JP2012077071A - Compound and resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound to be included in a resist composition giving a pattern having excellent line edge roughness.SOLUTION: There is provided, for example, a compound expressed by formula (III-2) obtained by reacting a compound expressed by formula (I-1) with a compound expressed by formula (II-2).

Description

  The present invention relates to a compound, a resist composition, and the like.

  Patent Document 1 describes a copolymer obtained by polymerizing 2-ethyl-2-adamantyl methacrylate and p-hydroxystyrene as a resin component of a resist composition.

JP 2005-97254 A

In a conventional copolymer which is a resin component of a resist composition, the line edge roughness of a resist pattern obtained from a resist composition containing the copolymer may not always be sufficiently satisfactory.
Therefore, it has been desired to develop a new compound that replaces the copolymer that is a resin component of the conventional resist composition.

［式（Ｉ）中、Ａ^１、Ａ^２、Ａ^３及びＡ^４は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、炭素数３〜１０の脂環式飽和炭化水素基、炭素数４〜２０の脂環式飽和炭化水素基を有するアルキル基、ヒドロキシ基、フェニル基又は炭素数７〜１２のフェニルアルキル基を表し、該アルキル基、該脂環式飽和炭化水素基、該フェニル基及び該フェニルアルキル基に含まれる水素原子は、ヒドロキシ基で置換されてもよい。］

［式（ＩＩ）中、Ｗ¹は、塩素原子、臭素原子、ヨウ素原子、メタンスルホニルオキシ基又はｐ−トルエンスルホニルオキシ基を表す。
Ｘ¹及びＸ²は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｎは、１〜４の整数を表す。
Ｚ¹は、炭素数１〜６のアルキル基又は炭素数３〜１０の脂環式飽和炭化水素基を表す。
環Ｙ¹は、炭素数３〜２０の飽和環を表す。］ The present invention includes the following inventions.
[1] A compound obtained by reacting a compound represented by formula (I) with a compound represented by formula (II).

[In the formula (I), A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, Represents an alkyl group, a hydroxy group, a phenyl group or a phenylalkyl group having 7 to 12 carbon atoms having an alicyclic saturated hydrocarbon group having 4 to 20 carbon atoms, the alkyl group, the alicyclic saturated hydrocarbon group, The hydrogen atom contained in the phenyl group and the phenylalkyl group may be substituted with a hydroxy group. ]

[In Formula (II), W ¹ represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group or a p-toluenesulfonyloxy group.
X ¹ and X ² each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
n represents an integer of 1 to 4.
Z ¹ represents an alkyl group having 1 to 6 carbon atoms or an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms.
Ring Y ¹ represents a saturated ring having 3 to 20 carbon atoms. ]

[2] The compound according to [1], wherein X ¹ and X ² are hydrogen atoms.

[3] The compound according to [1] or [2], which has a molecular weight of 700 to 10,000.

[4] A resist composition comprising the compound according to any one of [1] to [3] and an acid generator.

[5] The resist composition according to claim 4, comprising at least two compounds according to any one of [1] to [3].

［式（Ｉ）中、Ａ^１、Ａ^２、Ａ^３及びＡ^４は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、炭素数３〜１０の脂環式飽和炭化水素基、炭素数４〜２０の脂環式飽和炭化水素基を有するアルキル基、ヒドロキシ基、フェニル基又は炭素数７〜１２のフェニルアルキル基を表し、該アルキル基、該脂環式飽和炭化水素基、該フェニル基及び該フェニルアルキル基に含まれる水素原子は、ヒドロキシ基で置換されてもよい。］ [6] The resist composition according to [4] or [5], further comprising a compound represented by formula (I).

[In the formula (I), A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, Represents an alkyl group, a hydroxy group, a phenyl group or a phenylalkyl group having 7 to 12 carbon atoms having an alicyclic saturated hydrocarbon group having 4 to 20 carbon atoms, the alkyl group, the alicyclic saturated hydrocarbon group, The hydrogen atom contained in the phenyl group and the phenylalkyl group may be substituted with a hydroxy group. ]

[7] The method according to any one of [4] to [6], further comprising a resin having an acid labile group and insoluble or hardly soluble in an alkaline aqueous solution and soluble in an alkaline aqueous solution by the action of an acid. Resist composition.

[8] A method for producing a compound according to any one of [1] to [3],
A method for producing a compound comprising a step of reacting a compound represented by formula (I) with a compound represented by formula (II).

[9] The process for producing a compound according to [8], wherein the compound represented by the formula (I) and the compound represented by the formula (II) are reacted in the presence of a base.

［式（Ｉ’）中、Ａ^ｘ１、Ａ^ｘ２、Ａ^ｘ３及びＡ^ｘ４は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、炭素数３〜１０のシクロアルキル基、炭素数４〜２０のシクロアルキルアルキル基、ヒドロキシ基、フェニル基又は炭素数７〜１２のフェニルアルキル基を表し、該アルキル基、該シクロアルキル基、該シクロアルキルアルキル基、該フェニル基及び該フェニルアルキル基に含まれる水素原子は、ヒドロキシ基で置換されてもよい。］

［式（ＩＩ’）中、Ｗ^ｘ1は、塩素原子、臭素原子、ヨウ素原子、メタンスルホニルオキシ基又はｐ−トルエンスルホニルオキシ基を表す。
Ｘ^ｘ1及びＸ^ｘ2は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｎｘは、１〜４の整数を表す。
Ｚ^ｘ1は、炭素数１〜６のアルキル基又は炭素数３〜１０のシクロアルキル基を表す。
環Ｙ^ｘ1は、炭素数３〜２０の飽和環を表す。］ The present invention further includes the following inventions.
[10] A compound obtained by reacting a compound represented by the formula (I ′) with a compound represented by the formula (II ′).

[In Formula (I ′), A ^x1 , A ^x2 , A ^x3 and A ^x4 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or 4 carbon atoms. Represents a cycloalkylalkyl group having 20 to 20 carbon atoms, a hydroxy group, a phenyl group or a phenylalkyl group having 7 to 12 carbon atoms, the alkyl group, the cycloalkyl group, the cycloalkylalkyl group, the phenyl group and the phenylalkyl group The contained hydrogen atom may be substituted with a hydroxy group. ]

[In Formula (II ′), W ^x1 represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group or a p-toluenesulfonyloxy group.
X ^x1 and X ^x2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
nx represents an integer of 1 to 4.
Z ^x1 represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms.
Ring Y ^x1 represents a saturated ring having 3 to 20 carbon atoms. ]

［式（Ｉ’）中、Ａ^ｘ１、Ａ^ｘ２、Ａ^ｘ３及びＡ^ｘ４は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、炭素数３〜１０のシクロアルキル基、炭素数４〜２０のシクロアルキルアルキル基、ヒドロキシ基、フェニル基又は炭素数７〜１２のフェニルアルキル基を表し、該アルキル基、該シクロアルキル基、該シクロアルキルアルキル基、該フェニル基及び該フェニルアルキル基に含まれる水素原子は、ヒドロキシ基で置換されてもよい。］ [11] The resist composition according to [4] or [5], further comprising a compound represented by the formula (I ′).

[In Formula (I ′), A ^x1 , A ^x2 , A ^x3 and A ^x4 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or 4 carbon atoms. Represents a cycloalkylalkyl group having 20 to 20 carbon atoms, a hydroxy group, a phenyl group or a phenylalkyl group having 7 to 12 carbon atoms, the alkyl group, the cycloalkyl group, the cycloalkylalkyl group, the phenyl group and the phenylalkyl group The contained hydrogen atom may be substituted with a hydroxy group. ]

  According to the compound of the present invention, a resist pattern having excellent line edge roughness can be obtained from a resist composition containing the compound.

  The compound of the present invention is a compound obtained by reacting a compound represented by formula (I) with a compound represented by formula (II).

［式（Ｉ）中、Ａ^１、Ａ^２、Ａ^３及びＡ^４は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、炭素数３〜１０の脂環式飽和炭化水素基、炭素数４〜２０の脂環式飽和炭化水素基を有するアルキル基、ヒドロキシ基、フェニル基又は炭素数７〜１２のフェニルアルキル基を表し、該アルキル基、該脂環式飽和炭化水素基、該フェニル基及び該フェニルアルキル基に含まれる水素原子は、ヒドロキシ基で置換されてもよい。］ <Compound represented by formula (I)>

[In the formula (I), A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, Represents an alkyl group, a hydroxy group, a phenyl group or a phenylalkyl group having 7 to 12 carbon atoms having an alicyclic saturated hydrocarbon group having 4 to 20 carbon atoms, the alkyl group, the alicyclic saturated hydrocarbon group, The hydrogen atom contained in the phenyl group and the phenylalkyl group may be substituted with a hydroxy group. ]

Examples of the alkyl group having 1 to 6 carbon atoms in A ^{1 to} A ⁴ 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 neopentyl group. T-pentyl group, 1-methylbutyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, A 1,1-dimethylbutyl group, a 1-methyl-2-ethylpropyl group and the like can be mentioned, and a hydrogen atom, a methyl group, an ethyl group, an isopropyl group and a butyl group are preferable.

Examples of the alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms in A ^{1 to} A ⁴ include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group. Group, and the like.
Examples of the alkyl group having an alicyclic saturated hydrocarbon group having 4 to 20 carbon atoms in A ^{1 to} A ⁴ include a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, a cyclobutylpropyl group, a cyclopentylmethyl group, Cyclopentylethyl group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group, cyclohexylpentyl group, cyclohexylhexyl group, cycloheptyloctyl group, cyclooctyldecyl group, cyclononyldodecyl group, cyclodecylheptyl group, etc. Can be mentioned.

Examples of the phenylalkyl group having 7 to 12 carbon atoms in A ^{1 to} A ⁴ include a benzyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, and a phenylhexyl group.

Examples of the alkyl group having 1 to 6 carbon atoms substituted with a hydroxy group in A ^{1 to} A ⁴ include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxypentyl group, a hydroxyhexyl group, a 3-hydroxybutyl group, Etc.
Examples of the alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms that is substituted with a hydroxy group in A ^{1 to} A ⁴ include a hydroxycyclopropyl group, a hydroxycyclobutyl group, a hydroxyclopentyl group, a hydroxycyclohexyl group, 3,4 -A dihydroxycyclohexyl group, a hydroxycycloheptyl group, a hydroxynorbornyl group, a 4-hydroxycyclooctyl group, a 2-hydroxycyclononyl group, a 5-hydroxycyclodecyl group and the like can be mentioned.
Examples of the alkyl group having an alicyclic saturated hydrocarbon group having 4 to 20 carbon atoms that is substituted with a hydroxy group in A ^{1 to} A ⁴ include a hydroxycyclopropylmethyl group, a hydroxycyclopropylethyl group, and a hydroxycyclobutylmethyl group , Hydroxycyclobutylpropyl group, hydroxycyclopentylmethyl group, hydroxycyclopentylethyl group, hydroxycyclopentylbutyl group, hydroxycyclohexylmethyl group, hydroxycyclohexylethyl group, hydroxycyclohexylbutyl group, 3,4,5-trihydroxycyclohexylbutyl group, hydroxy Cyclohexylpentyl group, hydroxycyclohexylhexyl group, hydroxycycloheptyloctyl group, hydroxycyclooctyldecyl group, hydroxycyclononyl Sill group, hydroxycyclopentyl decyl heptyl, 3-hydroxy-6- (cyclohexyl) hexyl group, 4-hydroxy-13- (norbornyl) tridecyl group, and the like.
Examples of the phenyl group substituted with a hydroxy group in A ^{1 to} A ⁴ include 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2,4-dihydroxyphenyl group, 2,3,4- A trihydroxyphenyl group, 3,4,5-trihydroxyphenyl group, etc. are mentioned.
Examples of the phenylalkyl group having 7 to 12 carbon atoms substituted with a hydroxy group in A ^{1 to} A ⁴ include a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, a 4-hydroxybenzyl group, and a 2,4-dihydroxybenzyl group. 2,3,4-trihydroxybenzyl group, 2- (2-hydroxyphenyl) ethyl group, 2- (4-hydroxyphenyl) ethyl group, 3- (3,4-dihydroxyphenyl) propyl group, 4- ( 3-hydroxyphenyl) butyl group, 3- (3,5-dihydroxyphenyl) pentyl group, 5- (2-hydroxyphenyl) hexyl group, 6- (2,3,4,5-tetrahydroxyphenyl) hexyl group, etc. Is mentioned.

The method for synthesizing the compound represented by the formula (I) is described in “Tetrahedron Letters Vol. 34, No. 18, p. 2887 to 2890, 1993”.
Examples of the compound represented by the formula (I) include the following compounds.

［式（ＩＩ）中、Ｗ¹は、塩素原子、臭素原子、ヨウ素原子、メタンスルホニルオキシ基又はｐ−トルエンスルホニルオキシ基を表す。
Ｘ¹及びＸ²は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｎは、１〜４の整数を表す。
Ｚ¹は、炭素数１〜６のアルキル基又は炭素数３〜１０の脂環式飽和炭化水素基を表す。
環Ｙ¹は、炭素数３〜２０の飽和環を表す。］ <Compound represented by formula (II)>

[In Formula (II), W ¹ represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group or a p-toluenesulfonyloxy group.
X ¹ and X ² each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
n represents an integer of 1 to 4.
Z ¹ represents an alkyl group having 1 to 6 carbon atoms or an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms.
Ring Y ¹ represents a saturated ring having 3 to 20 carbon atoms. ]

The alkyl group having 1 to 6 carbon atoms in X ¹ and ^{X 2,} same as the above. X ¹ and X ² are preferably a hydrogen atom or a methyl group.
n is preferably 1 or 2.
Examples of the alkyl group having 1 to 6 carbon atoms in Z ¹ include the same ones as described above, and preferably include a methyl group, an ethyl group, or an isopropyl group.
Examples of the alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms in Z ¹ include the same ones as described above, and preferably include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
The saturated ring having 3 to 20 carbon atoms in Y ¹ is preferably a saturated hydrocarbon ring, for example, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, or a cyclodecane ring. , Cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloeicosane ring, norbornane ring, adamantane ring, diamantane Ring, dimethanodecalin ring, tetradecahydrotrimethanoanthracene ring, etc. A karin ring is mentioned, More preferably, an adamantane ring is mentioned.

Examples of the compound represented by the formula (II) include the following compounds.

  The compound represented by the formula (II) can be produced by, for example, a method described in Japanese Patent Application Laid-Open No. 2004-26798 or Japanese Patent No. 3008594.

<Reaction between the compound represented by the formula (I) and the compound represented by the formula (II)>
The reaction between the compound represented by the formula (I) and the compound represented by the formula (II) is performed in an inert solvent such as toluene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, and the reaction temperature is- 30-200 degreeC, Preferably, it is 0-150 degreeC. The reaction is preferably performed in the presence of a base. Examples of the base include triethylamine, pyridine, sodium methoxide, sodium ethoxide, potassium tert-butoxide and other organic bases, sodium hydride, potassium carbonate, and sodium hydroxide. Such inorganic bases or mixtures thereof are used.

The amount of the compound represented by the formula (II) is preferably 0.1 to 2 molar equivalents, more preferably 0.2 to 1 with respect to one hydroxy group of the compound represented by the formula (I). It is a molar equivalent, and the amount of the base used is preferably 1 to 6 times the molar amount, more preferably 1 to 3 times the molar amount relative to 1 mol of the compound represented by the formula (II).
In the reaction, a catalyst such as potassium iodide or a phase transfer catalyst such as tetrabutylammonium bromide can be added.

  The compound obtained by reacting the compound represented by the formula (I) with the compound represented by the formula (II) can be taken out by ordinary post-treatment. The compound obtained by reacting the compound represented by formula (I) with the compound represented by formula (II) is obtained by reacting the compound represented by formula (I) and the compound represented by formula (II). The compound obtained by the reaction is obtained as a mixture of a plurality of compounds having different substituent positions or different numbers, but can be purified by chromatography, recrystallization or distillation.

  The molecular weight of the compound obtained by reacting the compound represented by the formula (I) with the compound represented by the formula (II) is usually 700 to 10000, preferably 700 to 6000. The molecular weight can be measured by a known means such as mass spectrometry.

  The compound of the present invention is a compound having an acid labile group and insoluble or hardly soluble in an alkaline aqueous solution, and soluble in an alkaline aqueous solution by the action of an acid. The compound of the present invention and an acid generator Is suitable as a chemically amplified resist composition for forming a resist pattern by electron beam or EUV irradiation.

  The content of the compound obtained by reacting the compound represented by formula (I) and the compound represented by formula (II) in the resist composition is 5 to 99 based on the solid content of the resist composition. It is preferably about 8% by mass. The solid content of the resist composition means the total of the resist composition components excluding the solvent (E) described later. The solid content in the composition and the content of the compound corresponding thereto can be measured by a known analytical means such as liquid chromatography or gas chromatography.

<Acid generator (hereinafter sometimes referred to as "acid generator (B)")>
The acid generator used in the resist composition of the present invention is preferably one that decomposes when irradiated with light or radiation to generate an acid.
The acid generator (B) is classified into a nonionic type and an ionic type. Nonionic acid generators include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4). -Sulfonates), sulfones (e.g. disulfone, ketosulfone, sulfonyldiazomethane) and the like. The ionic acid generator is typically an onium salt containing an onium cation (for example, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of the anion of the onium salt include a sulfonate anion, a sulfonylimide anion, and a sulfonylmethide anion.

  Examples of the acid generator (B) include JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, JP-A 63-146038, JP-A 63-163452, JP-A-62-153853, JP-A-63-146029, U.S. Pat. No. 3,779,778, U.S. Pat. No. 3,849,137, German Patent 3914407, European Patent 126,712. The compound which generate | occur | produces an acid by the radiation as described in No. can be used.

  The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a sulfonate represented by the formula (B1).

［式（Ｂ１）中、
Ｑ¹及びＱ²は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^b1は、単結合又は炭素数１〜１７の２価の飽和炭化水素基を表し、前記２価の飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ｙは、置換基を有していてもよい炭素数１〜１８のアルキル基又は置換基を有していてもよい炭素数３〜１８の脂環式飽和炭化水素基を表し、前記アルキル基及び前記脂環式飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＳＯ_２−又は−ＣＯ−で置き換わっていてもよい。
Ｚ⁺は、有機カチオンを表す。］

[In the formula (B1),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group is replaced by —O— or —CO—. May be.
Y represents an alkyl group having 1 to 18 carbon atoms which may have a substituent or an alicyclic saturated hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and the alkyl group and —CH ₂ — contained in the alicyclic saturated hydrocarbon group may be replaced by —O—, —SO ₂ — or —CO—.
Z ⁺ represents an organic cation. ]

Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. It is done.
In formula (B1), Q ¹ and Q ² are each independently preferably a perfluoromethyl group or a fluorine atom, more preferably a fluorine atom.

Examples of the divalent saturated hydrocarbon group include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and two or more of these groups. May be combined.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 , 6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group , Dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1, Linear alkanediyl groups such as 17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-2,2-diyl group;
An alkyl group (particularly an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group); For example, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl A branched alkanediyl group such as a 2-methylbutane-1,4-diyl group;
In cycloalkanediyl groups such as cyclobutane-1,3-diyl group, 1,3-cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group silene group, cyclooctane-1,5-diyl group, etc. A monocyclic saturated cyclic hydrocarbon group;
Polycyclic alicyclic saturated carbonization such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, 1,5-adamantane-1,5-diyl group, adamantane-2,6-diyl group A hydrogen group etc. are mentioned.

Examples of the group in which —CH ₂ — contained in the saturated hydrocarbon group of L ^b1 is replaced by —O— or —CO— include groups represented by formulas (b1-1) to (b1-6). Can be mentioned. L ^b1 is preferably a group represented by any one of formulas (b1-1) to (b1-4), more preferably a group represented by formula (b1-1) or formula (b1-2). Can be mentioned. Incidentally, the formula (b1-1) ~ formula (b1-6) are described together the left and right in the equation (B1), the left ^{C (Q 1) (Q 2} ) - bound to, the right side Combines with -Y. The same applies to specific examples of the following formulas (b1-1) to (b1-6).

式（ｂ１−１）〜式（ｂ１−６）中、
Ｌ^b2は、単結合又は炭素数１〜１５の飽和炭化水素基を表す。
Ｌ^b3は、単結合又は炭素数１〜１２の飽和炭化水素基を表す。
Ｌ^b4は、炭素数１〜１３の飽和炭化水素基を表す。但しＬ^b3及びＬ^b4の炭素数上限は１３である。
Ｌ^b5は、炭素数１〜１５の飽和炭化水素基を表す。
Ｌ^b6及びＬ^b7は、それぞれ独立に、炭素数１〜１５の飽和炭化水素基を表す。但しＬ^b6及びＬ^b7の炭素数上限は１６である。
Ｌ^b8は、炭素数１〜１４の飽和炭化水素基を表す。
Ｌ^b9及びＬ^b10は、それぞれ独立に、炭素数１〜１１の飽和炭化水素基を表す。但しＬ^ｂ９及びＬ^ｂ１０の炭素数上限は１２である。
中でも、式（ｂ１−１）で表される２価の基が好ましく、Ｌ^b2が単結合又は−ＣＨ_２−である式（ｂ１−１）で表される２価の基がより好ましい。

In formula (b1-1) to formula (b1-6),
L ^b2 represents a single bond or a saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b3 represents a single bond or a saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b4 represents a saturated hydrocarbon group having 1 to 13 carbon atoms. However, the upper limit of the carbon number of L ^b3 and L ^b4 is 13.
L ^b5 represents a saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b6 and L ^b7 each independently represent a saturated hydrocarbon group having 1 to 15 carbon atoms. However, the upper limit of the carbon number of L ^b6 and L ^b7 is 16.
L ^b8 represents a saturated hydrocarbon group having 1 to 14 carbon atoms.
L ^b9 and L ^b10 each independently represent a saturated hydrocarbon group having 1 to 11 carbon atoms. However, the upper limit of the carbon number of L ^b9 and L ^b10 is 12.
Among these, a divalent group represented by the formula (b1-1) is preferable, and a divalent group represented by the formula (b1-1) in which L ^b2 is a single bond or —CH ₂ — is more preferable.

Examples of the divalent group represented by the formula (b1-1) include the following.

Examples of the divalent group represented by the formula (b1-2) include the following.

Examples of the divalent group represented by the formula (b1-3) include the following.

Examples of the divalent group represented by the formula (b1-4) include the following.

Examples of the divalent group represented by the formula (b1-5) include the following.

Examples of the divalent group represented by the formula (b1-6) include the following.

The saturated hydrocarbon group for L ^b1 may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, a carboxy group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, an acyl group having 2 to 4 carbon atoms, and a glycidyloxy group. Is mentioned.
Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group and the like.

As an alkyl group of Y, a C1-C6 alkyl group is preferable.
Examples of the substituent for the alkyl group and the alicyclic saturated hydrocarbon group include, for example, a halogen atom (excluding a fluorine atom), a hydroxy group, an oxo group, an alkyl group having 1 to 12 carbon atoms, and a hydroxy group-containing carbon number of 1 to 1 12 alkyl groups, alicyclic saturated hydrocarbon groups having 3 to 16 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms, aralkyl groups having 7 to 21 carbon atoms, carbon number 2-4 acyl group, a glycidyl group or a _{- (CH 2) j2 -O-} CO-R b1 group (wherein, R ^b1 represents an alkyl group having 1 to 16 carbon atoms, fat 3 to 16 carbon atoms Represents a cyclic saturated hydrocarbon group or an aromatic hydrocarbon group having 6 to 18 carbon atoms, j2 represents an integer of 0 to 4). The alkyl group, alicyclic saturated hydrocarbon group, aromatic hydrocarbon group, aralkyl group, and the like, which are substituents for Y, may further have a substituent. Examples of the substituent include an alkyl group, a halogen atom, a hydroxy group, and an oxo group.
Examples of the hydroxy group-containing alkyl group include a hydroxymethyl group and a hydroxyethyl group.
Examples of the group in which —CH ₂ — in the alkyl group and the alicyclic saturated hydrocarbon group of Y is replaced by —O—, —SO ₂ — or —CO— include, for example, a cyclic ether group (—CH ₂ — is —O - groups substituted with a) saturated cyclic hydrocarbon radical having an oxo group (-CH ₂ - is replaced by -CO- groups), sultone Hajime Tamaki (two adjacent -CH ₂ -, respectively, -O- Or a group substituted by —SO ₂ —) or a lactone ring group (a group in which two adjacent —CH ₂ — are each replaced by —O— or —CO—).

In particular, examples of the alicyclic saturated hydrocarbon group for Y include groups represented by formulas (Y1) to (Y26).

  Especially, it is preferably a group represented by any one of formulas (Y1) to (Y19), more preferably represented by formula (Y11), formula (Y14), formula (Y15) or formula (Y19). And more preferably a group represented by formula (Y11) or formula (Y14).

Examples of Y in the case of the alicyclic saturated hydrocarbon group having a substituent include the following.

  Y is preferably an adamantyl group optionally having a substituent (for example, an oxo group, an aromatic hydrocarbon group, etc.), more preferably an adamantyl group substituted with an adamantyl group, an aromatic hydrocarbon group, or An oxoadamantyl group;

Examples of the sulfonate anion in the salt represented by the formula (B1) include the following formulas (b1-1-1) to (b1-1-9) in which the substituent L ^b1 is the formula (b1-1). An anion represented by In the following formulae, the definition of the substituent has the same meaning as described above, and the substituents R ^b2 and R ^b3 each independently represent an alkyl group having 1 to 4 carbon atoms (preferably a methyl group).

Examples of the sulfonate anion include the following.

Among these, the following sulfonate anions are more preferable.

  Examples of the cation contained in the acid generator (B) include an onium cation such as a sulfonium cation, an iodonium cation, an ammonium cation, a benzothiazolium cation, and a phosphonium cation. Among these, a sulfonium cation and an iodonium cation are preferable, and an arylsulfonium cation is more preferable.

Z ⁺ in formula (B1) is preferably represented by any of formula (b2-1) to formula (b2-4).

In these formulas (b2-1) to (b2-4),
R ^{b4 to} R ^b6 each independently represents an alkyl group having 1 to 30 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and is contained in the alicyclic saturated hydrocarbon group. The hydrogen atom may be substituted with a halogen atom, an acyl group having 2 to 4 carbon atoms or a glycidyloxy group, and the aromatic hydrocarbon group includes a halogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, It may be substituted with an alicyclic saturated hydrocarbon group having 3 to 18 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.

R ^b7 and R ^b8 each independently represent a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represent an integer of 0 to 5.

R ^b9 and R ^b10 each independently represent an alkyl group having 1 to 18 carbon atoms or an alicyclic saturated hydrocarbon group having 3 to 18 carbon atoms.
R ^b11 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
The alkyl group of R ^{b9 to} R ^b11 preferably has 1 to 12 carbon atoms, and the alicyclic saturated hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.
R ^b12 represents an alkyl group having 1 to 12 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The aromatic hydrocarbon group is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 18 carbon atoms, or an alkylcarbonyloxy group having 1 to 12 carbon atoms. May be substituted.
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), These rings —CH ₂ — may be replaced by —O—, —S— or —CO—.

R ^{b13 to} R ^b18 each independently represent a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b11 represents -S- or -O-.
o2, p2, s2, and t2 each independently represents an integer of 0 to 5.
q2 and r2 each independently represents an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, the plurality of R ^b13 may be the same or different. When p2 is 2 or more, the plurality of R ^b14 may be the same or different. When q2 is 2 or more, the plurality of R ^b15 is When r2 is 2 or more, a plurality of R ^b16 may be the same or different. When s2 is 2 or more, a plurality of R ^b17 may be the same or different, and t2 is 2 or more. Sometimes, the plurality of R ^b18 may be the same or different.

  Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, Examples thereof include a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, and a 2-ethylhexylcarbonyloxy group.

Preferred alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl and 2-ethylhexyl.
Preferred alicyclic saturated hydrocarbon groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, 2-alkyl-2-adamantyl, 1- (1-adamantyl) -1-alkyl. 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 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.

式（ｂ２−１−１）中、
Ｒ^b19〜Ｒ^b21は、それぞれ独立に、ハロゲン原子（好ましくはフッ素原子）、ヒドロキシ基、炭素数１〜１８のアルキル基、炭素数３〜１８の脂環式飽和炭化水素基又は炭素数１〜１２のアルコキシ基を表す。
アルキル基は、好ましくは炭素数１〜１２であり、脂環式飽和炭化水素基は、好ましくは炭素数４〜１８である。
前記アルキル基は、ヒドロキシ基、炭素数１〜１２のアルコキシ基又は炭素数６〜１８の芳香族炭化水素基で置換されていてもよい。
前記脂環式飽和炭化水素基は、ハロゲン原子、炭素数２〜４のアシル基又はグリシジルオキシ基で置換されていてもよい。
ｖ２〜ｘ２は、それぞれ独立に０〜５の整数（好ましくは０又は１）を表す。ｖ２が２以上のとき、複数のＲ^b19は同一でも異なってもよく、ｗ２が２以上のとき、複数のＲ^b20は同一でも異なってもよく、ｘ２が２以上のとき、複数のＲ^b21は同一でも異なってもよい。
なかでも、Ｒ^b19〜Ｒ^b21は、それぞれ独立に、好ましくは、ハロゲン原子（好ましくはフッ素原子）、ヒドロキシ基、炭素数１〜１２のアルキル基、又は炭素数１〜１２のアルコキシ基である。

In formula (b2-1-1),
R ^{b19 to} R ^b21 each independently represent a halogen atom (preferably a fluorine atom), a hydroxy group, an alkyl group having 1 to 18 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 18 carbon atoms, or 1 to 1 carbon atoms. 12 alkoxy groups are represented.
The alkyl group preferably has 1 to 12 carbon atoms, and the alicyclic saturated hydrocarbon group preferably has 4 to 18 carbon atoms.
The alkyl group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
The alicyclic saturated hydrocarbon group may be substituted with a halogen atom, an acyl group having 2 to 4 carbon atoms, or a glycidyloxy group.
v2 to x2 each independently represents an integer of 0 to 5 (preferably 0 or 1). When v2 is 2 or more, the plurality of R ^b19 may be the same or different. When w2 is 2 or more, the plurality of R ^b20 may be the same or different. When x2 is 2 or more, the plurality of R ^b21 is It may be the same or different.
Among these, R ^{b19 to} R ^b21 are preferably each independently a halogen atom (preferably a fluorine atom), a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

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.

  The acid generator (B1) is a combination of the above-described sulfonate anion and organic cation. The above-mentioned anion and cation can be arbitrarily combined, but any one of anion (b1-1-1) to anion (b1-1-9) and a cation (b2-1-1), and an anion ( A combination of any one of b1-1-3) to (b1-1-5) and a cation (b2-3) is preferable.

  Preferred acid generators (B1) are those represented by formula (B1-1) to formula (B1-18). Among them, formula (B1-1), formula (B1-2), formula (B1-6), formula (B1-11), formula (B1-12), formula (B1) which are acid generators containing a triphenylsulfonium cation. -13), a compound represented by formula (B1-14), formula (B1-17) or formula (B1-18) is more preferable.

  The content of the acid generator (B) is preferably 1 part by mass or more (more preferably 3 parts by mass or more, still more preferably 10 parts by mass or more, particularly preferably 100 parts by mass of the solid content of the resist composition. Is 20 parts by mass or more), preferably 50 parts by mass or less (more preferably 40 parts by mass or less).

<Basic compound (hereinafter sometimes referred to as “basic compound (C)”)>
The resist composition of the present invention may contain 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, amine or ammonium hydroxide). 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).

ここで、Ａｒ^c1は、芳香族炭化水素基を表す。
Ｒ^c5及びＲ^c6は、それぞれ独立に、水素原子、アルキル基、脂環式飽和炭化水素基（好ましくはシクロアルキル基）又は芳香族炭化水素基を表す。但し前記アルキル基、前記脂環式飽和炭化水素基又は前記芳香族炭化水素基の水素原子は、ヒドロキシ基、アミノ基、又は炭素数１〜６のアルコキシ基で置換されていてもよく、前記アミノ基は、炭素数１〜４のアルキル基で置換されていてもよい。
前記アルキル基は、好ましくは炭素数１〜６程度であり、前記脂環式飽和炭化水素基は、好ましくは炭素数５〜１０程度であり、前記芳香族炭化水素基は、好ましくは炭素数６〜１０程度である。
Ｒ^c7は、アルキル基、アルコキシ基、脂環式飽和炭化水素基（好ましくはシクロアルキル基）又は芳香族炭化水素基を表す。但しアルキル基、アルコキシ基、脂環式飽和炭化水素基及び芳香族炭化水素基の水素原子は、上記と同様の置換基を有していてもよい。
ｍ３は０〜３の整数を表す。ｍ３が２以上のとき、複数のＲ^c7は、互いに同一でも異なってもよい。
Ｒ^c7のアルキル基、脂環式飽和炭化水素基及び芳香族炭化水素基の好ましい炭素数は、上記と同じであり、Ｒ^c7のアルコキシ基は、好ましくは炭素数１〜６程度である。

Here, Ar ^c1 represents an aromatic hydrocarbon group.
R ^c5 and R ^c6 each independently represents a hydrogen atom, an alkyl group, an alicyclic saturated hydrocarbon group (preferably a cycloalkyl group) or an aromatic hydrocarbon group. However, the hydrogen atom of the alkyl group, the alicyclic saturated hydrocarbon group or the aromatic hydrocarbon group may be substituted with a hydroxy group, an amino group, or an alkoxy group having 1 to 6 carbon atoms. The group may be substituted with an alkyl group having 1 to 4 carbon atoms.
The alkyl group preferably has about 1 to 6 carbon atoms, the alicyclic saturated hydrocarbon group preferably has about 5 to 10 carbon atoms, and the aromatic hydrocarbon group preferably has 6 carbon atoms. -10 or so.
R ^c7 represents an alkyl group, an alkoxy group, an alicyclic saturated hydrocarbon group (preferably a cycloalkyl group) or an aromatic hydrocarbon group. However, the hydrogen atom of an alkyl group, an alkoxy group, an alicyclic saturated hydrocarbon group, and an aromatic hydrocarbon group may have the same substituent as described above.
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.
The preferable carbon number of the alkyl group of R ^c7 , the alicyclic saturated hydrocarbon group and the aromatic hydrocarbon group is the same as described above, and the alkoxy group of R ^c7 preferably has about 1 to 6 carbon atoms.

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.

ここで、
Ｒ^c8は、上記Ｒ^c7で説明したいずれかの基を表す。
窒素原子と結合するＲ^c9、Ｒ^c10、Ｒ^c11〜Ｒ^c14、Ｒ^c16〜Ｒ^c19及びＲ^c22は、それぞれ独立に、Ｒ^c5及びＲ^c6で説明したいずれかの基を表す。
芳香族炭素と結合するＲ^c20、Ｒ^c21、Ｒ^c23〜Ｒ^c28は、それぞれ独立に、Ｒ^c7で説明したいずれかの基を表す。
ｏ３〜ｕ３は、それぞれ独立に０〜３の整数を表す。ｏ３が２以上のとき、複数のＲ^c20は同一でも異なってもよく、ｐ３が２以上のとき、複数のＲ^c21は同一でも異なってもよく、ｑ３が２以上のとき、複数のＲ^c24は同一でも異なってもよく、ｒ３が２以上のとき、複数のＲ^c25は同一でも異なってもよく、ｓ３が２以上のとき、複数のＲ^c26は同一でも異なってもよく、ｔ３が２以上のとき、複数のＲ^c27は同一でも異なってもよく、ｕ３が２以上のとき、複数のＲ^c28は同一でも異なってもよい。
Ｒ^c15は、アルキル基、脂環式飽和炭化水素基又はアルカノイル基を表す。
ｎ３は０〜８の整数を表す。ｎ３が２以上のとき、複数のＲ^c15は、互いに同一でも異なってもよい。
Ｒ^c15のアルキル基は、好ましくは炭素数１〜６程度であり、脂環式飽和炭化水素基は、好ましくは炭素数３〜６程度である。
アルカノイル基としては、アセチル基、２−メチルアセチル基、２，２−ジメチルアセチル基、プロピオニル基、ブチリル基、イソブチリル基、ペンタノイル基、２，２−ジメチルプロピオニル基等が挙げられ、好ましくは炭素数２〜６程度である。
Ｌ^c1及びＬ^c2は、それぞれ独立に、アルキレン基、−ＣＯ−、−Ｃ（＝ＮＨ）−、−Ｃ（＝ＮＲ^c3）−、−Ｓ−、−Ｓ−Ｓ−又はこれらの組合せを表す。前記２価のアルキレン基は、好ましくは炭素数１〜６程度である。
Ｒ^c3は、炭素数１〜４のアルキル基を表す。 Examples of the basic compound (C) include compounds represented by the formulas (C3) to (C11).

here,
R ^c8 represents any of the groups described for R ^c7 above.
R ^c9 , R ^c10 , R ^{c11 to} R ^c14 , R ^{c16 to} R ^c19 and R ^c22 bonded to the nitrogen atom each independently represent any of the groups described for R ^c5 and R ^c6 .
R ^c20 , R ^c21 and R ^{c23 to} R ^c28 bonded to the aromatic carbon each independently represents any of the groups described for R ^c7 .
o3 to u3 each independently represents an integer of 0 to 3. When o3 is 2 or more, the plurality of R ^c20 may be the same or different. When p3 is 2 or more, the plurality of R ^c21 may be the same or different. When q3 is 2 or more, the plurality of R ^c24 is When r3 is 2 or more, a plurality of R ^c25s may be the same or different. When s3 is 2 or more, a plurality of R ^c26s may be the same or different, and t3 is 2 or more. Sometimes, the plurality of R ^c27 may be the same or different, and when ^u3 is 2 or more, the plurality of R ^c28 may be the same or different.
R ^c15 represents an alkyl group, an alicyclic saturated hydrocarbon group or an alkanoyl group.
n3 represents an integer of 0 to 8. When n3 is 2 or more, the plurality of R ^c15 may be the same as or different from each other.
The alkyl group for R ^c15 preferably has about 1 to 6 carbon atoms, and the alicyclic saturated hydrocarbon group preferably has about 3 to 6 carbon atoms.
Examples of the alkanoyl group include an acetyl group, a 2-methylacetyl group, a 2,2-dimethylacetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pentanoyl group, and a 2,2-dimethylpropionyl group. It is about 2-6.
L ^c1 and L ^c2 each independently represent an alkylene group, —CO—, —C (═NH) —, —C (═NR ^c3 ) —, —S—, —S—S—, or a combination thereof. . The divalent alkylene group preferably has about 1 to 6 carbon atoms.
R ^c3 represents an alkyl group having 1 to 4 carbon atoms.

  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.

  Examples of ammonium hydroxide include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, and 3- (trifluoromethyl). ) Phenyltrimethylammonium hydroxide and choline.

<Solvent (sometimes referred to as "solvent (E)")
The resist composition of the present invention preferably contains a solvent (E). 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 preferably 90% by mass or more (more preferably 92% by mass or more, further preferably 94% by mass or more), preferably 99.9% by mass or less, based on the total amount of the resist composition. (More preferably 99% by mass or less). 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.

Next, the composition after application is dried to form a composition layer.
Drying is performed, for example, by evaporating and removing the solvent using a heating device such as a hot plate (so-called pre-baking), or using a decompression device. As for drying temperature, about 50-200 degreeC is illustrated, for example. The pressure is exemplified by about 1 to 1.0 × 10 ⁵ Pa.

The composition layer thus obtained is exposed using an exposure machine. At this time, exposure is usually performed through a mask corresponding to a required pattern. Exposure light sources include those that emit laser light in the ultraviolet region such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), solid-state laser light source (YAG or semiconductor laser) Etc.) that radiates far ultraviolet or vacuum ultraviolet harmonic laser light, emits extreme ultraviolet light (EUV) near the wavelength of 13 nm, or X-ray or electron beam ( Various light sources such as EB) can be used. In this specification, irradiation with these radiations may be collectively referred to as “exposure”.

The composition layer after exposure is subjected to heat treatment (so-called post-exposure baking) 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 resist pattern.

<Application>
The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for EB irradiation, or a resist composition for EUV irradiation. It is suitable as a resist composition for irradiation or a resist composition for EUV irradiation.

  Next, the present invention will be described more specifically with reference to examples. In the examples, “%” and “part” representing the content or amount used are based on weight unless otherwise specified.

The structure of the compound was confirmed by NMR (JNM-ECA-500; manufactured by JEOL Ltd.) and LC-MS.
The measurement conditions for LC-MS are as follows.
LC condition: Agilent 1100
Column TSKgel SuperHZ
Eluent: Tetrahydrofuran; 0.25 ml / min
MS conditions: HP LC / MSD 6130
Ionization: ESI +
Post column: 0.5 mM NaCl (water: acetonitrile = 1: 1)
25 μl / min
Or
0.5 mM KCl (water: acetonitrile = 1: 1)
25 μl / min

  The compound represented by the formula (I-1) is obtained by the method described in Tetrahedron Letters Vol. 34, No. 18, p2887-2890 (1993), and the compound represented by the formula (II-1) The compound represented by (II-2) was synthesized by the method described in JP-A-2004-26798. The compound represented by the formula (II-4) was synthesized by the method described in Japanese Patent No. 3008594.

［式（ＩＩＩ−１）中、ｍは１〜４の整数を表す。］ Example 1 Synthesis of a compound obtained by reacting a compound represented by the formula (I-1) with a compound represented by the formula (II-1)

[In formula (III-1), m represents the integer of 1-4. ]

Compound represented by formula (I-1) (compound represented by formula (I-1-1), compound represented by formula (I-1-2), represented by formula (I-1-3)) A mixture of the compound represented by formula (I-1-4) and a solution obtained by dissolving 5.0 parts (8.1 mmol) in 40 parts of anhydrous dimethyl sulfoxide. 3.9 parts (16.1 mmol) of the compound to be obtained, 3.3 parts (23.9 mmol) of potassium carbonate and 0.3 part (1.8 mmol) of potassium iodide were added, followed by heating at 75 ° C. for 6 hours. Stir. The reaction solution was cooled, adjusted to pH 3 with 150 parts of 2% aqueous oxalic acid, and the organic layer was extracted with ethyl acetate. The extracted organic layer was washed with pure water, dried over magnesium sulfate, and concentrated. 2. A compound represented by formula (III-1), which is a compound obtained by reacting a compound represented by formula (I-1) and a compound represented by formula (II-1) as a mixture; 9 parts were obtained.
As a result of LC-MS analysis, the isomer ratio was as follows.
The 1-substituted product refers to a compound in which one of the —OH groups of the compound represented by the formula (I-1) has reacted with the compound represented by the formula (II-1).
The disubstituted product refers to a compound in which two of the —OH groups of the compound represented by formula (I-1) have reacted with the compound represented by formula (II-1).
The trisubstituted product refers to a compound in which three of the —OH groups of the compound represented by formula (I-1) have reacted with the compound represented by formula (II-1).
The 4-substitution refers to a compound in which four of the —OH groups of the compound represented by formula (I-1) have reacted with the compound represented by formula (II-1).

1-substituted product (m = 1) [M + Na] ⁺ = 853.2 (M ⁺ = 830.36)
Disubstituted (m = 2) [M + Na] ⁺ = 1059.3 (M ⁺ = 1036.49)
Trisubstituted (m = 3) [M + Na] ⁺ = 1265.4 (M ⁺ = 1242.62)
4-substitution (m = 4) [M + Na] ⁺ = 1471.5 (M ⁺ = 1448.75)
1-substituted product: 2-substituted product: 3-substituted product: 4-substituted product = 12: 29: 30: 29 (molar ratio)

Example 2 Synthesis of Compound Represented by Formula (III-2)

Compound represented by formula (I-1) (compound represented by formula (I-1-1), compound represented by formula (I-1-2), represented by formula (I-1-3)) Of the compound represented by formula (I-1-4)) in a solution of 5.0 parts (8.1 mmol) dissolved in 40 parts of anhydrous N, N-dimethylformamide, 2 parts of compound (4.1) (16.0 mmol), potassium carbonate 3.3 parts (23.9 mmol) and potassium iodide 0.3 part (1.8 mmol) were added, and 75 ° C. For 6 hours. The reaction solution was cooled, adjusted to pH 3 with 150 parts of 2% aqueous oxalic acid, and the organic layer was extracted with ethyl acetate. The extracted organic layer was washed with pure water, dried over magnesium sulfate, and concentrated. As a mixture, 3.2 parts of the compound represented by the formula (III-2) was obtained.
As a result of LC-MS analysis, the isomer ratio was as follows.
The 1-substituted product refers to a compound in which one of the —OH groups of the compound represented by formula (I-1) has reacted with the compound represented by formula (II-2).
The disubstituted product refers to a compound in which two of the —OH groups of the compound represented by the formula (I-1) have reacted with the compound represented by the formula (II-2).
The trisubstituted product refers to a compound in which three of the —OH groups of the compound represented by the formula (I-1) have reacted with the compound represented by the formula (II-2).
The 4-substitution refers to a compound in which four of the —OH groups of the compound represented by formula (I-1) have reacted with the compound represented by formula (II-2).

1-substituted product (m = 1) [M + K] ⁺ = 883.3 (M ⁺ = 844.38)
Disubstituted product (m = 2) [M + K] ⁺ = 1103.4 (M ⁺ = 1064.52)
Trisubstituted (m = 3) [M + K] ⁺ = 1323.5 (M ⁺ = 1284.67)
4-substitution (m = 4) [M + K] ⁺ = 1543.6 (M ⁺ = 1504.82)
1-substituted product: 2-substituted product: 3-substituted product: 4-substituted product = 11: 30: 36: 23 (molar ratio)

式（ＩＶ−１）で表される化合物４０．０部（０．２１モル）をトルエン２００部に溶解した。このトルエン溶液に、式（Ｖ−１）で表される化合物１１６部（０．８２モル）、炭酸カリウム１７１部（１．２３モル）及びＮ−メチルピロリジン８．８部（０．１モル）を仕込み、内温１１２℃で８時間加熱還流した。反応溶液を冷却して、塩をろ過して除いた。ろ液に５％シュウ酸２００部を加えて、酢酸エチルで抽出した。有機層を純水で洗浄して、硫酸マグネシウムで乾燥した後、減圧下に濃縮して、粗生成物１４０部を得た。得られた粗生成物をシリカゲルクロマトグラフィー（展開液；ヘキサン／酢酸エチル）で精製して、化合物（ＩＩ−３）を４３．７部（収率７１．０％）得た。 Synthesis Example 1 Synthesis of Compound Represented by Formula (II-3)

40.0 parts (0.21 mol) of the compound represented by the formula (IV-1) was dissolved in 200 parts of toluene. In this toluene solution, 116 parts (0.82 mol) of the compound represented by the formula (V-1), 171 parts (1.23 mol) of potassium carbonate and 8.8 parts (0.1 mol) of N-methylpyrrolidine. And heated to reflux at an internal temperature of 112 ° C. for 8 hours. The reaction solution was cooled and the salt was removed by filtration. To the filtrate, 200 parts of 5% oxalic acid was added and extracted with ethyl acetate. The organic layer was washed with pure water, dried over magnesium sulfate, and concentrated under reduced pressure to obtain 140 parts of a crude product. The resulting crude product was purified by silica gel chromatography (developing solution; hexane / ethyl acetate) to obtain 43.7 parts (yield 71.0%) of compound (II-3).

¹ H-NMR (measurement solvent CDCl ₃ ; internal standard substance tetramethylsilane): δ (ppm) 3.61 (t, J = 6.1 Hz, 2H); 2.60 (2H); 2.50 (t, J = 7.7 Hz, 2H); 2.42 (m, J = 6.9 Hz, 1H); 2.08 (m, 2H); 1.90 to 1.62 (12H); 0.97 (d, (J = 6.9Hz, 6H)

¹³ C-NMR (measurement solvent CDCl ₃ ; internal standard substance tetramethylsilane): δ (ppm) 16.97; 26.58; 26.91; 27.90; 31.25; 32.25; 33.96; 34.42; 38.22; 44.27; 92.16; 171.84

式（Ｉ−１）で表される化合物（式（Ｉ−１−１）で表される化合物、式（Ｉ−１−２）で表される化合物、式（Ｉ−１−３）で表される化合物及び式（Ｉ−１−４）で表される化合物の混合物）２．７部（４．３ミリモル）を無水Ｎ，Ｎ−ジメチルホルムアミド３０部に溶解した溶液に、式（ＩＩ−３）で表される化合物３．９部（１３．０ミリモル）、炭酸カリウム２．７部（１９．５ミリモル）及びヨウ化カリウム０．１部（０．６ミリモル）を加えて、１２０℃で２時間過熱攪拌した。反応溶液を冷却後、２％シュウ酸水１５０部でｐＨ３に調整して、有機層を酢酸エチルで抽出した。抽出した有機層を純水で洗浄して、硫酸マグネシウムで乾燥した後、濃縮した。混合物として式（ＩＩＩ−３）で表される化合物を３．６部得た。
ＬＣ−ＭＳ分析を行った結果、以下のような異性体比であった。
１置換体とは、式（Ｉ−１）で表される化合物の−ＯＨ基のうち１個が、式（ＩＩ−３）で表される化合物と反応した化合物をいう。
２置換体とは、式（Ｉ−１）で表される化合物の−ＯＨ基のうち２個が、式（ＩＩ−３）で表される化合物と反応した化合物をいう。
３置換体とは、式（Ｉ−１）で表される化合物の−ＯＨ基のうち３個が、式（ＩＩ−３）で表される化合物と反応した化合物をいう。
４置換体とは、式（Ｉ−１）で表される化合物の−ＯＨ基のうち４個が、式（ＩＩ−３）で表される化合物と反応した化合物をいう。 Example 3 Synthesis of Compound Represented by Formula (III-3)

Compound represented by formula (I-1) (compound represented by formula (I-1-1), compound represented by formula (I-1-2), represented by formula (I-1-3)) Mixture of the compound represented by formula (I-1-4) and a solution obtained by dissolving 2.7 parts (4.3 mmol) in 30 parts anhydrous N, N-dimethylformamide. 3) 3.9 parts (13.0 mmol) of the compound represented by 3), 2.7 parts (19.5 mmol) of potassium carbonate and 0.1 part (0.6 mmol) of potassium iodide were added, And stirred for 2 hours. The reaction solution was cooled, adjusted to pH 3 with 150 parts of 2% aqueous oxalic acid, and the organic layer was extracted with ethyl acetate. The extracted organic layer was washed with pure water, dried over magnesium sulfate, and concentrated. As a mixture, 3.6 parts of the compound represented by the formula (III-3) was obtained.
As a result of LC-MS analysis, the isomer ratio was as follows.
The 1-substituted product refers to a compound in which one of the —OH groups of the compound represented by formula (I-1) has reacted with the compound represented by formula (II-3).
The disubstituted product refers to a compound in which two of the —OH groups of the compound represented by the formula (I-1) have reacted with the compound represented by the formula (II-3).
The tri-substituted product refers to a compound in which three of the —OH groups of the compound represented by formula (I-1) have reacted with the compound represented by formula (II-3).
The 4-substitution refers to a compound in which four of the —OH groups of the compound represented by formula (I-1) have reacted with the compound represented by formula (II-3).

Monosubstituted (m = 1) [M + K] ⁺ = 925.4 (M ⁺ = 886.42)
Disubstituted product (m = 2) [M + K] ⁺ = 1187.6 (M ⁺ = 1148.62)
Trisubstituted product (m = 3) [M + K] ⁺ = 1449.8 (M ⁺ = 1410.81)
4-substitution (m = 4) [M + K] ⁺ = 1712.0 (M ⁺ = 1673.00)
1-substituted product: 2-substituted product: 3-substituted product: 4-substituted product = 5: 21: 44: 30 (molar ratio)

式（Ｉ−１）で表される化合物（式（Ｉ−１−１）で表される化合物、式（Ｉ−１−２）で表される化合物、式（Ｉ−１−３）で表される化合物及び式（Ｉ−１−４）で表される化合物の混合物）２．７部（４．３ミリモル）を無水Ｎ、Ｎ−ジメチルホルムアミド３０部に溶解した溶液に、式（ＩＩ−３）で表される化合物２．６部（８．７ミリモル）、炭酸カリウム１．８部（１３．０ミリモル）及びヨウ化カリウム０．１部（０．６ミリモル）を加えて、１２０℃で３時間過熱攪拌した。反応溶液を冷却後、２％シュウ酸水１５０部でｐＨ３に調整して、有機層を酢酸エチルで抽出した。抽出した有機層を純水で洗浄して、硫酸マグネシウムで乾燥した後、濃縮した。混合物として式（ＩＩＩ−４）で表される化合物を３．４部得た。
ＬＣ−ＭＳ分析を行った結果、以下のような異性体比であった。
１置換体とは、式（Ｉ−１）で表される化合物の−ＯＨ基のうち１個が、式（ＩＩ−３）で表される化合物と反応した化合物をいう。
２置換体とは、式（Ｉ−１）で表される化合物の−ＯＨ基のうち２個が、式（ＩＩ−３）で表される化合物と反応した化合物をいう。
３置換体とは、式（Ｉ−１）で表される化合物の−ＯＨ基のうち３個が、式（ＩＩ−３）で表される化合物と反応した化合物をいう。
４置換体とは、式（Ｉ−１）で表される化合物の−ＯＨ基のうち４個が、式（ＩＩ−３）で表される化合物と反応した化合物をいう。 Example 4 Synthesis of Compound Represented by Formula (III-4)

Compound represented by formula (I-1) (compound represented by formula (I-1-1), compound represented by formula (I-1-2), represented by formula (I-1-3)) A mixture of the compound represented by formula (I-1-4) and a solution obtained by dissolving 2.7 parts (4.3 mmol) in 30 parts anhydrous N, N-dimethylformamide. 2.6 parts (8.7 mmol) of the compound represented by 3), 1.8 parts (13.0 mmol) of potassium carbonate and 0.1 part (0.6 mmol) of potassium iodide were added at 120 ° C. For 3 hours. The reaction solution was cooled, adjusted to pH 3 with 150 parts of 2% aqueous oxalic acid, and the organic layer was extracted with ethyl acetate. The extracted organic layer was washed with pure water, dried over magnesium sulfate, and concentrated. As a mixture, 3.4 parts of the compound represented by the formula (III-4) was obtained.
As a result of LC-MS analysis, the isomer ratio was as follows.
The 1-substituted product refers to a compound in which one of the —OH groups of the compound represented by formula (I-1) has reacted with the compound represented by formula (II-3).
The disubstituted product refers to a compound in which two of the —OH groups of the compound represented by the formula (I-1) have reacted with the compound represented by the formula (II-3).
The tri-substituted product refers to a compound in which three of the —OH groups of the compound represented by formula (I-1) have reacted with the compound represented by formula (II-3).
The 4-substitution refers to a compound in which four of the —OH groups of the compound represented by formula (I-1) have reacted with the compound represented by formula (II-3).

Monosubstituted (m = 1) [M + K] ⁺ = 925.4 (M ⁺ = 886.42)
Disubstituted product (m = 2) [M + K] ⁺ = 1187.6 (M ⁺ = 1148.62)
Trisubstituted product (m = 3) [M + K] ⁺ = 1449.8 (M ⁺ = 1410.81)
4-substitution (m = 4) [M + K] ⁺ = 1712.0 (M ⁺ = 1673.00)
1-substituted product: 2-substituted product: 3-substituted product: 4-substituted product = 10: 36: 32: 22 (molar ratio)

式（Ｉ−１）で表される化合物（式（Ｉ−１−１）で表される化合物、式（Ｉ−１−２）で表される化合物、式（Ｉ−１−３）で表される化合物及び式（Ｉ−１−４）で表される化合物の混合物）２．７部（４．３ミリモル）を無水Ｎ、Ｎ−ジメチルホルムアミド３０部に溶解した溶液に、式（ＩＩ−３）で表される化合物１．６部（８．７ミリモル）、炭酸カリウム１．８部（１３．０ミリモル）及びヨウ化カリウム０．１部（０．６ミリモル）を加えて、８０℃で５時間過熱攪拌した。反応溶液を冷却後、２％シュウ酸水１５０部でｐＨ３に調整して、有機層を酢酸エチルで抽出した。抽出した有機層を純水で洗浄して、硫酸マグネシウムで乾燥した後、濃縮した。混合物として式（ＩＩＩ−５）で表される化合物を３．５部得た。
ＬＣ−ＭＳ分析を行った結果、以下のような異性体比であった。
１置換体とは、式（Ｉ−１）で表される化合物の−ＯＨ基のうち１個が、式（ＩＩ−４）で表される化合物と反応した化合物をいう。
２置換体とは、式（Ｉ−１）で表される化合物の−ＯＨ基のうち２個が、式（ＩＩ−４）で表される化合物と反応した化合物をいう。
３置換体とは、式（Ｉ−１）で表される化合物の−ＯＨ基のうち３個が、式（ＩＩ−４）で表される化合物と反応した化合物をいう。
４置換体とは、式（Ｉ−１）で表される化合物の−ＯＨ基のうち４個が、式（ＩＩ−４）で表される化合物と反応した化合物をいう。 Example 5 Synthesis of Compound Represented by Formula (III-5)

Compound represented by formula (I-1) (compound represented by formula (I-1-1), compound represented by formula (I-1-2), represented by formula (I-1-3)) A mixture of the compound represented by formula (I-1-4) and a solution obtained by dissolving 2.7 parts (4.3 mmol) in 30 parts anhydrous N, N-dimethylformamide. 1.6 parts (8.7 mmol) of the compound represented by 3), 1.8 parts (13.0 mmol) of potassium carbonate and 0.1 part (0.6 mmol) of potassium iodide were added, For 5 hours. The reaction solution was cooled, adjusted to pH 3 with 150 parts of 2% aqueous oxalic acid, and the organic layer was extracted with ethyl acetate. The extracted organic layer was washed with pure water, dried over magnesium sulfate, and concentrated. As a mixture, 3.5 parts of a compound represented by the formula (III-5) was obtained.
As a result of LC-MS analysis, the isomer ratio was as follows.
The 1-substituted product refers to a compound in which one of the —OH groups of the compound represented by the formula (I-1) has reacted with the compound represented by the formula (II-4).
The disubstituted product refers to a compound in which two of the —OH groups of the compound represented by the formula (I-1) have reacted with the compound represented by the formula (II-4).
The trisubstituted product refers to a compound in which three of the —OH groups of the compound represented by formula (I-1) have reacted with the compound represented by formula (II-4).
The 4-substitution refers to a compound in which four of the —OH groups of the compound represented by formula (I-1) have reacted with the compound represented by formula (II-4).

Monosubstituted (m = 1) [M + K] ⁺ = 817.3 (M ⁺ = 778.33)
Disubstituted product (m = 2) [M + K] ⁺ = 971.4 (M ⁺ = 932.43)
Trisubstituted (m = 3) [M + K] ⁺ = 1125.5 (M ⁺ = 1086.53)
4-substitution (m = 4) [M + K] ⁺ = 1279.6 (M ⁺ = 1240.63)
1-substituted product: 2-substituted product: 3-substituted product: 4-substituted product = 14: 33: 29: 24 (molar ratio)

Synthesis of Comparative Resin (H1) Copolymer (1) (molar ratio = 20: 80) of p-hydroxystyrene and 2-ethyl-2-adamantyl methacrylate, and 2-ethyl-2-adamantyl methacrylate A copolymer (2) with p-hydroxystyrene (molar ratio = 30: 70) was synthesized according to JP-A-2003-107708.
A mixture obtained by mixing the copolymer (1) and the copolymer (2) at a weight ratio of 50:50 was used as a comparative resin (H1).

Examples and Comparative Examples The following components were mixed and dissolved in the number of parts shown in Table 1, and further filtered through a fluoropolymer filter having a pore size of 0.2 μm to prepare a resist composition.

［表１中、PB/PEB以外の数値の単位は「部」である。］

[In Table 1, the unit of numerical values other than PB / PEB is “part”. ]

<Resin>
H1: Resin for comparison (H1)

<Acid generator>
B1: Triphenylsulfonium {3- (4-methylphenyl) adamantan-1-yl} methoxycarbonyldifluoromethanesulfonate

<Basic compound: Quencher>
C1: Tris [2- (2-methoxyethoxy) ethyl] amine

<Solvent>
E1:
Cyclohexanone 700 parts E2:
Propylene glycol monomethyl ether acetate 450 parts Propylene glycol monomethyl ether 100 parts

A silicon wafer is treated on a direct hot plate with hexamethyldisilazane at 90 ° C. for 60 seconds, and then spin-coated so that the film thickness after drying (pre-baking) the resist composition is 60 nm. did. After application of the resist composition, a composition layer was formed by pre-baking on a direct hot plate at the temperature indicated in the column “PB” in Table 1 for 60 seconds. A line and space pattern is formed on each wafer on which the resist film (composition layer) has been formed in this manner by using an electron beam drawing machine ("HL-800D 50 KeV" manufactured by Hitachi, Ltd.) and changing the exposure stepwise. Was exposed.
After exposure, post-exposure baking is performed on the hot plate at the temperature indicated in the column “PEB” in Table 1 for 60 seconds, followed by 60-second paddle development with an aqueous 2.38 mass% tetramethylammonium hydroxide solution. A resist pattern was obtained.
The obtained resist pattern was observed with a scanning electron microscope, and the results are shown in Table 3.

Effective sensitivity: Displayed with an exposure amount at which the line width and space width of a 200 nm line and space pattern are 1: 1.
Line edge roughness (LER): Shaking of the side wall of the pattern was evaluated at an exposure amount at which the line width and space width of the 200 nm line and space pattern were 1: 1.
○ when the fluctuation width of the side wall is 7 nm or less, △ when the fluctuation width of the side wall is more than 7 nm and less than 10 nm, and × when the fluctuation width of the side wall is more than 10 nm write. Figures are shown in parentheses.

  The resist pattern obtained from the resist composition of the example had better line edge roughness than the comparative example.

  According to the compound of the present invention, a resist pattern having excellent line edge roughness can be obtained from a resist composition containing the compound.

Claims (9)

A compound obtained by reacting a compound represented by formula (I) with a compound represented by formula (II).

[In the formula (I), A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, Represents an alkyl group, a hydroxy group, a phenyl group or a phenylalkyl group having 7 to 12 carbon atoms having an alicyclic saturated hydrocarbon group having 4 to 20 carbon atoms, the alkyl group, the alicyclic saturated hydrocarbon group, The hydrogen atom contained in the phenyl group and the phenylalkyl group may be substituted with a hydroxy group. ]

[In Formula (II), W ¹ represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group or a p-toluenesulfonyloxy group.
X ¹ and X ² each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
n represents an integer of 1 to 4.
Z ¹ represents an alkyl group having 1 to 6 carbon atoms or an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms.
Ring Y ¹ represents a saturated ring having 3 to 20 carbon atoms. ] The compound according to claim 1, wherein X ¹ and X ² are hydrogen atoms.   The compound according to claim 1 or 2, which has a molecular weight of 700 to 10,000.   A resist composition comprising the compound according to claim 1 and an acid generator.   The resist composition of Claim 4 containing at least 2 or more types of the compounds in any one of Claims 1-3. The resist composition according to claim 4 or 5, further comprising a compound represented by formula (I).

[In the formula (I), A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, Represents an alkyl group, a hydroxy group, a phenyl group or a phenylalkyl group having 7 to 12 carbon atoms having an alicyclic saturated hydrocarbon group having 4 to 20 carbon atoms, the alkyl group, the alicyclic saturated hydrocarbon group, The hydrogen atom contained in the phenyl group and the phenylalkyl group may be substituted with a hydroxy group. ]   The resist composition according to any one of claims 4 to 6, further comprising a resin having an acid labile group and insoluble or hardly soluble in an aqueous alkali solution and capable of being dissolved in an aqueous alkali solution by the action of an acid. It is a manufacturing method of the compound in any one of Claims 1-3, Comprising:
A method for producing a compound comprising a step of reacting a compound represented by formula (I) with a compound represented by formula (II).   The method for producing a compound according to claim 8, wherein the compound represented by the formula (I) and the compound represented by the formula (II) are reacted in the presence of a base.