroform and 10.00 parts of 1N hydrochloric acid were added, and the mixture was stirred and separated. The recovered organic layer was repeatedly washed with 10.00 parts of ion-exchanged water until the aqueous layer became neutral. After the collected organic layer is concentrated, the resulting concentrate is fractionated in a column (Merck silica gel 60-200 mesh developing solvent: chloroform / methanol = 5/1) to obtain a salt represented by the formula (B3). 0.12 parts were obtained.

MS (ESI (+) Spectrum): M ⁺ 263.1
MS (ESI (-) Spectrum): M ^- 547.2

式（Ｂ４−ａ）で表される塩２．４０部、モノクロロベンゼン５０．００部及び式（Ｂ１−ｄ）で表される化合物２．４３部を仕込み、２３℃で３０分間攪拌した後、硫酸０．２０部及びモレキュラーシーブ（商品名：モレキュラーシーブ ４Ａ、和光純薬製）１０．００部を仕込み、１３０℃で３時間還流脱水した。得られた反応物を濃縮後、クロロホルム１００部及びイオン交換水５０部を仕込み、攪拌、分液を行った。水洗を３回行った。得られた有機層に活性炭１．００部を仕込み、２３℃で３０分間攪拌した後、ろ過した。ろ液を濃縮した後、得られた濃縮物に、アセトニトリル２０部を添加して溶解し、濃縮し、酢酸エチル２０部を加えて攪拌し、上澄液を除去した。得られた残渣にｔｅｒｔ−ブチルメチルエーテル２０部を加えて攪拌し、上澄液を除去した。得られた残渣をクロロホルムに溶解し、濃縮することにより、式（Ｂ４）で表される塩０．８８部を得た。 Example 4: Synthesis of salt represented by formula (B4)

After charging 2.40 parts of a salt represented by the formula (B4-a), 50.00 parts of monochlorobenzene and 2.43 parts of a compound represented by the formula (B1-d) and stirring at 23 ° C. for 30 minutes, 0.20 parts of sulfuric acid and 10.00 parts of molecular sieve (trade name: Molecular Sieve 4A, manufactured by Wako Pure Chemical Industries, Ltd.) were charged, followed by reflux dehydration at 130 ° C. for 3 hours. After concentrating the obtained reaction product, 100 parts of chloroform and 50 parts of ion-exchanged water were added, followed by stirring and liquid separation. Water washing was performed 3 times. The obtained organic layer was charged with 1.00 part of activated carbon, stirred at 23 ° C. for 30 minutes, and then filtered. After the filtrate was concentrated, 20 parts of acetonitrile was added to the resulting concentrate to dissolve it, concentrated, 20 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 20 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in chloroform and concentrated to obtain 0.88 parts of the salt represented by the formula (B4).

MS (ESI (+) Spectrum): M ⁺ 305.1
MS (ESI (-) Spectrum): M ^- 561.2

式（Ｂ５−ａ）で表される塩２．２８部、モノクロロベンゼン５０．００部及び式（Ｂ１−ｄ）で表される化合物２．４３部を仕込み、２３℃で３０分間攪拌した後、硫酸０．２０部及びモレキュラーシーブ（商品名：モレキュラーシーブ ４Ａ、和光純薬製）１０．００部を仕込み、１３０℃で３時間還流脱水した。得られた反応物を濃縮後、クロロホルム１００部及びイオン交換水５０部を仕込み、攪拌、分液を行った。水洗を３回行った。得られた有機層に活性炭１．００部を仕込み、２３℃で３０分間攪拌した後、ろ過した。ろ液を濃縮した後、得られた濃縮物をカラム（メルク シリカゲル６０−２００メッシュ 展開溶媒：クロロホルム／メタノール＝５／１）分取することにより、式（Ｂ５）で表される塩０．５２部を得た。 Example 5: Synthesis of salt represented by formula (B5)

After 2.28 parts of a salt represented by the formula (B5-a), 50.00 parts of monochlorobenzene and 2.43 parts of a compound represented by the formula (B1-d) were charged and stirred at 23 ° C. for 30 minutes, 0.20 parts of sulfuric acid and 10.00 parts of molecular sieve (trade name: Molecular Sieve 4A, manufactured by Wako Pure Chemical Industries, Ltd.) were charged, followed by reflux dehydration at 130 ° C. for 3 hours. After concentrating the obtained reaction product, 100 parts of chloroform and 50 parts of ion-exchanged water were added, followed by stirring and liquid separation. Water washing was performed 3 times. The obtained organic layer was charged with 1.00 part of activated carbon, stirred at 23 ° C. for 30 minutes, and then filtered. After concentrating the filtrate, the resulting concentrate is fractionated in a column (Merck silica gel 60-200 mesh developing solvent: chloroform / methanol = 5/1) to obtain 0.52 salt represented by the formula (B5). Got a part.

MS (ESI (+) Spectrum): M ⁺ 281.0
MS (ESI (-) Spectrum): M ^- 561.2

式（Ｂ６−ａ）で表される塩１．９１部、モノクロロベンゼン５０．００部及び式（Ｂ１−ｄ）で表される化合物２．４３部を仕込み、２３℃で３０分間攪拌した後、硫酸０．２０部及びモレキュラーシーブ（商品名：モレキュラーシーブ ４Ａ、和光純薬製）１０．００部を仕込み、１３０℃で３時間還流脱水した。得られた反応物を濃縮後、クロロホルム１００部及びイオン交換水５０部を仕込み、攪拌、分液を行った。水洗を３回行った。得られた有機層に活性炭１．００部を仕込み、２３℃で３０分間攪拌した後、ろ過した。ろ液を濃縮した後、得られた濃縮物をカラム（メルク シリカゲル６０−２００メッシュ 展開溶媒：クロロホルム／メタノール＝５／１）分取することにより、式（Ｂ６）で表される塩０．２８部を得た。 Example 6: Synthesis of salt represented by formula (B6)

1.91 parts of a salt represented by the formula (B6-a), 50.00 parts of monochlorobenzene and 2.43 parts of a compound represented by the formula (B1-d) were charged and stirred at 23 ° C. for 30 minutes. 0.20 parts of sulfuric acid and 10.00 parts of molecular sieve (trade name: Molecular Sieve 4A, manufactured by Wako Pure Chemical Industries, Ltd.) were charged, followed by reflux dehydration at 130 ° C. for 3 hours. After concentrating the obtained reaction product, 100 parts of chloroform and 50 parts of ion-exchanged water were added, followed by stirring and liquid separation. Water washing was performed 3 times. The obtained organic layer was charged with 1.00 part of activated carbon, stirred at 23 ° C. for 30 minutes, and then filtered. After concentrating the filtrate, the resulting concentrate was fractionated in a column (Merck silica gel 60-200 mesh developing solvent: chloroform / methanol = 5/1) to obtain 0.28 salt represented by the formula (B6). Got a part.

MS (ESI (+) Spectrum): M ^<+> 207.1
MS (ESI (-) Spectrum): M ^- 561.2

式（Ｂ４−ａ）で表される塩２．４０部、モノクロロベンゼン５０．００部及び式（Ｂ２−ｅ）で表される化合物２．４３部を仕込み、２３℃で３０分間攪拌した後、硫酸０．２０部及びモレキュラーシーブ（商品名：モレキュラーシーブ ４Ａ、和光純薬製）１０．００部を仕込み、１３０℃で３時間還流脱水した。得られた反応物を濃縮後、クロロホルム１００部及びイオン交換水５０部を仕込み、攪拌、分液を行った。水洗を３回行った。得られた有機層に活性炭１．００部を仕込み、２３℃で３０分間攪拌した後、ろ過した。ろ液を濃縮した後、得られた濃縮物に、アセトニトリル２０部を添加して溶解し、濃縮し、酢酸エチル２０部を加えて攪拌し、上澄液を除去した。得られた残渣にｔｅｒｔ−ブチルメチルエーテル２０部を加えて攪拌し、上澄液を除去した。得られた残渣をクロロホルムに溶解し、濃縮することにより、式（Ｂ７）で表される塩１．４９部を得た。 Example 7: Synthesis of salt represented by formula (B7)

After charging 2.40 parts of the salt represented by the formula (B4-a), 50.00 parts of monochlorobenzene and 2.43 parts of the compound represented by the formula (B2-e), and stirring at 23 ° C. for 30 minutes, 0.20 parts of sulfuric acid and 10.00 parts of molecular sieve (trade name: Molecular Sieve 4A, manufactured by Wako Pure Chemical Industries, Ltd.) were charged, followed by reflux dehydration at 130 ° C. for 3 hours. After concentrating the obtained reaction product, 100 parts of chloroform and 50 parts of ion-exchanged water were added, followed by stirring and liquid separation. Water washing was performed 3 times. The obtained organic layer was charged with 1.00 part of activated carbon, stirred at 23 ° C. for 30 minutes, and then filtered. After the filtrate was concentrated, 20 parts of acetonitrile was added to the resulting concentrate to dissolve it, concentrated, 20 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 20 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in chloroform and concentrated to obtain 1.49 parts of the salt represented by the formula (B7).

MS (ESI (+) Spectrum): M ⁺ 305.1
MS (ESI (-) Spectrum): M ^- 561.2

式（Ｂ５−ａ）で表される塩２．２８部、モノクロロベンゼン５０．００部及び式（Ｂ２−ｅ）で表される化合物２．４３部を仕込み、２３℃で３０分間攪拌した後、硫酸０．２０部及びモレキュラーシーブ（商品名：モレキュラーシーブ ４Ａ、和光純薬製）１０．００部を仕込み、１３０℃で３時間還流脱水した。得られた反応物を濃縮後、クロロホルム１００部及びイオン交換水５０部を仕込み、攪拌、分液を行った。水洗を３回行った。得られた有機層に活性炭１．００部を仕込み、２３℃で３０分間攪拌した後、ろ過した。ろ液を濃縮した後、得られた濃縮物をカラム（メルク シリカゲル６０−２００メッシュ 展開溶媒：クロロホルム／メタノール＝５／１）分取することにより、式（Ｂ８）で表される塩１．２１部を得た。 Example 8: Synthesis of salt represented by formula (B8)

After 2.28 parts of a salt represented by the formula (B5-a), 50.00 parts of monochlorobenzene and 2.43 parts of a compound represented by the formula (B2-e) were charged and stirred at 23 ° C. for 30 minutes, 0.20 parts of sulfuric acid and 10.00 parts of molecular sieve (trade name: Molecular Sieve 4A, manufactured by Wako Pure Chemical Industries, Ltd.) were charged, followed by reflux dehydration at 130 ° C. for 3 hours. After concentrating the obtained reaction product, 100 parts of chloroform and 50 parts of ion-exchanged water were added, followed by stirring and liquid separation. Water washing was performed 3 times. The obtained organic layer was charged with 1.00 part of activated carbon, stirred at 23 ° C. for 30 minutes, and then filtered. After concentrating the filtrate, the obtained concentrate is fractionated in a column (Merck silica gel 60-200 mesh developing solvent: chloroform / methanol = 5/1) to obtain a salt 1.21 represented by the formula (B8). Got a part.

MS (ESI (+) Spectrum): M ⁺ 281.0
MS (ESI (-) Spectrum): M ^- 561.2

式（Ｂ６−ａ）で表される塩１．９１部、モノクロロベンゼン５０．００部及び式（Ｂ２−ｅ）で表される化合物２．４３部を仕込み、２３℃で３０分間攪拌した後、硫酸０．２０部及びモレキュラーシーブ（商品名：モレキュラーシーブ ４Ａ、和光純薬製）１０．００部を仕込み、１３０℃で３時間還流脱水した。得られた反応物を濃縮後、クロロホルム１００部及びイオン交換水５０部を仕込み、攪拌、分液を行った。水洗を３回行った。得られた有機層に活性炭１．００部を仕込み、２３℃で３０分間攪拌した後、ろ過した。ろ液を濃縮した後、得られた濃縮物をカラム（メルク シリカゲル６０−２００メッシュ 展開溶媒：クロロホルム／メタノール＝５／１）分取することにより、式（Ｂ９）で表される塩０．５８部を得た。 Example 9: Synthesis of salt represented by formula (B9)

1.91 parts of a salt represented by the formula (B6-a), 50.00 parts of monochlorobenzene and 2.43 parts of a compound represented by the formula (B2-e) were charged and stirred at 23 ° C. for 30 minutes. 0.20 parts of sulfuric acid and 10.00 parts of molecular sieve (trade name: Molecular Sieve 4A, manufactured by Wako Pure Chemical Industries, Ltd.) were charged, followed by reflux dehydration at 130 ° C. for 3 hours. After concentrating the obtained reaction product, 100 parts of chloroform and 50 parts of ion-exchanged water were added, followed by stirring and liquid separation. Water washing was performed 3 times. The obtained organic layer was charged with 1.00 part of activated carbon, stirred at 23 ° C. for 30 minutes, and then filtered. After concentrating the filtrate, the resulting concentrate is fractionated in a column (Merck silica gel 60-200 mesh developing solvent: chloroform / methanol = 5/1) to obtain 0.58 salt represented by the formula (B9). Got a part.

MS (ESI (+) Spectrum): M ^<+> 207.1
MS (ESI (-) Spectrum): M ^- 561.2

Example 10: Synthesis of salt represented by formula (B10)

6.08 parts of the compound represented by the formula (B2-e) and 25 parts of tetrahydrofuran were charged, stirred at room temperature, and after confirming the dissolution of the compound represented by the formula (B2-e), 1.43 parts of pyridine were charged. The temperature was raised to 40 ° C. Further, a mixed solution of 2.55 parts of chloroacetyl chloride and 5 parts of tetrahydrofuran was added dropwise over 1 hour. After dropping, the mixture was stirred at 40 ° C. for 5 hours, and the temperature was lowered to 5 ° C. 10 parts of ion-exchanged water cooled to 5 ° C. and 40 parts of ethyl acetate were added, stirred and separated. 10 parts of 10% aqueous potassium carbonate solution at 5 ° C. is added to the collected organic layer for washing, liquid separation is performed to collect the organic layer, and then 10 parts of ion exchange water is further added to the collected organic layer. The organic layer was recovered by washing with water and liquid separation. This washing operation was repeated 5 times. After the collected organic layer was concentrated, 5.88 parts of a compound represented by the formula (B10-a) was obtained by fractionating the column under the following conditions.
Developing medium; silica gel 60-200 mesh; made by Merck developing solvent: ethyl acetate

式（Ｂ１０−ｂ）で表される塩２．５０部及びジメチルホルムアミド１２．９６部を仕込み、２３℃で３０分間攪拌した。得られた混合物に、炭酸カリウム０．７９部及びヨウ化カリウム０．２４部を仕込み、４０℃で１時間撹拌した後、式（Ｂ１０−ａ）で表される化合物２．２８部をジメチルホルムアミド４．５６部に溶解した溶液を１時間かけて滴下した。４０℃で６時間撹拌した後、２３℃に冷却した。得られた反応物に、クロロホルム９４．０２部、５％シュウ酸水溶液１４．３８部及びイオン交換水８．６４部を仕込み、攪拌、分液を行った。回収された有機層に、イオン交換水３８．０２部を仕込み、攪拌、分液を行った。水洗を７回行った。得られた有機層に活性炭１．００部を仕込み、２３℃で３０分間攪拌した後、ろ過した。ろ液を濃縮した後、得られた濃縮物に、アセトニトリル１０部を添加して溶解し、濃縮し、酢酸エチル１０部を加えて攪拌し、上澄液を除去した。得られた残渣にｔｅｒｔ−ブチルメチルエーテル１０部を加えて攪拌し、上澄液を除去した。得られた残渣をクロロホルムに溶解し、濃縮した後、得られた濃縮物をカラム（メルク シリカゲル６０−２００メッシュ 展開溶媒：クロロホルム／メタノール＝５／１）分取することにより、式（Ｂ１０）で表される塩０．７４部を得た。

2.50 parts of a salt represented by the formula (B10-b) and 12.96 parts of dimethylformamide were added and stirred at 23 ° C. for 30 minutes. To the obtained mixture, 0.79 part of potassium carbonate and 0.24 part of potassium iodide were added and stirred at 40 ° C. for 1 hour, and then 2.28 parts of the compound represented by the formula (B10-a) was added to dimethylformamide. The solution dissolved in 4.56 parts was added dropwise over 1 hour. After stirring at 40 ° C. for 6 hours, the mixture was cooled to 23 ° C. The obtained reaction product was charged with 94.02 parts of chloroform, 14.38 parts of a 5% oxalic acid aqueous solution and 8.64 parts of ion-exchanged water, and stirred and separated. The recovered organic layer was charged with 38.02 parts of ion-exchanged water and stirred and separated. Washing with water was performed 7 times. The obtained organic layer was charged with 1.00 part of activated carbon, stirred at 23 ° C. for 30 minutes, and then filtered. After concentrating the filtrate, 10 parts of acetonitrile was added to the resulting concentrate to dissolve it, concentrated, 10 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 10 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in chloroform and concentrated, and the resulting concentrate was fractionated in a column (Merck silica gel 60-200 mesh developing solvent: chloroform / methanol = 5/1) to obtain the formula (B10). 0.74 parts of the salt represented were obtained.

MS (ESI (+) Spectrum): M ⁺ 263.1
MS (ESI (-) Spectrum): M ^- 619.2

Example 11: Synthesis of salt represented by formula (B11)

First, 101.50 parts of the compound represented by the formula (B11-a) and 253.75 parts of acetic acid were added, stirred at room temperature, 61.17 parts of 31% hydrogen peroxide was added dropwise over 10 minutes, Stir for hours. To the obtained reaction mass, 253.75 parts of ion-exchanged water was added, stirred, and filtered to obtain 96.93 parts of a compound represented by the formula (B11-b).

28.00 parts of the compound represented by the formula (B11-b) and 140.00 parts of tetrahydrofuran were charged, stirred at room temperature, and 28.13 parts of trimethylsilyl chloride was added dropwise over 10 minutes. 73.36 parts (purity 32%) of the compound represented by the formula (B11-c) was dropped into the obtained mixed mass over 25 minutes while keeping the temperature at 40 ° C. or lower, and the mixture was stirred at 23 ° C. for 1 hour. To the obtained reaction mass, 70 parts of 1N hydrochloric acid was added dropwise, followed by stirring and liquid separation. To the recovered aqueous layer, 70 parts of tert-butyl methyl ether was added, stirred, and separated. To the recovered aqueous layer, 210 parts of chloroform was added and stirred, and after liquid separation, the recovered organic layer was filtered. After the filtrate was concentrated, 16.06 parts of acetonitrile was added and dissolved in the resulting concentrate, and then 200.78 parts of tert-butyl methyl ether was added and stirred, followed by filtration. 27.84 parts of the salt represented by B11-d) were obtained.

式（Ｂ１１−ｆ）で表される塩２．２６部、モノクロロベンゼン５０．００部及び式（Ｂ２−ｅ）で表される化合物２．４３部を仕込み、２３℃で３０分間攪拌した後、硫酸０．２０部及びモレキュラーシーブ（商品名：モレキュラーシーブ ４Ａ、和光純薬製）１０．００部を仕込み、１３０℃で３時間還流脱水した。得られた反応物を濃縮後、クロロホルム１００部及びイオン交換水５０部を仕込み、攪拌、分液を行った。水洗を３回行った。得られた有機層に活性炭１．００部を仕込み、２３℃で３０分間攪拌した後、ろ過した。ろ液を濃縮した後、得られた濃縮物に、アセトニトリル２０部を添加して溶解し、濃縮し、酢酸エチル２０部を加えて攪拌し、上澄液を除去した。得られた残渣にｔｅｒｔ−ブチルメチルエーテル２０部を加えて攪拌し、上澄液を除去した。得られた残渣をクロロホルムに溶解し、濃縮することにより、式（Ｂ１１）で表される塩１．１８部を得た。 It was obtained by charging 5.91 parts of the salt represented by the formula (B11-d), 3.74 parts of the salt represented by the formula (B11-e) and 16.26 parts of ion-exchanged water and stirring at room temperature. To the mixed mass, 1.97 parts of 35% hydrochloric acid was added and stirred at 23 ° C. for 5 hours. After removing the supernatant of the obtained reaction mass, 20 parts of acetonitrile was added to the resulting residue to dissolve, concentrate, and 24.81 parts of tert-butyl methyl ether was added and stirred. Was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 5.17 parts of the salt represented by the formula (B11-f).

After 2.26 parts of a salt represented by the formula (B11-f), 50.00 parts of monochlorobenzene and 2.43 parts of a compound represented by the formula (B2-e) were charged and stirred at 23 ° C. for 30 minutes, 0.20 parts of sulfuric acid and 10.00 parts of molecular sieve (trade name: Molecular Sieve 4A, manufactured by Wako Pure Chemical Industries, Ltd.) were charged, followed by reflux dehydration at 130 ° C. for 3 hours. After concentrating the obtained reaction product, 100 parts of chloroform and 50 parts of ion-exchanged water were added, followed by stirring and liquid separation. Water washing was performed 3 times. The obtained organic layer was charged with 1.00 part of activated carbon, stirred at 23 ° C. for 30 minutes, and then filtered. After the filtrate was concentrated, 20 parts of acetonitrile was added to the resulting concentrate to dissolve it, concentrated, 20 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 20 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in chloroform and concentrated to obtain 1.18 parts of the salt represented by the formula (B11).

MS (ESI (+) Spectrum): M ⁺ 277.1
MS (ESI (-) Spectrum): M ^- 561.2

Synthesis Example 1: Synthesis of Resin A1 Monomer E, monomer F, monomer B, monomer C and monomer D were charged in a molar ratio of 30: 14: 6: 20: 30. Subsequently, 1.5 mass times dioxane was added with respect to the total mass of all the monomers. Into the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were respectively added to 1.00 mol% and 3.00 mol% with respect to the total number of moles of all monomers. And heated at 73 ° C. for about 5 hours. Thereafter, the reaction solution is purified by performing the operation of pouring into a large amount of methanol / water mixed solvent (4: 1) and precipitating three times, and the weight average molecular weight is about 8.1 × 10 ^3. The coalescence was obtained with a yield of 65%. The obtained copolymer has a structural unit derived from each monomer of the following formula, and this was designated as resin A1.

Synthesis Example 2: Synthesis of Resin A2 Monomer A, monomer B and monomer C were charged in a molar ratio of 50:25:25, and then 1.5 mass times dioxane was added to the total mass of all monomers. It was. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in proportions of 1 mol% and 3 mol%, respectively, with respect to the total number of moles of all monomers. This was heated at 77 ° C. for about 5 hours. Thereafter, the reaction solution is purified by pouring it into a large amount of methanol / water mixed solvent (3: 1) and precipitating three times, and the weight average molecular weight is about 8.0 × 10 ^3. The coalescence was obtained in 60% yield. This copolymer has a structural unit derived from each monomer of the following formula, and this was designated as resin A2.

Synthesis Example 3: Synthesis of Resin A3 Monomer A, monomer F, monomer B, monomer C, and monomer D were charged in a molar ratio of 30: 14: 6: 20: 30. Subsequently, 1.5 mass times dioxane was added with respect to the total mass of all the monomers. Into the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were respectively added to 1.00 mol% and 3.00 mol% with respect to the total number of moles of all monomers. And heated at 73 ° C. for about 5 hours. Thereafter, the reaction solution is purified by pouring it into a large amount of methanol / water mixed solvent (4: 1) and precipitating three times, and the weight average molecular weight is about 7.8 × 10 ^3. The coalescence was obtained with a yield of 68%. The obtained copolymer has a structural unit derived from each monomer of the following formula, and this was designated as resin A3.

  As shown in Table 1, a chemically amplified photoresist composition was prepared by filtering a mixture obtained by mixing and dissolving the following components through a fluororesin filter having a pore size of 0.2 μm.

酸発生剤Ｈ２：

<Resin>
Resins A1 to A3
<Acid generator>
Acid generator B1: Hydrochloric acid generator represented by formula (B1) B2: Hydrochloric acid generator represented by formula (B2) B3: Hydrochloric acid generator represented by formula (B3) B4: Expressed by formula (B4) Hydrochloric acid generator B5: Hydrochloric acid generator represented by formula (B5) B6: Hydrochloric acid generator represented by formula (B6) B7: Hydrochloric acid generator represented by formula (B7) B8: Formula (B8) Hydrochloric acid generator B9: Hydrochloric acid generator represented by formula (B9) B10: Hydrochloric acid generator represented by formula (B10) B11: Hydrochloric acid generator represented by formula (B11) H1:

Acid generator H2:

<Basic compound: Quencher>
Quencher C1: 2,6-diisopropylaniline <solvent>
Propylene glycol monomethyl ether acetate 265 parts 2-heptanone 20.0 parts Propylene glycol monomethyl ether 20.0 parts γ-butyrolactone 3.5 parts

An organic antireflective coating composition [ARC-29; manufactured by Nissan Chemical Co., Ltd.] was applied onto a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to obtain a thickness of 780 mm. An organic antireflection film was formed. Next, the above resist composition was spin-coated on the organic antireflection film so that the film thickness after drying was 85 nm.
After applying the resist composition, the obtained silicon wafer was pre-baked (PB) for 60 seconds on a direct hot plate at the temperature described in the “PB” column of Table 1. Using the ArF excimer stepper for immersion exposure [XT: 1900 Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized light] on the wafer on which the resist composition film is thus formed, the exposure amount is stepwise. The line and space pattern was subjected to immersion exposure.
After the exposure, post exposure bake (PEB) is performed on the hot plate at a temperature described in the “PEB” column of Table 1 for 60 seconds, and further with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds. Paddle development was performed.

  In each resist film, the exposure amount at which the 50 nm line and space pattern becomes an exposure amount of 1: 1 was defined as the effective sensitivity.

  Resolution evaluation: The case where the resolution in effective sensitivity was 43 nm or less was marked with ◎, the case where it exceeded 43 nm and 45 nm or less was marked with ○, and the case where it exceeded 45 nm was marked with ×. Numerical values in parentheses indicate resolution (nm).

  Shape evaluation: A 50 nm line and space pattern was observed with a scanning electron microscope. A case where the top shape and the skirt shape were close to a rectangle was good, and a case where the top shape was round or close to a T-shape or a skirt was seen was judged as x.

  Line edge roughness evaluation (LER): The surface of the resist pattern after the lithography process is observed with a scanning electron microscope, and the contact width of the unevenness on the side wall of the resist pattern is 5 nm or less. did. The numerical value in the parenthesis indicates the touch width (nm) of the unevenness.

  According to the salt of the present invention, a pattern having excellent resolution can be obtained from a resist composition containing the salt.

Claims (11)

A salt represented by the formula (I).

[In the formula (I),
Q ¹ and Q ² each independently represent a fluorine atom or a C _1-6 perfluoroalkyl group.
L ¹ and L ² each independently represent a C _1-17 alkylene group, and —CH ₂ — contained in the alkylene group may be replaced by —O— or —CO—.
Ring W ¹ represents a C _3-36 saturated hydrocarbon ring.
R ² represents a C _1-6 alkyl group or a C _1-6 alkoxy group.
s represents the integer of 0-2. When s is 2, the plurality of R ² may be the same or different.
Ring ^{W 2} represents an adamantane ring.
R ⁴ represents a hydroxyl group, a C _1-6 hydroxyalkyl group or a C _1-6 hydroxyalkoxy group, and a hydrogen atom contained in the hydroxyalkyl group and the hydroxyalkoxy may be substituted with a halogen atom.
v represents an integer of 1 to 3. When v is 2 or 3, the plurality of R ⁴ may be the same or different.
R ⁵ represents a C _1-6 alkyl group or a C _1-6 alkoxy group.
w represents an integer of 0 to 2. When w is 2, the plurality of R ⁵ may be the same or different.
Z ⁺ represents an organic counter ion. ] A salt represented by the formula (I1) .

[In the formula (I1),
Q ¹ and Q ² each independently represent a fluorine atom or a C _1-6 perfluoroalkyl group.
L ¹ and L ² each independently represent a C _1-17 alkylene group, and —CH ₂ — contained in the alkylene group may be replaced by —O— or —CO—.
Ring W ¹ represents a C _3-36 saturated hydrocarbon ring.
R ² represents a C _1-6 alkyl group or a C _1-6 alkoxy group.
s represents the integer of 0-2. When s is 2, the plurality of R ² may be the same or different.
Ring W ² represents a C _3-36 saturated hydrocarbon ring.
R ⁴ represents a hydroxyl group, a C _1-6 hydroxyalkyl group or a C _1-6 hydroxyalkoxy group, and a hydrogen atom contained in the hydroxyalkyl group and the hydroxyalkoxy may be substituted with a halogen atom.
v represents an integer of 1 to 3. When v is 2 or 3, the plurality of R ⁴ may be the same or different.
R ⁵ represents a C _1-6 alkyl group or a C _1-6 alkoxy group.
w represents an integer of 0 to 2. When w is 2, the plurality of R ⁵ may be the same or different.
Z ⁺ represents an organic counter ion.
R ¹ is, to display the _{C 1 -6} alkyl group. ] Salt according to claim 2 wherein ring W ² is adamantane ring. L ¹ is ^* —CO—O—L ³ —, ^* —CO—O—L ⁴ —O—, —L ⁵ —O—CO— or ^* —CO—O—L ⁶ —CO—O— (L ³ represents a single bond or a C _1-6 alkylene group, L ⁴ , L ⁵ and L ⁶ each independently represent a C _1-6 alkylene group, and * represents —C (Q ¹ ) (Q ² ). The salt according to any one of claims 1 to 3 , which represents a bond with- . L ² is ^* -OL ⁷ -CO-O-, ^* -OL ⁸ -CO-OL ⁹ -O-, ^* -CO-OL ¹⁰ -CO-O-, ^* -O —CO—L ¹¹ —O— or ^* —O—L ¹² —O— (L ^{7 to} L ¹² each independently represents a C _1-6 alkylene group, and * represents a bond to ring W ^1. The salt according to any one of claims 1 to 4 , wherein Salts according to claim 1-5 ring W ¹ is adamantane ring. The salt according to any one of claims 1 to 6, wherein Z ⁺ is a triarylsulfonium cation.   The acid generator containing the salt in any one of Claims 1-7.   A resin comprising the acid generator according to claim 8 and a resin, wherein the resin has an acid labile group, is insoluble or hardly soluble in an alkaline aqueous solution, and is soluble in an alkaline aqueous solution by the action of an acid. A resist composition.   Furthermore, the resist composition of Claim 9 containing a basic compound. (1) The process of apply | coating the resist composition of Claim 9 or 10 on a board | substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer using an exposure machine;
(4) A step of heating the composition layer after exposure,
(5) a step of developing the heated composition layer using a developing device;
A method for producing a resist pattern including: