JP2009221195A - Ester compound, and method of preparing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ester compound useful as an intermediate of a photoacid generator for use in preparing a compound that gives a chemical-amplification type resist composition suitable for electron beam lithography or EUV lithography and excellent in line-edge roughness in particular in addition to its characteristics of high resolution and high sensitivity. <P>SOLUTION: Disclosed is an ester compound represented by formula (I) (in the formula, Q<SP>1</SP>and Q<SP>2</SP>each independently represent a fluorine atom or a 1-6C perfluoroalkyl group, U represents a 1-20C divalent hydrocarbon group, L represents a halogen atom, a 1-12C alkylsulfonyloxy group or a 6-12C arylsulfonyloxy group provided that a carbon atom of the aryl group may be substituted with a hetero atom, and A<SP>+</SP>represents an organic pair ion). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an ester compound useful as an intermediate of a photoacid generator used in a chemically amplified resist material used for semiconductor microfabrication and a method for producing the same.

  As the fine processing of semiconductors progresses, it is required to improve the resolution. In principle, it is possible to increase the resolution as the exposure wavelength is shorter. The exposure light source for lithography used for manufacturing semiconductors is a g-line with a wavelength of 436 nm, an i-line with a wavelength of 365 nm, a KrF excimer laser with a wavelength of 248 nm, a wavelength 193 nm ArF excimer laser and the wavelength is getting shorter year by year. As a next-generation exposure light source, soft X-rays (EUV) having a wavelength of 13 nm or less have been proposed as a light source. Electron beam lithography is also used for semiconductor manufacturing because it does not require an expensive mask.

  Along with further advancement of microfabrication technology, there is a demand for better performance than conventional chemically amplified resist compositions, such as resolution, sensitivity, pattern shape, and better line edge roughness. In particular, as the pattern becomes finer in recent years, the level required for line edge roughness has become comparable to the size of resin molecules that are normally used. Is becoming the limit.

JP, 2006-58739, A Claim 7

  The object of the present invention is to provide a compound suitable for electron beam lithography or EUV lithography, particularly for producing a compound that gives a chemically amplified resist composition having good line edge roughness in addition to performance such as resolution and sensitivity. An object of the present invention is to provide an ester compound useful as an intermediate of an acid generator.

  As a result of intensive studies on the compound for the chemically amplified resist composition, the present inventors have found an ester compound that is useful as an intermediate of a photoacid generator for producing the compound.

  That is, the present invention provides the following.

1. An ester compound represented by the formula (I).

(In the formula (I), ^{Q 1} and ^{Q 2} each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
U represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
L represents a halogen atom, an alkylsulfonyloxy group having 1 to 12 carbon atoms, or an arylsulfonyloxy group having 6 to 12 carbon atoms. The carbon atom of the aryl group may be substituted with a hetero atom.
A ⁺ represents an organic counter ion. )

2. ^2. The ester compound according to 1 above, wherein Q ¹ and Q ² are each independently a fluorine atom or a trifluoromethyl group.

3. The ester compound according to 1 or 2 above, wherein Q ¹ and Q ² are fluorine atoms.

4). 4. The ester compound according to any one of 1 to 3 above, wherein A ⁺ is at least one cation selected from the group consisting of cations represented by any one of formulas (IIa) to (IId).

(In Formula (IIa), P ^{1 to} P ³ independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, and the alkyl group and the alkoxy group May be linear or branched.)

(In Formula (IIb), P ⁴ and P ⁵ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, and the alkyl group and the alkoxy group May be linear or branched.)

(In Formula (IIc), P ⁶ and P ⁷ each independently represent a C 1-12 alkyl group or a C 3-12 cycloalkyl group, or P ⁶ and P ⁷ are bonded to each other. , S ⁺ and a ring having 2 to 2 carbon atoms may be formed.
P ⁸ represents a hydrogen atom, and P ⁹ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an optionally substituted aromatic ring group, or P ⁸ and P ⁹ Represents a divalent hydrocarbon group having 3 to 12 carbon atoms. Here, any carbon atom contained in the divalent hydrocarbon group may be substituted with a carbonyl group, an oxygen atom, or a sulfur atom. )

(In Formula (IId), P ^{10 to} P ²¹ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
B represents a sulfur atom or an oxygen atom.
m represents 0 or 1. )

5. The ester compound according to any one of 1 to 4 above, wherein A ⁺ is a cation represented by the formula (IIe).

(In formula (IIe), P ^{22 to} P ²⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

6). An ester compound represented by the formula (III):

(In Formula (III), Q < ¹ > and Q < ² > represent a fluorine atom or a C1-C6 perfluoroalkyl group mutually independently.
U represents a C1-C20 bivalent hydrocarbon group.
L represents a halogen atom, an alkylsulfonyloxy group having 1 to 12 carbon atoms, or an arylsulfonyloxy group having 6 to 12 carbon atoms. The carbon atom of the aryl group may be substituted with a hetero atom.
M ⁺ represents Li ⁺ , Na ⁺ , K ⁺ or Ag ⁺ . )

7). 7. The ester compound according to 6 above, wherein Q ¹ and Q ² are each independently a fluorine atom or a trifluoromethyl group.

8). 8. The ester compound according to 6 or 7 above, wherein Q ¹ and Q ² are fluorine atoms.

9. A method for producing an ester compound represented by the formula (III), wherein the alcohol represented by the formula (IV) is esterified with the carboxylic acid represented by the formula (V).

(In Formula (IV) and Formula (III), U represents a C1-C20 bivalent hydrocarbon group.
L represents a halogen atom, an alkylsulfonyloxy group having 1 to 12 carbon atoms, or an arylsulfonyloxy group having 6 to 12 carbon atoms. The carbon atom of the aryl group may be substituted with a hetero atom.
In formula (V) and formula (III), Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
M ⁺ represents Li ⁺ , Na ⁺ , K ⁺ or Ag ⁺ . )

10. 10. The production method according to 9 above, wherein Q ¹ and Q ² are each independently a fluorine atom or a trifluoromethyl group.

11. 11. The production method according to 9 or 10 above, wherein Q ¹ and Q ² are fluorine atoms.

12 The alcohol represented by the formula (IV) and the carboxylic acid represented by the formula (VI) are esterified to obtain a sulfonyl fluoride derivative represented by the formula (IIIa), and the sulfonyl fluoride derivative is hydrolyzed. A method for producing an ester compound represented by the formula (III), which comprises decomposing.

(In formula (IV), formula (IIIa) and formula (III), U represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
L represents a halogen atom, an alkylsulfonyloxy group having 1 to 12 carbon atoms, or an arylsulfonyloxy group having 6 to 12 carbon atoms. The carbon atom of the aryl group may be substituted with a hetero atom.
In formula (VI), formula (IIIa) and formula (III), Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group. )

13. 13. The production method according to 12 above, wherein Q ¹ and Q ² are each independently a fluorine atom or a trifluoromethyl group.

14 14. The production method according to 12 or 13 above, wherein Q ¹ and Q ² are fluorine atoms.

  A method for producing an ester compound represented by formula (I), comprising reacting an ester compound represented by formula (III) with a compound represented by formula (VII).

(In Formula (III) and Formula (I), Q < ¹ > and Q < ² > represent a fluorine atom or a C1-C6 perfluoroalkyl group mutually independently.
U represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
L represents a halogen atom, an alkylsulfonyloxy group having 1 to 12 carbon atoms, or an arylsulfonyloxy group having 6 to 12 carbon atoms. The carbon atom of the aryl group may be substituted with a hetero atom.
M ⁺ represents Li ⁺ , Na ⁺ , K ⁺ or Ag ⁺ .
In formula (VII) and formula (I), A ⁺ represents an organic counter ion.
Z ⁻ represents F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , BF ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , PF ₆ ⁻ or ClO ₄ ⁻ . )

  The ester compound of the present invention is industrially useful as an intermediate for producing a photoacid-generating group-bonded polyhydric phenol derivative. For example, when the photoacid-generating group-bonded polyhydric phenol derivative is used as a chemically amplified positive resist composition, it is suitable for electron beam lithography or EUV lithography, and has resolution and sensitivity in microfabrication for semiconductor manufacturing. In addition to being excellent, the line edge roughness is good.

  The ester compound of the present invention is represented by the formula (I).

(In the formula (I), ^{Q 1} and ^{Q 2} each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
U represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
L represents a halogen atom, an alkylsulfonyloxy group having 1 to 12 carbon atoms, or an arylsulfonyloxy group having 6 to 12 carbon atoms. The carbon atom of the aryl group may be substituted with a hetero atom.
A ⁺ represents an organic counter ion. )

As the perfluoroalkyl group having 1 to 6 carbon atoms, a perfluoromethyl group, a perfluoroethyl group, a perfluoro-n-propyl group, a perfluoroisopropyl group, a perfluoro n-butyl group, a perfluoro-sec-butyl group, Examples include a perfluoro-tert-butyl group, a perfluoro-n-pentyl group, and a perfluoro-n-hexyl group.
Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include methylene group, dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, Undecylmethylene group, dodecylmethylene group, tridecylmethylene group, tetradecylmethylene group, pentadecylmethylene group, hexadecylmethylene group, heptadecylmethylene group, octadecylmethylene group, nonadecylmethylene group, isocosanylene group, propylene group, ethyl An ethylene group etc. are mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkylsulfonyloxy group having 1 to 12 carbon atoms include methylsulfonyloxy group, ethylsulfonyloxy group, n-propylsulfonyloxy group, isopropylsulfonyloxy group, n-butylsulfonyloxy group, sec-butylsulfonyloxy group, tert -Butylsulfonyloxy group, n-pentylsulfonyloxy group, n-hexylsulfonyloxy group, n-heptylsulfonyloxy group, n-octylsulfonyloxy group, n-nonylsulfonyloxy group, n-decylsulfonyloxy group, n- An undecylsulfonyloxy group, n-dodecylsulfonyloxy group, etc. are mentioned.
Examples of the C6-C12 arylsulfonyloxy group include a phenylsulfonyloxy group and a naphthylsulfonyloxy group.

A ⁺ in formula (I) represents an organic counter ion, and includes at least one cation selected from the group consisting of cations represented by any of formulas (IIa) to (IId).

(In formula (IIa), P ^{1 to} P ³ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.)

Examples of the alkyl 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, and 2-ethylhexyl group. Can be mentioned.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, an octyloxy group, and a 2-ethylhexyloxy group.

  Among the cations represented by the formula (IIa), the cation represented by the formula (IIe) is preferable because its production is easy.

(In formula (IIe), P ^{22 to} P ²⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

（式（ＩＩｂ）中、Ｐ^４及びＰ^５は、互いに独立に、水素原子、水酸基、炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシ基を表す。）

(In Formula (IIb), P ⁴ and P ⁵ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.)

  The alkyl group and the alkoxy group have the same meaning as the alkyl group and alkoxy group in the formula (IIa).

(In formula (IIc), P ⁶ and P ⁷ each independently represent a C 1-12 alkyl group or a C 3-12 cycloalkyl group.)

Specific examples of the alkyl group include the same alkyl groups in formula (IIa).
Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclodecyl group. Alternatively, P ⁶ and P ⁷ may be bonded to form a ring containing S ⁺ having 3 to 12 carbon atoms.
P ⁸ represents a hydrogen atom, and P ⁹ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an optionally substituted aromatic ring group, or P ⁸ and P ⁹ are A divalent hydrocarbon group having 3 to 12 carbon atoms such as an alkylene group is bonded.
Specific examples of the alkyl 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, 2-ethylhexyl. Groups and the like. When P ⁹ is a cycloalkyl group, examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclodecyl group. Here, any carbon atom contained in the divalent hydrocarbon group in formula (VIc) may be substituted with a carbonyl group, an oxygen atom, or a sulfur atom.
Examples of the aromatic ring group which may be substituted include a phenyl group and a benzyl group.

  Examples of the cation represented by the formula (IIa) include a cation represented by the following formula.

  Examples of the cation represented by the formula (IIb) include a cation represented by the following formula.

  Examples of the cation represented by the formula (IIc) include a cation represented by the following formula.

  Examples of the cation represented by the formula (IId) include a cation represented by the following formula.

  Among the above cations, an arylsulfonium cation is preferable, and a cation represented by the formula (IIe) is particularly preferable.

(In formula (IIe), P ^{22 to} P ²⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

  Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.

  Examples of the cation represented by the formula (IIe) include a cation represented by the following formula.

Specific examples of Q ¹ and Q ² include fluorine atom, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, perfluoropentyl group, and perfluorohexyl group. Among these, Q ¹ and Q ² are preferably each independently a fluorine atom or a trifluoromethyl group, and more preferably a fluorine atom at the same time.

U in the formula (I) is a divalent hydrocarbon group having 1 to 20 carbon atoms, and the methylene group in the hydrocarbon group is an oxygen atom, nitrogen atom, sulfur atom, alkylamino group, carbonyl group, carbonyl group It may be substituted with an oxy group.
Examples of the divalent hydrocarbon group include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecameric group. Methylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, hexadecamethylene group, heptacamethylene group, octadecamethylene group, nonacamethylene group, eicosamethylene group, ethylenecarbonylethyl Specific examples of the chemical structure are listed below, but the present invention is not limited thereto. A line having one end represents a bond.

  The ester compound represented by the formula (I) can be obtained by a cation exchange reaction between the ester compound represented by the formula (III) and the salt represented by the formula (VII).

(In Formula (III) and Formula (I), Q < ¹ > and Q < ² > represent a fluorine atom or a C1-C6 perfluoroalkyl group mutually independently.
U represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
L represents a halogen atom, an alkylsulfonyloxy group having 1 to 12 carbon atoms, or an arylsulfonyloxy group having 6 to 12 carbon atoms. The carbon atom of the aryl group may be substituted with a hetero atom.
M ⁺ represents Li ⁺ , Na ⁺ , K ⁺ or Ag ⁺ .
In formula (VII) and formula (I), A ⁺ represents an organic counter ion.
Z ⁻ represents F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , BF ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , PF ₆ ⁻ or ClO ₄ ⁻ . )

  The cation exchange reaction may be, for example, chloroform, methylene chloride, ethylene dichloride, monochlorobenzene, acetone, methyl ethyl ketone, toluene, xylene, anisole, tetrahydrofuran, methanol, ethanol, isopropanol, dimethylformamide, dimethyl sulfoxide, or an organic solvent or water, or The reaction is carried out in a mixed solvent thereof, and the reaction temperature is -30 to 200 ° C, preferably -10 to 100 ° C.

  The amount of the salt represented by the formula (VII) is 0.5 to 5 times, preferably 1 to 2 times the amount of 1 mol of the ester compound represented by the formula (III). .

  The obtained ester compound can be taken out by ordinary post-treatment. This ester compound can also be purified by chromatography, recrystallization or distillation.

  The ester compound represented by the formula (III) can be obtained by reacting the alcohol derivative represented by the formula (IV) with the carboxylic acid derivative represented by the formula (V) in the presence of an acid catalyst. .

(In Formula (IV) and Formula (III), U represents a C1-C20 bivalent hydrocarbon group.
L represents a halogen atom, an alkylsulfonyloxy group having 1 to 12 carbon atoms, or an arylsulfonyloxy group having 6 to 12 carbon atoms. The carbon atom of the aryl group may be substituted with a hetero atom.
In formula (V) and formula (III), Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
M ⁺ represents Li ⁺ , Na ⁺ , K ⁺ or Ag ⁺ . )

  The dehydration esterification reaction of the alcohol derivative represented by the formula (IV) and the carboxylic acid derivative represented by the formula (V) is, for example, chloroform, methylene chloride, ethylene dichloride, monochlorobenzene, toluene, xylene, anisole, The reaction is carried out in an inert solvent such as dimethylformamide and dimethyl sulfoxide, and the reaction temperature is -30 to 200 ° C, preferably the boiling point to 150 ° C of the solvent used. The reaction is preferably carried out by adding an acid catalyst base, for example, organic acids such as trifluorosulfonic acid, toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, or inorganic acids such as concentrated sulfuric acid, hydrochloric acid, hydrogen chloride, Alternatively, a mixture of these is used.

The used amount of the carboxylic acid derivative represented by the formula (V) is 0.5 to 5 times, preferably 0.8 to 2 times the amount of 1 mol of the alcohol derivative represented by the formula (IV). The amount of the acid catalyst used is 0.001 to 3 times, preferably 0.01 to 1 times.
It is also possible to add a strongly acidic sulfonic acid resin such as Nafion to the reaction.

  The resulting condensate can be removed by ordinary post-treatment. This condensate can also be purified by chromatography, recrystallization or distillation.

  The dehydration esterification reaction between the alcohol derivative represented by the formula (IV) and the carboxylic acid derivative represented by the formula (V) is, for example, chloroform, methylene chloride, ethylene dichloride, monochlorobenzene, acetone, methyl ethyl ketone, toluene, It is also possible to use a dehydrating agent in an inert solvent such as xylene, anisole, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide. The reaction temperature is -30 to 200 ° C, preferably -20 to 150 ° C. Examples of the dehydrating agent include dicyclohexylcarbodiimide (DCC), 1-alkyl-2-halopyridinium salt, 1,1-carbonyldiimidazole, bis (2-oxo-3-oxazolidinyl) phosphine acid chloride, 1-ethyl- 3- (3-dimethylaminopropyl) carbodiimide hydrochloride, di-2-pyridyl carbonate, di-2-pyridylthiono carbonate, 6-methyl-2-nitrobenzoic anhydride / 4- (dimethylamino) pyridine (catalyst ).

  The used amount of the carboxylic acid derivative represented by the formula (V) is 0.5 to 5 times, preferably 0.8 to 2 times the amount of 1 mol of the alcohol derivative represented by the formula (IV). The amount of the dehydrating agent used is 1 to 3 times the molar amount, preferably 1 to 2 times the molar amount. The resulting condensate can be removed by ordinary post-treatment. This condensate can also be purified by chromatography, recrystallization or distillation.

  By carrying out esterification reaction of the alcohol represented by the formula (IV) and the carboxylic acid represented by the formula (VI), the fluorosulfonyl compound represented by the formula (IIIa) is also an acid-catalyzed ester as described above. It can be carried out by an esterification reaction or an esterification reaction with a dehydrating agent.

(In formula (IV) and formula (IIIa), U represents a C1-C20 divalent hydrocarbon group.
L represents a halogen atom, an alkylsulfonyloxy group having 1 to 12 carbon atoms, or an arylsulfonyloxy group having 6 to 12 carbon atoms. The carbon atom of the aryl group may be substituted with a hetero atom.
In formula (VI) and formula (IIIa), Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group. )

  A salt represented by the formula (III) can be produced by hydrolyzing the obtained fluorosulfonyl compound (IIIa). The hydrolysis reaction is performed using a base, for example, in an inert solvent such as chloroform, methylene chloride, ethylene dichloride, monochlorobenzene, acetone, methyl ethyl ketone, toluene, xylene, anisole, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, The reaction temperature is -30 to 200 ° C, preferably -10 to 150 ° C. Examples of the base used include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and the like. In order to obtain a silver salt, for example, there is a method in which a sodium salt is used and then cation exchange is performed with silver nitrate. As a quantity of a base, it is 1-5 times mole amount with respect to 1 mol of fluorosulfonic acids, Preferably, it is 1-2 times mole amount.

  EXAMPLES Next, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples. In the examples, “%” and “part” representing the content or amount used are based on weight unless otherwise specified.

Example 1
Synthesis of triphenylsulfonium 12-bromo-1-dodecyloxycarbonyldifluoromethanesulfonate (compound (A))

  Sodium salt (21 g) of difluorosulfoacetic acid (RN = 422-67-3) and 12-bromo-1-dodecanol (25 g) were added to toluene (300 g), and a catalytic amount of p-toluenesulfonic acid was added. The mixture was cooled by reflux dehydration reaction for 13 hours. The precipitated crystals were filtered, washed with a small amount of toluene, and then dried to obtain 12-bromo-1-dodecyloxycarbonyldifluoromethanesulfonic acid / sodium salt (34.1 g; yield 81.2%). .

¹ H-NMR (CDCl ₃ ; internal standard substance tetramethylsilane): δ (ppm) 4.33 (t, 2H, J = 6.9 Hz); 3.40 (t, 2H, J = 6.9 Hz); 1.85 (m, 2H); 1.78-1.10 (m, 18H)
MS (ESI (−) Spectrum): M-421 (C ₁₄ H ₂₄ BrF ₂ O ₅ S ⁻ = 421.05)

  Then, 12-bromo-1-dodecyloxycarbonyldifluoromethanesulfonic acid / sodium salt (34.1 g) was dissolved in chloroform (200 g). An aqueous solution of triphenylsulfonium chloride (192 g; 13.1%) was added and stirred overnight at room temperature. The organic layer was washed with ion-exchanged water and concentrated to obtain triphenylsulfonium · 12-bromo-1-dodecyloxycarbonyldifluoromethanesulfonate (compound (A): 48.7 g; yield 92.7%). .

¹ H-NMR (DMSO-d ₆ ; internal standard substance tetramethylsilane): δ (ppm) 7.87 to 7.76 (m, 15H); 4.17 (t, 2H, J = 6.9 Hz); 3.50 (t, 2H, J = 6.9 Hz); 1.75 (m, 2H); 1.57 (m, 2H); 1.37 to 1.23 (m, 16H)
¹⁹ F-NMR (DMSO-d ₆ , internal standard substance fluorobenzene): δ (ppm) −105.19
MS (ESI (−) Spectrum): M-421 (C ₁₄ H ₂₄ BrF ₂ O ₅ S ⁻ = 421.05)
MS (ESI (+) Spectrum): M + 263 (C ₁₈ H ₁₅ S ⁺ = 263.09)

Example 2
Synthesis of triphenylsulfonium 6-bromo-1-hexyloxycarbonyldifluoromethanesulfonate (compound (B))

  Sodium salt (10 g) of difluorosulfoacetic acid (RN = 422-67-3) and 6-bromo-1-hexanol (10.8 g) were added to toluene (50 g), and a catalytic amount of trifluoromethanesulfonic acid was added. The mixture was cooled by performing a reflux dehydration reaction for 9 hours. The precipitated crystals were filtered, washed with a small amount of toluene, and then dried to obtain 6-bromo-1-hexyloxycarbonyldifluoromethanesulfonic acid / sodium salt (12.3 g; yield 72.0%). .

¹ H-NMR (CDCl ₃ ; internal standard substance tetramethylsilane): δ (ppm) 4.35 (2H); 3.42 (t, 2H, J = 6.9 Hz); 1.86 (m, 2H) 1.73 (m, 2H); 1.47 (m, 2H); 1.40 (m, 2H)
MS (ESI (−) Spectrum): M-337 (C ₈ H ₁₂ BrF ₂ O ₅ S ⁻ = 336.96)

  Subsequently, 6-bromo-1-hexyloxycarbonyldifluoromethanesulfonic acid / sodium salt (12.1 g) was dissolved in chloroform (200 g). An aqueous solution of triphenylsulfonium chloride (84.1 g; 13.1%) was added and stirred overnight at room temperature. The organic layer was washed with ion-exchanged water and concentrated to obtain triphenylsulfonium 6-bromo-1-hexyloxycarbonyldifluoromethanesulfonate (compound (B): 17.2 g; yield 85.3%). .

¹ H-NMR (DMSO-d ₆ ; internal standard substance tetramethylsilane): δ (ppm) 7.77 to 7.68 (m, 15H); 4.25 (t, 2H, J = 6.9 Hz); 3.37 (t, 2H, J = 6.9 Hz); 1.81 (m, 2H); 1.70 (m, 2H); 1.45 to 1.36 (m, 4H)
¹⁹ F-NMR (DMSO-d ₆ ; internal standard substance fluorobenzene): δ (ppm) −106.42
MS (ESI (−) Spectrum): M-337 (C ₈ H ₁₂ BrF ₂ O ₅ S ⁻ = 336.96)
MS (ESI (+) Spectrum): M + 263 (C ₁₈ H ₁₅ S ⁺ = 263.09)

Example 3
Synthesis of triphenylsulfonium 2- [2- (2-chloroethoxy) ethoxy] ethyloxycarbonyldifluoromethanesulfonate (compound (C))

  A sodium salt of difluorosulfoacetic acid (RN = 422-67-3) (10 g) and 2- [2- (2-chloroethoxy) ethoxy] ethanol (7.5 g) were added to toluene (50 g) to obtain trifluoromethanesulfone. A catalytic amount of acid was added. The mixture was cooled by refluxing dehydration reaction for 10 hours. The reaction solution was concentrated to obtain 2- [2- (2-chloroethoxy) ethoxy] ethyloxycarbonyldifluoromethanesulfonic acid / sodium salt (17.8 g; yield quantitative).

¹ H-NMR (CDCl ₃ ; internal standard substance tetramethylsilane): δ (ppm) 3.88 to 3.63 (12H)
MS (ESI (−) Spectrum): M-325 (C ₈ H ₁₂ ClF ₂ O ₇ S ⁻ = 325.00)

  2- [2- (2-Chloroethoxy) ethoxy] ethyloxycarbonyldifluoromethanesulfonic acid / sodium salt (17.8 g) was dissolved in chloroform (200 g). An aqueous solution of triphenylsulfonium chloride (128.1 g; 13.1%) was added and stirred overnight at room temperature. The organic layer was washed with ion-exchanged water, concentrated, and triphenylsulfonium 2- [2- (2-chloroethoxy) ethoxy] ethyloxycarbonyldifluoromethanesulfonate (compound (C): 18.0 g; yield 59). 0.9%).

¹ H-NMR (DMSO-d ₆ ; internal standard substance tetramethylsilane): δ (ppm) 7.78 to 7.65 (m, 15H); 3.79 to 3.57 (12H)
¹⁹ F-NMR (DMSOd ₆ , internal standard substance fluorobenzene): δ (ppm) −106.50
MS (ESI (−) Spectrum): M-325 (C ₈ H ₁₂ ClF ₂ O ₇ S ⁻ = 325.00)
MS (ESI (+) Spectrum): M + 263 (C ₁₈ H ₁₅ S ⁺ = 263.09)

Example 4
Synthesis of tri (4-tert-butylphenyl) sulfonium · 12-bromo-1-dodecyloxycarbonyldifluoromethanesulfonate (compound (D))

  12-Bromo-1-dodecyloxycarbonyldifluoromethanesulfonic acid / sodium salt (20.0 g) was dissolved in chloroform (120 g). An aqueous solution of tri (4-tert-butylphenyl) sulfonium chloride (210 g; 10%) was added and stirred overnight at room temperature. The organic layer was washed with ion-exchanged water and concentrated to obtain tri (4-tert-butylphenyl) sulfonium · 12-bromo-1-dodecyloxycarbonyldifluoromethanesulfonate (compound (D): 33.4 g; yield 87). 0.1%).

¹ H-NMR (CDCl ₃ -d ₁ ; internal standard substance tetramethylsilane): δ (ppm) 7.71 to 7.67 (m, 12H); 4.26 (t, 2H, J = 6.9 Hz) 3.41 (t, 2H, J = 6.9 Hz); 1.86 (m, 2H); 1.70 (m, 2H); 1.46 to 1.21 (m, 16H); 1.33 (S, 27H)
¹⁹ F-NMR (DMSO-d ₆ , internal standard substance fluorobenzene): δ (ppm) −106.03
_{^{MS (ESI (-) Spectrum)}} : M - 422,423 (C 14 H 24 BrF 2 O 5 S 2- = 421.05)
_{^{MS (ESI (+) Spectrum)}} : M + 431 (C 30 H 39 S - = 431.28)

Example 5
Synthesis of tetrahydro-1- (2-oxo-2-phenylethyl) thiophenium · 12-oxy-1-dodecyloxycarbonyldifluoromethanesulfonate (compound (E))

  12-Bromo-1-dodecyloxycarbonyldifluoromethanesulfonic acid / sodium salt (15.0 g) was dissolved in chloroform (100 g). Tetrahydro-1- (2-oxo-2-phenylethyl) thiophenium bromide (9.7 g) was added and stirred overnight at room temperature. Ion exchange water (20 g) was added to the reaction solution, and the organic layer was separated. The organic layer was washed with ion-exchanged water, concentrated, and tetrahydro-1- (2-oxo-2-phenylethyl) thiophenium · 12-oxy-1-dodecyloxycarbonyldifluoromethanesulfonate (compound (E)): 12 0.4 g; yield 58.5%).

¹ H-NMR (CDCl 3 -d ₁ ; internal standard substance tetramethylsilane): δ (ppm) 7.9 (d, 2H, J = 6.9 Hz); 7.60 (t, 1H, J = 7.7 Hz) 7.45 (t, 2H, J = 8.4 Hz); 5.35 (s, 2H); 4.11 (t, 2H, J = 6.9 Hz); 2.48 to 2.43 (m) 4H); 2.30-2.26 (m, 4H); 1.86 (m, 2H); 1.60 (m, 2H); 1.42 (m, 2H); 1.28-1. 24 (m, 14H)
¹⁹ F-NMR (DMSO-d ₆ , internal standard substance fluorobenzene): δ (ppm) −106.39
_{^{MS (ESI (-) Spectrum)}} : M - 422,423 (C 14 H 24 BrF 2 O 5 S 2- = 421.05)
^{MS (ESI (+) Spectrum)} : M + 207 (C 12 H 15 OS + = 207.08)

Synthesis example of photoacid generator-binding molecular resist using the compound of the present invention 2,6-bis [4-hydroxy-3- {2- (2-methyl-2-adamantyloxycarbonylmethoxy) -5-methylbenzyl} -2,5-Dimethylbenzyl] -4-methyl-1- (triphenylsulfonium 12-oxy-1-dodecyloxycarbonyldifluoromethanesulfonate) benzene

  Mainly composed of 2,6-bis [4-hydroxy-3- {2- (2-methyl-2-adamantyloxycarbonylmethoxy) -5-methylbenzyl} -2,5-dimethylbenzyl] -4-methylphenol Mixture (compound 1: 7.5 g) and triphenylsulfonium 12-bromo-1-dodecyloxycarbonyldifluoromethanesulfonate (compound A: 5.0 g; 1 equivalent) and potassium carbonate (1.5 g; 1.5 Eq) was refluxed in acetone (60 g) for 4 h. After cooling, the mixture was neutralized with 2% oxalic acid and diluted with ethyl acetate. The organic layer was washed with ion exchanged water and concentrated to 2,6-bis [4-hydroxy-3- {2- (2-methyl-2-adamantyloxycarbonylmethoxy) -5-methylbenzyl} -2, 5-Dimethylbenzyl] -4-methyl-1- (triphenylsulfonium · 12-oxy-1-dodecyloxycarbonyldifluoromethanesulfonate) benzene (compound (P-1): 8.9 g; yield 75.2% )

MS (ESI (-) Spectrum) : M- 1369 (C 81 H 103 F 2 O 14 S - = 1369.70)
MS (ESI (+) Spectrum): M + 263 (C ₁₈ H ₁₅ S ⁺ = 263.09)

Reference Example A resist composition was prepared with the following composition.

P-1 / mixture 1/5 nucleus = 3 parts / 5 parts / 2 parts Qa / Qb = 0.2 parts / 0.05 parts Solvent = 320 parts

Compound 1

2,6-bis [4-hydroxy-3- {2- (2-methyl-2-hydroxy) -5-methylbenzyl} -2,5-dimethylbenzyl] -4-methylphenol (pentanuclear body; 10 g) Was dissolved in N, N-dimethylformamide (DMF; 100 g), and potassium carbonate (6.8 g; 3 moles) was added and stirred. A DMF (40 g) solution of chloroacetic acid · 2-methyl-2-adamantyl (7.9 g; 2 moles) was added dropwise at 50 ° C. or lower. To the reaction solution was added potassium iodide (0.6 g; 0.2-fold mol), and the mixture was further stirred at 50 ° C. for 5 hours. After cooling, the mixture was diluted with 1% oxalic acid aqueous solution and extracted with ethyl acetate. The organic layer was washed with water, dried and decolorized (magnesium sulfate / activated carbon), and concentrated to give a brown solid (mixture 1: 15.3 g).
The mixture 1 is a compound represented by the formula (F), wherein one of Y ^{1 to} Y ⁵ is a group represented by the formula (L) and four are hydrogen atoms (F1), Y ¹ To Y ⁵ , two are groups represented by the formula (L), three are hydrogen atoms (F2), and Y ^{1 to} Y ⁵ , three are groups represented by the formula (L) And a mixture of compounds (F3) in which two are hydrogen atoms.

LC-MS analysis: (F1) [M + K] ⁺ = 861.4 (M ⁺ = 822.45)
(F2) [M + K] ⁺ = 1067.4 (M ⁺ = 1028.58)
(F3) [M + K] ⁺ = 1273.6 (M ⁺ = 1234.71)

  The mixture 1 was analyzed by liquid chromatography. The result was (F1) :( F2) :( F3) = 6: 92: 2.

Pentanuclear

Qa; 2,6-diisopropylaniline Qb; tetrabutylammonium hydroxide solvent; propylene glycol monomethyl ether acetate

The silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 110 ° C. for 60 seconds, and then the above resist solution was spin-coated so that the film thickness after drying was 0.10 μm. After applying the resist solution, pre-baking was performed at 110 ° C. for 60 seconds on a direct hot plate. Each wafer on which the resist film was thus formed was exposed to a line-and-space pattern using an electron beam drawing machine [HL-800D; manufactured by Hitachi, Ltd .; 50 KeV] while changing the exposure stepwise.
After exposure, post-exposure baking was performed on a hot plate at 100 ° C. for 60 seconds, and paddle development was further performed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds.
When the developed pattern on a silicon substrate was observed with a scanning electron microscope, the effective sensitivity was 18 μC, the resolution was 70 nm, and the line edge roughness was good.

  The photoacid generator intermediate of the present invention is suitable for the production of a photoacid generator-bonded resist material, and the resist obtained thereby can provide a high-performance resist pattern, and is a useful intermediate. is there.

Claims (15)

An ester compound represented by the formula (I).

(In the formula (I), ^{Q 1} and ^{Q 2} each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
U represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
L represents a halogen atom, an alkylsulfonyloxy group having 1 to 12 carbon atoms, or an arylsulfonyloxy group having 6 to 12 carbon atoms. The carbon atom of the aryl group may be substituted with a hetero atom.
A ⁺ represents an organic counter ion. ) The ester compound according to claim ^1, wherein Q ¹ and Q ² are each independently a fluorine atom or a trifluoromethyl group. The ester compound according to claim 1 or 2, wherein Q ¹ and Q ² are fluorine atoms. The ester compound according to any one of claims 1 to 3, wherein A ⁺ is at least one cation selected from the group consisting of cations represented by any one of formulas (IIa) to (IId).

(In Formula (IIa), P ^{1 to} P ³ independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, and the alkyl group and the alkoxy group May be linear or branched.)

(In Formula (IIb), P ⁴ and P ⁵ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, and the alkyl group and the alkoxy group May be linear or branched.)

(In Formula (IIc), P ⁶ and P ⁷ each independently represent a C 1-12 alkyl group or a C 3-12 cycloalkyl group, or P ⁶ and P ⁷ are bonded to each other. , S ⁺ and a ring having 2 to 2 carbon atoms may be formed.
P ⁸ represents a hydrogen atom, and P ⁹ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an optionally substituted aromatic ring group, or P ⁸ and P ⁹ Represents a divalent hydrocarbon group having 3 to 12 carbon atoms. Here, any carbon atom contained in the divalent hydrocarbon group may be substituted with a carbonyl group, an oxygen atom, or a sulfur atom. )

(In Formula (IId), P ^{10 to} P ²¹ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
B represents a sulfur atom or an oxygen atom.
m represents 0 or 1. ) The ester compound according to any one of claims 1 to 4, wherein A ⁺ is a cation represented by the formula (IIe).

(In formula (IIe), P ^{22 to} P ²⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) An ester compound represented by the formula (III):

(In Formula (III), Q < ¹ > and Q < ² > represent a fluorine atom or a C1-C6 perfluoroalkyl group mutually independently.
U represents a C1-C20 bivalent hydrocarbon group.
L represents a halogen atom, an alkylsulfonyloxy group having 1 to 12 carbon atoms, or an arylsulfonyloxy group having 6 to 12 carbon atoms. The carbon atom of the aryl group may be substituted with a hetero atom.
M ⁺ represents Li ⁺ , Na ⁺ , K ⁺ or Ag ⁺ . ) The ester compound according to claim 6, wherein Q ¹ and Q ² are each independently a fluorine atom or a trifluoromethyl group. The ester compound according to claim 6 or 7, wherein Q ¹ and Q ² are fluorine atoms. A method for producing an ester compound represented by the formula (III), wherein the alcohol represented by the formula (IV) is esterified with the carboxylic acid represented by the formula (V).

(In Formula (IV) and Formula (III), U represents a C1-C20 bivalent hydrocarbon group.
L represents a halogen atom, an alkylsulfonyloxy group having 1 to 12 carbon atoms, or an arylsulfonyloxy group having 6 to 12 carbon atoms. The carbon atom of the aryl group may be substituted with a hetero atom.
In formula (V) and formula (III), Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
M ⁺ represents Li ⁺ , Na ⁺ , K ⁺ or Ag ⁺ . ) The production method according to claim 9, wherein Q ¹ and Q ² are each independently a fluorine atom or a trifluoromethyl group. Q ¹ and ^{Q 2} The production method of claim 9 or 10, wherein a fluorine atom. The alcohol represented by the formula (IV) and the carboxylic acid represented by the formula (VI) are esterified to obtain a sulfonyl fluoride derivative represented by the formula (IIIa), and the sulfonyl fluoride derivative is hydrolyzed. A method for producing an ester compound represented by the formula (III), which comprises decomposing.

(In formula (IV), formula (IIIa), and formula (III), U represents a C1-C20 bivalent hydrocarbon group.
L represents a halogen atom, an alkylsulfonyloxy group having 1 to 12 carbon atoms, or an arylsulfonyloxy group having 6 to 12 carbon atoms. The carbon atom of the aryl group may be substituted with a hetero atom.
In formula (VI), formula (IIIa) and formula (III), Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group. ) The production method according to claim 12, wherein Q ¹ and Q ² are each independently a fluorine atom or a trifluoromethyl group. Q ¹ and ^{Q 2} is The process of claim 12 or 13, wherein a fluorine atom. A method for producing an ester compound represented by formula (I), comprising reacting an ester compound represented by formula (III) with a compound represented by formula (VII).

(In Formula (III) and Formula (I), Q < ¹ > and Q < ² > represent a fluorine atom or a C1-C6 perfluoroalkyl group mutually independently.
U represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
L represents a halogen atom, an alkylsulfonyloxy group having 1 to 12 carbon atoms, or an arylsulfonyloxy group having 6 to 12 carbon atoms. The carbon atom of the aryl group may be substituted with a hetero atom.
M ⁺ represents Li ⁺ , Na ⁺ , K ⁺ or Ag ⁺ .
In the formula (VII) and the formula (I), A ⁺ represents an organic counter ion.
Z ⁻ represents F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , BF ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , PF ₆ ⁻ or ClO ₄ ⁻ . )