JP2003327572A - New sulfonic acid derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photo acid generator which has excellent solubility in resist solvents and excellent compatibility with resins and is used for resist materials not producing foreign matters when forming a pattern after developed and when peeling a resist, scarcely causing adverse effects such as edge roughness and the like, giving an excellent pattern shape, and having excellent PED stability, and to provide a light-emitting acid. <P>SOLUTION: This sulfonic acid derivative represented by the general formula (1) [R is a 1 to 20C linear, branched or cyclic alkyl, a substituted or non- substituted arylalkyl; Rf is a 1 to 20C linear, branched or cyclic perfluoroalkyl; M<SP>m+</SP>is a counter ion; (m) is an integer]. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a sulfonic acid derivative which exhibits strong acidity and is useful as a photoacid generator used in semiconductor manufacturing processes. Here, the sulfonic acid derivative means sulfonic acid and salts thereof.

[0002]

2. Description of the Related Art In the field of microfabrication represented by a semiconductor manufacturing process, miniaturization of processing in a photolithography process is required in order to obtain higher integration.

In recent years, the exposure apparatus used for photolithography to form an ultrafine pattern has been shortened in wavelength to a KrF excimer laser (wavelength 24).
8 nm), ArF excimer laser (wavelength 193n
m), deep ultraviolet rays such as F2 excimer laser, electron beam and X-ray have been put to practical use or studied.

As a resist suitable for such an exposure wavelength, US Pat. No. 4,491,628 and European Patent 24
"Chemically amplified resist materials" described in JP-A-9,139, etc. are receiving attention. This resist material contains a radiation-sensitive acid generator (hereinafter, referred to as “photo-acid generator”) that forms an acid by irradiation with radiation (hereinafter, referred to as “exposure”) and catalyzes the acid generated by exposure. The pattern forming material changes the solubility of the exposed portion and the non-exposed portion with respect to the developing solution, thereby forming a pattern.

This chemically amplified resist material is classified into a positive type and a negative type. As the positive type, a system composed of a resin having a group having a group which becomes alkaline-soluble upon decomposition with an acid and a photo-acid generator is known. Furthermore, if necessary, a dissolution inhibiting / dissolution promoting compound in which an acid labile group is introduced into a hydroxyl group such as a carboxylic acid or a phenol derivative, a carboxylic acid compound for improving dissolution characteristics, PED (from exposure to heat treatment after exposure) Retention time: Post Exposure Time Del
ay) Basic compounds for improving stability and contrast,
A surfactant or the like is added to improve coatability.

Further, as the negative type, a system comprising an alkali-soluble resin and a crosslinking agent having a function of crosslinking the alkali-soluble resin with an acid is known.

Photoacid generators used in such chemically amplified resists include onium sulfonates such as iodonium sulfonate and sulfonium sulfonate, sulfonate esters, N-imide sulfonate, N-oxime sulfonate, o-nitrobenzyl sulfonate, and pyrogallol. Tris methanesulfonate and the like are known.

However, with further miniaturization, even if these photo-acid generators derived from existing sulfonic acids are used, the resolution is low, the stability to the environment is low, and when developing with an alkali developing solution. There is a problem such as foreign matter.

As the acid generated from this photo-acid generator upon exposure, alkanesulfonic acid, arylsulfonic acid, partially or completely fluorinated arylsulfonic acid, alkanesulfonic acid and the like are used.

Since the photoacid generator which generates an alkanesulfonic acid has a weak acid strength, a protective group which is easily deprotected is introduced into the resin used for the chemically amplified resist material to study the miniaturization. In order to use a protective group that is easily deprotected, sulfonic acid having a large molecule and low diffusibility such as camphorsulfonic acid has been used as an effective sulfonic acid. However, the use of a sulfonic acid having a low diffusivity requires a large amount of generated acid, resulting in a large amount of exposure and a decrease in productivity.

It has been reported that a large number of acid generators that generate aryl sulfonic acids are effective because the adjustment of the strength of the generated acid and the size of the molecule can be studied relatively easily. Has been done. However, KrF,
In exposure at shorter wavelengths such as ArF, strong absorption of the aryl group exists, so that the transmittance of the resist film at the exposure wavelength is low and a sufficient depth of focus cannot be obtained, or the light absorption of the photo-acid generator is insufficient. There is a problem that the quantum yield of the photodegradable group is lowered and the sensitivity is lowered, if not sufficiently performed.

Acid generators which generate completely fluorinated alkane sulfonic acids have sufficient acid strength for the deprotection reaction of protective groups that are difficult to deprotect, and most of them have been put to practical use. However, when the acid strength is too strong, an unexpected reaction occurs in the elimination reaction of the protective group that converts the dissolution contrast of the resin, and there is a problem that foreign substances are generated after alkali development or when the resist is peeled off. Therefore, it has been reported that the problem was solved by using a known sulfonic acid having a medium acid strength in which the alkyl group of the alkanesulfonic acid was partially replaced with a fluorine atom, a nitro group or the like which is an electron-withdrawing group (Japanese Patent Laid-Open No. Hei 10 (1999) -135242). 10-7
650). However, it has been reported that, with a compound that generates a sulfonic acid having three or more fluorine atoms, a foreign substance is generated after alkali development or when the resist is peeled off, and a satisfactory result is not obtained (Japanese Patent Laid-Open No. 2001-2001). 172251).

Further, it is known to use a photo-acid generator in which two or more kinds of acids are combined in order to improve resolution, eliminate edge roughness and roughen the film surface (Japanese Patent Laid-Open No. 11-72921).
Issue). In this publication, a sulfonic acid having three or more fluorine atoms and a sulfonic acid containing no fluorine atom are used in combination. However, the problem of foreign matter has not been solved.

[0014]

As described above, satisfactory results corresponding to further miniaturization have not been obtained with the above-mentioned existing acid generators that generate sulfonic acid.

In view of such circumstances, the present invention is a photo-acid generator excellent in solubility in a resist solvent and compatibility with a resin, and produces a foreign substance during pattern formation after development and during resist stripping. Therefore, it is an object of the present invention to provide a photo-acid generator and a photo-acid which are used in a resist material which are less affected by edge roughness, have an excellent pattern shape, and have excellent PED stability.

[0016]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that the photoacid generator has excellent solubility in a resist solvent and compatibility with a resin.
It is represented by the following general formula (1), which is used for a resist material that does not generate foreign matter during pattern formation after development and resist stripping, is less affected by edge roughness, has an excellent pattern shape, and has excellent PED stability. We have found a photo-acid generator that generates a new acid with strong acidity.

That is, by introducing the perfluoroalkyl group, the problems of the solubility of the photoacid generator in the resist solvent and the compatibility with the resin were solved. Furthermore, by introducing an electron-donating alkyl or arylalkyl group (hereinafter referred to as "alkyl groups") into the α carbon atom of methanesulfonic acid substituted with a perfluoroalkyl group, it is possible to weaken the acid strength. Thus, the problem that foreign matters are generated during pattern formation after development and during resist stripping despite the substitution of perfluoroalkyl groups was solved. In addition, the problem of edge roughness was solved by the presence of an alkyl chain (chain of alkyl groups) and a perfluoroalkyl chain in the molecule. By finding these effects, it was found that the present compound is an acid effective in the field of chemically amplified resist, and the present invention has been completed.

Alkyl groups and perfluoroalkyl groups are introduced at the α-carbon atom of methanesulfonic acid, and these two groups are sterically crowded to reduce the degree of freedom of the perfluoroalkyl chain. It can be used as

As shown in the following general formula (2), a hybrid surfactant having an alkyl chain and a perfluoroalkyl chain and having two effects of reducing surface tension and interfacial tension is already known. Ori (J. Phys.
Chem., 96, 6738 (1992), J. Phys. Chem., 96, 10068
(1992)), its effect as a surfactant has been recognized, but the compound represented by the general formula (1) of the present invention is not a sulfuric acid ester type represented by the formula (2) but a sulfonic acid type. Therefore, a sufficient surfactant effect can be expected as compared with the surfactant of formula (2).

[0020]

[Chemical 2]

The present invention provides a sulfonic acid derivative represented by the following general formula (1).

[0022]

[Chemical 3]

(In the formula, R represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylalkyl group. Rf represents 1 to 10 carbon atoms.
20 represents a linear, branched or cyclic perfluoroalkyl group. M ^{m +} is a counter cation, and m is an integer. )

The sulfonic acid derivative of the formula (1) of the present invention may be optically active or inactive.

In this formula, R represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted arylalkyl group.

Specific examples of R include linear alkyl groups such as methyl group, ethyl group, n-propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group, i
Examples thereof include branched alkyl groups such as so-propyl group, cycloalkyl groups such as cyclohexyl group, cyclohexylmethyl group and cyclohexylethyl group, and arylalkyl groups such as benzyl group, phenylethyl group, phenylbutyl group and tolylmethyl group. The alkyl portion of the arylalkyl group may be linear, branched or cyclic.

Further, the aryl group of the arylalkyl group may have a substituent at an appropriate position. As the substituent, an alkyl group having 1 to 13 carbon atoms (eg, methyl group, ethyl group, propyl group, Butyl group, hexyl group, etc.), alkoxy group having 1 to 13 carbon atoms (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), acyloxy group having 2 to 13 carbon atoms (eg, acetyloxy group, benzoyloxy group, etc.) ), An aralkyl group having 7 to 13 carbon atoms (eg, benzyl group, diphenylmethyl group, phenylpropyl group, etc.), nitro group, cyano group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom). You can Two or more kinds of these substituents may be present.

Rf is a straight chain having 1 to 20 carbon atoms,
It is a branched or cyclic perfluoroalkyl group.
Rf is a linear perfluoro group such as a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group or a perfluorooctyl group. A branched perfluoroalkyl group such as an alkyl group, a perfluoroisopropyl group, a perfluoroisobutyl group, a perfluoro-t-butyl group and a perfluoroisopentyl group, and a cyclic perfluoroalkyl group such as a perfluorocyclohexyl group are preferably used. To be

Counter cation M which forms a salt with sulfonic acid
Specific examples of ^{m +} include hydrogen ions, metal ions, and onium ions.

More specific metal ions include lithium ions, sodium ions, potassium ions and the like.
Monovalent cation due to group element, magnesium ion (I
I), divalent cations of Group 2 elements such as calcium ion (II), iron ion (II), iron ion (III), copper ion
(I), copper ions (II), nickel ions (II), transition metal ions such as nickel ions (III), heavy metal ions such as lead ions (II), and these metal ions form ligands and complexes. It may be formed.

Examples of the onium ion include onium salts composed of nitrogen atom, sulfur atom, halogen atom, phosphorus atom and the like. Ammonium ion, methylammonium ion, dimethylammonium ion,
Trimethylammonium ion, tetramethylammonium ion, phenylammonium ion, diphenylammonium ion, triphenylammonium ion, dimethylphenylammonium ion, trimethylphenylammonium ion, pyridinium ion, alkylpyridinium ion, fluoropyridinium ion, chloropyridinium ion, bromopyridinium ion , An onium salt composed of nitrogen atoms such as tetramethylammonium ion, imidazolium ion, quinolinium ion, trimethylsulfonium ion,
Tributylsulfonium ion, dimethyl (2-oxocyclohexyl) sulfonium ion, bis (2-oxocyclohexyl) methylsulfonium ion, (10
-Camphenoyl) methyl (2-oxocyclohexyl) sulfonium ion, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium ion, triphenylsulfonium ion, diphenyltolylsulfonium ion, diphenylxylylsulfonium ion, mesityldiphenylsulfonium ion, (T-butylphenyl) diphenylsulfonium ion, (octylphenyl) diphenylsulfonium ion, (cyclohexylphenyl) diphenylsulfonium ion,
Biphenyldiphenylsulfonium ion, (hydroxymethylphenyl) diphenylsulfonium ion,
(Methoxymethylphenyl) diphenylsulfonium ion, (acetylphenyl) diphenylsulfonium ion, (benzoylphenyl) diphenylsulfonium ion, (hydroxycarbonylphenyl) diphenylsulfonium ion, (methoxycarbonylphenyl)
Diphenylsulfonium ion, (trifluoromethylphenyl) diphenylsulfonium ion, (fluorophenyl) diphenylsulfonium ion, (chlorophenyl) diphenylsulfonium ion, (bromophenyl) diphenylsulfonium ion, (iodophenyl) diphenylsulfonium ion, pentafluorophenyldiphenylsulfonium ion Ion, (hydroxyphenyl) diphenylsulfonium ion, (methoxyphenyl) diphenylsulfonium ion, (butoxyphenyl) diphenylsulfonium ion, (acetyloxyphenyl) diphenylsulfonium ion, (benzoyloxyphenyl) diphenylsulfonium ion, (dimethylcarbamoylphenyl) diphenyl Sulfonium ion, ( Cetylamidophenyl) diphenylsulfonium ion, phenylditolylsulfonium ion, phenyldixylsulfonium ion, dimesitylphenylsulfonium ion, bis (t-butylphenyl) phenylsulfonium ion, bis (octylphenyl) phenylsulfonium ion, bis (cyclohexyl) Phenyl) phenylsulfonium ion, dibiphenylphenylsulfonium ion, bis (hydroxymethylphenyl) phenylsulfonium ion, bis (methoxymethylphenyl) phenylsulfonium ion, bis (acetylphenyl) phenylsulfonium ion, bis (benzoylphenyl) phenylsulfonium ion, Bis (hydroxycarbonylphenyl) phenylsulfonium ion, bis (meth) Alkoxycarbonyl phenyl) phenyl sulfonium ion, bis (trifluoromethyl) phenyl sulfonium ions,
Bis (fluorophenyl) phenylsulfonium ion, bis (chlorophenyl) phenylsulfonium ion, bis (bromophenyl) phenylsulfonium ion, bis (iodophenyl) phenylsulfonium ion, dipentafluorophenylphenylsulfonium ion, bis (hydroxyphenyl) phenylsulfonium ion Ion, bis (methoxyphenyl) phenylsulfonium ion, bis (butoxyphenyl) phenylsulfonium ion, bis (acetyloxyphenyl) phenylsulfonium ion, bis (benzoyloxyphenyl) phenylsulfonium ion, bis (dimethylcarbamoylphenyl) phenylsulfonium ion, Bis (acetylamidophenyl) phenylsulfonium ion, tristrilus Fonium ion, triskisilylsulfonium ion, trismesitylphenylsulfonium ion, tris (t-butylphenyl) sulfonium ion, tris (octylphenyl) sulfonium ion, tris (cyclohexylphenyl) sulfonium ion, tribiphenylsulfonium ion, tris (hydroxymethyl) Phenyl) sulfonium ion, tris (methoxymethylphenyl) sulfonium ion,
Tris (acetylphenyl) sulfonium ion, tris (benzoylphenyl) sulfonium ion, tris (hydroxycarbonylphenyl) sulfonium ion, tris (methoxycarbonylphenyl) sulfonium ion, tris (trifluoromethylphenyl) sulfonium ion, tris (fluorophenyl) sulfonium Ion, tris (chlorophenyl) sulfonium ion, tris (bromophenyl) sulfonium ion,
Tris (iodophenyl) sulfonium ion, dipentafluorophenylsulfonium ion, tris (hydroxyphenyl) sulfonium ion, tris (methoxyphenyl) sulfonium ion, tris (butoxyphenyl) sulfonium ion, tris (acetyloxyphenyl) sulfonium ion, tris ( Benzoyloxyphenyl) sulfonium ion, tris (dimethylcarbamoylphenyl) sulfonium ion, tris (acetylamidophenyl) sulfonium ion, methyldiphenylsulfonium ion, ethyldiphenylsulfonium ion, butyldiphenylsulfonium ion, hexyldiphenylsulfonium ion, octyldiphenylsulfonium ion, Cyclohexyl diphenyl sulfonium Ion, 2-oxocyclohexyldiphenylsulfonium ion, norbornyldiphenylsulfonium ion, camphenoyldiphenylsulfonium ion, pinanoyldiphenylsulfonium ion, naphthyldiphenylsulfonium ion, anthranyldiphenylsulfonium ion, benzyldiphenylsulfonium ion, trifluoromethyldiphenylsulfonium ion Ion, methoxycarbonylmethyldiphenylsulfonium ion, butoxycarbonylmethyldiphenylsulfonium ion, benzoylmethyldiphenylsulfonium ion, (methylthiophenyl) diphenylsulfonium ion, (phenylthiophenyl)
Diphenylsulfonium ion, (acetylphenylthiophenyl) diphenylsulfonium ion, dimethylphenylsulfonium ion, diethylphenylsulfonium ion, dibutylphenylsulfonium ion,
Dihexylphenylsulfonium ion, dioctylphenylsulfonium ion, dicyclohexylphenylsulfonium ion, bis (2-oxocyclohexyl) phenylsulfonium ion, dinorbornylphenylsulfonium ion, dicamphenoylphenylsulfonium ion, dipinanoylphenylsulfonium ion, dinaphthyl Phenylsulfonium ion, dibenzylphenylsulfonium ion, trifluoromethyldiphenylsulfonium ion, bis (methoxycarbonylmethyl) phenylsulfonium ion, bis (butoxycarbonylmethyl) phenylsulfonium ion, dibenzoylmethylphenylsulfonium ion,
Bis (methylthiophenyl) phenylsulfonium ion, bis (phenylthiophenyl) phenylsulfonium ion, bis (acetylphenylthiophenyl) phenylsulfonium ion, dimethyl (2-oxocyclohexyl) sulfonium ion, bis (2-oxocyclohexyl) methylsulfonium ion , (10-camphenoyl) methyl (2-oxocyclohexyl) sulfonium ion, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium ion, trimethylsulfonium ion, triethylsulfonium ion,
Tributylsulfonium ion, dihexylmethylsulfonium ion, trioctylsulfonium ion, dicyclohexylethylsulfonium ion, methyltetrahydrothiophenium ion, methyltetrahydrothiophenium ion, triphenyloxosulfonium ion, bis [4- (diphenylsulfonio) phenyl] sulfide- There are onium salts composed of sulfur atoms such as bis ions and onium salts composed of phosphorus atoms such as tetraphenylphosphonium ions. As the halonium salt, diphenyliodonium ion,
Bis- (t-butylphenyl) iodonium cation,
(Methoxyphenyl) phenyliodonium ion,
(Butoxyphenyl) phenyliodonium ion, trifluoroethylphenyliodonium ion, pentafluorophenylphenyliodonium ion and the like can be mentioned, with preference given to sulfonium ion and iodonium ion.

The sulfonic acid derivative of the formula (1) of the present invention is
All of them are new compounds not published in the literature, and can be synthesized, for example, by the reaction pathway shown in [Chemical Formula 4] below. That is, by using α-perfluoroalkylalkanol represented by the general formula (3) as a starting material and reacting with trifluoromethanesulfonic anhydride in an organic solvent in the presence of a base, trifluoromethanesulfonic acid ester (4) is synthesized. And react with sodium thiocyanate (4) (5)
And thiol (6) are obtained with a reducing agent such as lithium aluminum hydride. The sulfonic acid of formula (1) can be obtained by oxidizing this thiol (6) with an oxidizing agent such as hydrogen peroxide. When this sulfonic acid is neutralized with, for example, sodium hydroxide, it becomes a sulfonate. Further, salt exchange can be easily carried out with M mentioned above based on a conventional method.

[0033]

[Chemical 4]

(In the formula, R and Rf are as described above, and R'is an optionally substituted carbon atom of 2).
It represents an alkyl group, a cycloalkyl group, a perfluoroalkyl group, an aromatic organic group or an aralkyl group having 5 or less. )

Further, the synthesis of the sulfonic acid ester of (4) is carried out, for example, by RK Crossland, KL Servis, J. Org. Che.
m., 35, 3195 (1970).
The functional group conversion from (4) to (5) is described in JP-A-10-2875.
96, J.-M. Vatele, Tetrahedron, 42, 16, 44.
43 (1986) and the like. The reduction reaction from thiocyanate ester of (5) to thiol is
GL O'Connor, HRNace, J. Am. Chem. Soc., 75,
2118 (1953), RK Olsen, HR Snyder, J. Org. Che
m., 30, 184, 187 (1965) etc. can be achieved. Further, it was found from our study that the synthesis of (4) to (6) can be achieved by using (4) and a sulfurizing agent such as thiourea. Details are described in Example 3. The oxidation reaction of (6) to (1) can be achieved by oxidizing with hydrogen peroxide solution, nitric acid, bromine solution, hypochlorite, potassium permanganate, chromate or the like.

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples, but the Examples given here are merely examples, and the present invention is not limited at all in describing them.

[Example 1] 3-cyclohexyl-1,
Synthesis of sodium 1,1-trifluoropropane-2-sulfonate (Step 1) NaH (24 mmol, under nitrogen atmosphere)
60%, 0.96 g) was added to dry ether (40 ml) and stirred. In this solution, 3-
Cyclohexyl-1,1,1-trifluoropropane-
2-all (CAS # 157330-89-7, 20m
mol, 4.57 g) in ether (10 ml) was added dropwise at room temperature until the evolution of hydrogen gas ceased.
Stir for minutes. Then, the reaction solution was cooled to 5 to 10 ° C., and trifluoromethanesulfonic anhydride (24 mmol, 4.
1 ml) was added dropwise at 10 ° C. or lower, and the mixture was stirred at room temperature for 3 hours, and then the reaction solution was cooled to 5 to 10 ° C.
l) was added to stop the reaction. After liquid separation, the aqueous layer was extracted again with ethyl acetate, the organic layers were combined and washed with pure water.
The organic layer was dried over anhydrous magnesium sulfate and filtered. Then, the solvent was distilled off with an evaporator to give 3-cyclohexyl-1,1,1-represented by the following formula (8).
Trifluoropropan-2-yl trifluoromethanesulfonate was obtained. The crude weight was 6.71 g.

[0038]

[Chemical 5]

[0039]

[Chemical 6]

(Step 2) 3-Cyclohexyl-1,1,1-trifluoropropan-2-yl trifluoromethanesulfonate (18.17 mmol, 5.
96 g), sodium thiocyanate (72.7 mmo
1, 5.95 g) to dimethylformamide (180 m
1) and the reaction solution was stirred at 90 ° C. for 1 hour. After returning to room temperature, pure water (180 ml) was added, the mixture was extracted with hexane, the organic layer was dried with anhydrous magnesium sulfate and filtered. Then, the solvent was distilled off with an evaporator, and 3-cyclohexyl-1,1,1-represented by the following formula (9) was used.
Trifluoropropan-2-yl thiocyanate 4.4
g was obtained. Its structure was confirmed by the following spectral data.

¹ H-NMR (CDCl ₃ ): δ 0.8
6 to 1.33 m 5H, δ 1.36 to 1.88 m
8H, delta 3.47-3.56 m 1H. IR (NaCl): 2927, 2855 (Alky
l), 2162 (SCN), 1451, 1257, 11
88, 1161, 1119

[0042]

[Chemical 7]

(Step 3) Lithium aluminum hydride (60 mmol, 2.28 g) was suspended in anhydrous tetrahydrofuran (240 ml) at 5-10 ° C. under a nitrogen stream. The above-mentioned 3-cyclohexyl-1,1,1-
A large amount of trifluoropropan-2-yl thiocyanate (120 mmol, 35.56 g) was dissolved in tetrahydrofuran (60 ml), and the anhydrous lithium suspension of lithium aluminum hydride was added dropwise to this solution for 3 hours. The reaction was carried out at room temperature. Then, cool to 5-10 ° C with an ice bath and add 1N HCl.
(200 ml) was added to stop the reaction. After liquid separation, the mixture was further extracted with ethyl acetate, the organic layer was washed with pure water, dried over anhydrous magnesium sulfate, and filtered. Then, the solvent was distilled off with an evaporator, and the residue was purified by vacuum distillation to obtain 3-cyclohexyl-1,1,1-trifluoropropane-2-thiol (17.60 g) represented by the following formula (10). . Its structure was confirmed by the following spectral data.

¹ H-NMR (CDCl ₃ ): δ 0.7
1-1.68 m 13H, δ 3.15-3.27
m 1H. IR (NaCl): 2926, 2854 (Alky
l), 1450, 1259, 1184, 1155, 11
Thirteen

[0045]

[Chemical 8]

(Step 4) The obtained 3-cyclohexyl-1,1,1-trifluoropropane-2-thiol (70 mmol, 16.0 g) was dissolved in acetic acid (70 ml) and heated to 40 ° C. to give a 30% excess. Hydrogen oxide water (40 ml)
Was added dropwise and reacted at 40 ° C. for 6 hours. After returning to room temperature, it was washed with hexane to remove unreacted thiols and disulfides, and the solvent was distilled off with an evaporator. After adding pure water (10 ml), 1N NaOH (50 m
The reaction solution was neutralized with 1), and sodium sulfite (14.
The peroxide was neutralized with 87 g). The obtained solid was suction filtered and then recrystallized from pure water (10 ml) to obtain a crude crystal. Further, it was recrystallized with pure water (16 ml) to give pure 3-cyclohexyl-1, represented by the following formula (11):
Sodium 1,1-trifluoropropane-2-sulfonate (10.94 g, yield 55.4%) was obtained. Its structure was confirmed by the following spectral data.

¹ H-NMR (D ₂ O): δ 0.92
0.95 m 2H, δ 1.21-1.26 m 3
H, δ1.51 to 1.92 m 9H, δ3.76 m
1H (3-trimethylsilyl-2,2,3,3-D-
Sodium propionate was used as a standard). ¹⁹ F-NMR (D ₂ O): δ-66.83 d J =
9.19 Hz (trichlorofluoromethane was used as standard). IR (NaCl): 2931, 2854 (Alky
l), 1447, 1253, 1203, 1080, 10
60

[0048]

[Chemical 9]

Example 2 Synthesis of triphenylsulfonium 3-cyclohexyl-1,1,1-trifluoropropane-2-sulfonate Triphenylsulfonium chloride (5 mmol,
1.51 g) and sodium 3-cyclohexyl-1,1,1-trifluoropropane-2-sulfonate (5 mmol, 1.40 g) synthesized in Example 1 were added to pure water (20 m).
It was dissolved in 1) and reacted. The obtained crystals were dissolved in methanol (5 ml) and added dropwise to pure water (50 ml). The obtained solid was taken out by suction filtration, dried under reduced pressure, and triphenylsulfonium 3-cyclohexyl-
1.3 g of 1,1,1-trifluoropropane-2-sulfonate was obtained.

Example 3 Synthesis of Sodium 1,1,1-Trifluorononane-2-Sulfonate (Step 1) By the method described in Step 1 of Example 1, 3
-Cyclohexyl-1,1,1-trifluoropropan-2-ol was added to 1,1,1-trifluorononane-2-
Change to all (80 mmol scale), 1,1,1-
Trifluorononan-2-yl trifluoromethanesulfonate was synthesized and distilled under reduced pressure (90 to 92 ° C./20 mm
Hg). The obtained ester body is 18.49 g.
The yield was 70.0%.

(Step 2) By the method described in Step 2 of Example 1, 3-cyclohexyl-1,1,1-trifluoropropan-2-yl trifluoromethanesulfonate was changed to the above ester body (55 mmol scale), and 1 , 1,1-Trifluorononan-2-yl thiocyanate (9.37 g, yield 71.2%) was obtained.

(Step 3) By the method described in Step 3 of Example 1, 3-cyclohexyl-1,1,1-trifluoropropan-2-yl thiocyanate was changed to the above cyanate compound (39 mmol scale) to give 1,1. ，
6.66 g of 1-trifluorononane-2-thiol,
The yield was 72.1%.

(Step 4) 3-Cyclohexyl-1,1,1-trifluoropropane-2-thiol was added to the above thiol compound (30) by the method described in Step 4 of Example 1.
mmol scale), sodium 1,1,1-trifluorononane-2-sulfonate (2.98 g, yield 34.9%) was obtained.

An example of the reaction of the trifluoromethanesulfonic acid ester (4) with thiourea described in the detailed description, that is, from the raw material of Step 2 to Step
An example of obtaining the product of 3 is described below.

1,1,1-Trifluorononane-2-yl trifluoromethanesulfonate (100 mmol, 33.03 g) obtained in Step 1 and thiourea (200
mmol, 15.22 g) was dissolved in DMF (100 ml) and reacted at 100 ° C. for 1 hour. After cooling to 10 ° C. or lower, 1N NaOH (100 ml) was added, and the mixture was reacted at room temperature for 2 hours. The desired product was extracted with hexane, washed with pure water, the organic layer was dried over anhydrous magnesium sulfate, and filtered. The solvent was distilled off with an evaporator, and the crude 22.
71 g were obtained. This crude was purified by vacuum distillation,
1,1-trifluorononane-2-thiol 11.6
Obtained in 2 g, 54.2% yield.

Example 4 Triphenylsulfonium
Synthesis of 1,1,1-trifluorononane-2-sulfonate 1,1,1-trifluorononane synthesized in Example 3
Sodium 2-sulfonate (10 mmol, 2.84)
g), triphenylsulfonium chloride (10 m
mol (2.98 g) was dissolved in 25 ml of pure water. Thirty
After stirring for a minute, an oil was obtained. This was extracted with dichloromethane, the organic layer was washed with pure water, dried over anhydrous magnesium sulfate, and filtered. Then, the solvent was distilled off with an evaporator to obtain 1.54 g of crude. This crude was subjected to silica gel chromatography (SiO ₂ ,
(Dichloromethane-methanol) and crystallized from ether to give triphenylsulfonium
1.26 g of 1,1,1-trifluorononane-2-sulfonate was obtained. Its structure was confirmed by the following spectral data.

¹ H-NMR (CDCl ₃ ): δ 0.8
6 t J = 6.79 Hz 3H, δ1.25-1.2
9 m 8H, δ 1.58 to 1.59 m 2H, δ
1.86-1.97 m 2H, δ 2.17-2.
26 m 1H, δ 3.29 to 3.45 m 1H,
δ 7.66 to 7.80 m 15H. ¹³ C-NMR (CDCl ₃ ): 14.15, 22.6.
7, 27.09, 28.27, 29.09, 29.7
0, 31.87, 62.30, 124.76, 131.
29, 131.33, 134.24

Example 5 Synthesis of Sodium 1,1,1-Trifluoroheptane-2-sulfonate (Step 1-1) Trifluoroacetic Anhydride (500 m
mol, 71 ml), hexanoyl chloride (500
mmol, 72 ml) to dichloromethane (500 ml)
Added to. Pyridine (1.5 mmol, 122 ml) was added to this solution while maintaining 20 ° C., and the mixture was stirred for 1 hour. Pure water (500 ml) was added while cooling to 10 ° C. to stop the reaction. After liquid separation, the organic layer was washed with pure water and further washed with saturated sodium carbonate. After washing with pure water, the organic layer was dried with magnesium sulfate and filtered. After that, the solvent was distilled off with an evaporator and vacuum distillation (20 mmHg
/ 50 ° C.) to give 1,1,1-trifluoroheptan-2-one (25.84 g) in a yield of 30.7%. Its structure was confirmed by the following spectral data.

¹ H-NMR (CDCl ₃ ): δ 0.9
1 t J = 7.2 Hz 3H, δ1.32 to 1.37
m 4H, δ 1.69 tt J = 7.2Hz 2
H, δ 2.71 t J = 7.2 Hz 2H. ¹³ C-NMR (CDCl ₃ ): 13.81, 22.1.
2, 22, 31, 30.92, 36.36, 115.5
5 q J = 291.6 Hz, 191.48 qJ = 3
4.3 Hz. IR (NaCl): 2962 (Alkyl), 2876
(Alkyl), 1766 (C = O), 1207, 11
Fifty

(Step 1-2) The above-mentioned 1,1,1-trifluoroheptan-2-one (25.84 g, 15)
3.66 mmol) of anhydrous tetrahydrofuran (80 m
l) and dissolved in sodium borohydride (2.90 g,
76.83 mmol) was added at 0 ° C., and the mixture was reacted for 3 hours at room temperature. After cooling to 0 ° C., 1N HCl (100 ml) was added to stop the reaction. After ethyl acetate (100 ml) was added and liquid-separated, the aqueous layer was extracted again with ethyl acetate, the organic layers were combined, washed with pure water, dried over anhydrous magnesium sulfate, and filtered. Then, the solvent was distilled off with an evaporator to obtain 1,1,1-trifluoroheptan-2-ol (18.51 g) in a yield of 70.8%.
Got with. Its structure was confirmed by the following spectral data.

¹ H-NMR (CDCl ₃ ): δ 0.9
1 t J = 8.0 Hz 3H, δ1.33 to 1.43
m 5H, δ 1.54 to 1.73 m 3H, δ
2.12 d J = 6.0 Hz 1H (OH), δ
3.86-3.96 m1H (CH-O). ¹³ C-NMR (CDCl ₃ ): 14.00, 22.4.
8, 24.63, 29.59, 31.41, 70.53
q J = 30.6 Hz, 125.15 q J = 28
1.6 Hz. IR (NaCl): 3384 (OH), 2959 (Al
kyl), 2934 (Alkyl), 2866 (Alk)
yl), 1460, 1278, 1173, 1144, 6
95.

(Step 1-3) The above 1,1,1-trifluoroheptan-2-ol (100 mmol, 1
8.46 g), pyridine (110 mmol, 8.94)
Dissolve g) in dichloromethane (100 ml) for 5-10
Cooled to ° C. Trifluoromethanesulfonic anhydride (110 mmol, 18.69 ml) was added dropwise to this solution. After reacting for 3 hours at room temperature, it was cooled to 5 to 10 ° C. and pure water (100 ml) was added to stop the reaction.
After liquid separation, the organic layer was washed with pure water, dried over anhydrous magnesium sulfate, and filtered. Then, the solvent was distilled off with an evaporator, and 1,1,1-trifluoroheptan-2-yl trifluoromethanesulfonate (1
7.03 g) was obtained with a yield of 56.4%. Its structure was confirmed by the following spectral data.

¹ H-NMR (CDCl ₃ ): δ 0.9
2 t J = 5.79 Hz 3 H, δ1.35 to 1.5
5 m 6H, δ 1.89 to 1.97 m 2H, δ
4.97-5.04 m1H (CH-O). ¹³ C-NMR (CDCl ₃ ): 13.83, 22.2.
1, 23.68, 28.51, 30.98, 81.94
q J = 34.2 Hz, 118.26 q J = 31
8.6 Hz, 122.04 q J = 280.0 Hz. IR (NaCl): 2964 (Alkyl), 2878
(Alkyl), 1424, 1217, 1143, 94
1.

(Step 2) By the method described in Step 2 of Example 1, 3-cyclohexyl-1,1,1-trifluoropropan-2-yl trifluoromethanesulfonate was changed to the above ester body (55 mmol scale), and 1 , 1,1-trifluoroheptan-2-yl
Thiocyanate was obtained in a yield of 91% (9.6 g). Its structure was confirmed by the following spectral data.

¹ H-NMR (CDCl ₃ ): δ 0.9
3 t J = 6.79 Hz 3H, δ1.36 to 1.3
8 m 4H, δ 1.44 to 1.51 m 1H, δ
1.69 to 1.70 m 1H, δ 1.76 to 1.
86 m 1H, δ 2.04 to 2.12 m 1H,
3.38-3.47 m 1H. ¹³ C-NMR (CDCl3): 13.91, 22.2.
7, 25.92, 27.67, 30.82, 50.12
q J = 31.5 Hz, 108.15 (SCN), 1
24.77 q J = 278.8 Hz. IR (NaCl): 2961 (Alkyl), 2836
(Alkyl), 2867 (Alkyl), 2164
(SCN), 1260, 1172, 1130, 110
4.

(Step 3) By the method described in Step 3 of Example 1, 3-cyclohexyl-1,1,1-trifluoropropan-2-yl thiocyanate was replaced with this cyanate compound (50 mmol scale), and silica gel column chromatography was performed. Purified with 4.1 g of 1,1,1-trifluoroheptane-2-thiol, yield 48.
Obtained at 5%. Its structure was confirmed by the following spectral data.

¹ H-NMR (CDCl ₃ ): δ 0.9
1 t J = 6.79 Hz 3H, δ1.27 to 1.5
5 m 6H, δ 1.65 m 1H, δ 1.76
dJ = 7.99Hz 1H, delta 1.93-2.00
m 1H, δ 3.12 to 3.24 m 1H. ¹³ C-NMR (CDCl ₃ ): 14.02, 22.4.
1, 26.23, 30.78, 30.80, 31.1
3, 42.31 q J = 29.82 Hz, 126.2
2 q J = 276.6 Hz. IR (NaCl): 2959 (Alkyl), 2865
(Alkyl), 1261, 1164, 1123, 11
00.

At this time, 1,1,
1-Trifluoro-2-heptane disulfide (yield 0.57 g, yield 6.2%) was obtained. Its structure is
It was confirmed from the following spectrum data.

¹ H-NMR (CDCl ₃ ): δ 0.9
1 t J = 6.39 Hz 6H, δ1.33 to 1.7
2 m 14H, δ 1.83 to 1.89 m 2H,
δ 3.09 to 3.24 m 2H. ¹³ C-NMR (CDCl ₃ ): 13.98, 22.3.
6, 26.10, 26.18, 27.22, 27.8
3, 31.22, 31.27, 54.52 q J = 2
7.31 Hz, 56.44 q J = 27.31 Hz,
126.32 qJ = 278.31 Hz, 126.38
qJ = 278.31 Hz. IR (NaCl): 2960 (Alkyl), 2933
(Alkyl), 2865, 1258, 1165, 11
20, 1097.

(Step 4) The above 1,1,1-trifluoroheptane-2-thiol (3.72 g, 20 mm)
ol) was dissolved in acetic acid (20 ml). 48% peracetic acid (125 mmol, 15.84 at a rate not exceeding 60 ° C.
g) was added dropwise and the mixture was reacted for 3 hours, formaldehyde (60 mmol, 2.64 g) was added, and the mixture was further reacted for 1 hour. After returning to room temperature, the solvent was distilled off with an evaporator. The obtained oil was dissolved in pure water (20 ml) and neutralized with 1N NaOH (12 ml). The solvent was distilled off with an evaporator to obtain sodium 1,1,1-trifluoroheptane-2-sulfonate (4.01 g) in a yield of 78.2%. Its structure was confirmed by the following spectral data.

¹ H-NMR (D ₂ O): δ 0.89
tJ = 6.99Hz 3H, delta 1.31-1.35.
m 4H, δ 1.54 to 1.60 m 2H, δ
1.89 to 2.04 m 2H, δ 3.61 to 3.7
1 m 1H.

[Example 6] Synthesis of potassium 1,1,1-trifluoroundecane-2-sulfonate (Step 1-1) Hexanoyl chloride was converted into decanoyl chloride (Step 1-1) by the method described in Step 1-1 of Example 5. (1 mol scale), 1,1,1-trifluoroundecane-2-one was synthesized and distilled under reduced pressure (75-
Purified at 76 ° C / 10 mmHg). The obtained ketone body was 112.40 g, and the yield was 50.1%, and its structure was confirmed by the following spectrum data.

¹ H-NMR (CDCl ₃ ): δ 0.8
8 t J = 6.39 Hz 3H, δ1.27 to 1.3
1 m 12H, δ 1.66 to 1.69 m 2H,
δ 2.71 t J = 6.79 Hz 2H. ¹³ C-NMR (CDCl ₃ ): 14.16, 22.4.
4, 22.72, 28.80, 29.26, 29.3
8, 31.88, 36.41, 115.22 qJ = 2
91.6 Hz, 191.50 q J = 34.8 Hz. IR (NaCl): 2928 (Alkyl), 2858
(Alkyl), 1766 (C = O), 1209, 10
20.

(Step1-2) Step1 of the fifth embodiment
2, 1,1,1-trifluoroheptan-2-one is changed to the above-mentioned ketone body (500 mmol scale) to prepare 1,1,1-trifluoroundecane-
2-ol was synthesized and distilled under reduced pressure (82 ° C / 2mmHg)
Purified in. The obtained alcohol body is 104.78 g,
The yield was 95.14%, and its structure was confirmed by the following spectral data.

¹ H-NMR (CDCl ₃ ): δ 0.8
1 t J = 6.39 Hz 3H, δ1.15 to 1.3
8 m 13H, δ 1.45 to 1.56 m 2H,
δ 1.58 to 1.70 m 1H, δ 2.06 to 2.
02 m 1H, δ 3.80 to 3.85 m 1H. IR (NaCl): 3372 (OH), 2927 (Al
kyl), 2857 (Alkyl), 1468, 127
9, 1172, 1142, 1114, 695.

(Step1-3) Step1 of the fifth embodiment
-1,3,1-trifluoroheptan-2-ol was changed to the above alcohol compound (450 mmol scale) by the method described in -3, and 1,1,1-trifluoroundecane-2-yl trifluoromethanesulfonate ( 15
7.95 g) was obtained with a yield of 97.95%. Its structure is
It was confirmed from the following spectrum data.

¹ H-NMR (CDCl ₃ ): δ 0.8
9 t J = 6.79 Hz 3H, δ1.28 to 1.5
5 m 14H, δ 1.91 to 1.97 m 2H,
δ 4.96 to 5.04 m 1H. ¹³ C-NMR (CDCl ₃ ): 14.11, 22.7.
3, 24.06, 28.57, 28.91, 29.1
7, 29.27, 29.41, 31.89, 81.96
q J = 33.94 Hz, 118.29 q J = 3
18.33 Hz, 122.08 q J = 279.95
Hz.

(Step 2) By the method described in Step 2 of Example 1, 3-cyclohexyl-1,1,1-trifluoropropan-2-yl trifluoromethanesulfonate was changed to the above ester body (400 mmol scale), and 1 , 1,1-Trifluoroundecane-2-yl thiocyanate (76.92 g) was obtained in a yield of 71.93.
Earned in%. Its structure was confirmed by the following spectral data.

¹ H-NMR (CDCl ₃ ): δ 0.8
9 t J = 6.79 Hz 3H, δ1.28 to 1.4
9 m 13H, δ 1.63 to 1.69 m 1H,
δ 1.76 to 1.86 m 1H, δ 2.04 to 2.
12 m 1H, δ 3.38 to 3.47 m 1H. ¹³ C-NMR (CDCl ₃ ): 14.15, 22.7.
0, 26.26, 27.71, 28.71, 29.1
9, 29.24, 29.41, 31.86, 50.12
q J = 30.72 Hz, 108.15 (SCN),
124.77 qJ = 279.11 Hz. IR (NaCl): 2928 (Alkyl), 2857
(Alkyl), 2163 (SCN), 1259, 11
78, 1130, 1111.

(Step 3) By the method described in Step 3 of Example 1, 3-cyclohexyl-1,1,1-trifluoropropan-2-yl thiocyanate was replaced with the above thiocyanate compound (280 mmol scale),
61.7 g of 1,1,1-trifluoroundecane-2-thiol was obtained with a yield of 93.8%. Its structure was confirmed by the following spectral data.

¹ H-NMR (CDCl ₃ ): δ 0.8
8 t J = 6.79 Hz 3H, δ1.27 to 1.5
4 m 14H, δ 1.62 to 1.65 m 1H,
δ 1.76 d J = 8.39 Hz 1H, δ 1.9
2 to 2.00 m 1H, δ 3.12 to 3.22 m
1H. ¹³ C-NMR (CDCl ₃ ): 14.18, 227.
4, 26.57, 28.98, 29.32, 29.3
6, 29.52, 30.83, 31.91, 42.31
qJ = 29.82Hz, 126.22qJ = 2
76.60 Hz. IR (NaCl): 2927 (Alkyl), 2857
(Alkyl), 1260, 1162, 1126, 11
07.

(Step 4) 1,1,1-trifluoroundecane-2-thiol (50 mmol, 1
4.99 g) was dissolved in acetic acid (50 ml), 48% peracetic acid (250 mmol, 39.61 g) was added dropwise at a temperature of 50 ° C. or lower, and the mixture was reacted for 3 hours. After that, acetaldehyde (150 mmol) was added and the reaction was further performed for 1 hour. After cooling, the solvent was distilled off with an evaporator. Pure water (50 ml) was added to dissolve the resulting oil, and neutralization with potassium hydroxide revealed precipitation of crystals. The crystals are suction filtered and washed with ethyl acetate to
9.53 g of potassium 1,1-trifluoroundecane-2-sulfonate was obtained at a yield of 58.0%. Its structure was confirmed by the following spectral data.

¹ H-NMR (D ₂ O): δ 0.88
t J = 6.19 Hz 3H, δ 1.30 m 12
H, delta 1.55 to 1.58 m 2H, delta 1.86
~ 1.95 m 1H, δ 2.00 to 2.09 m
1H, δ 3.47 to 3.57m 1H. IR (NaCl): 2925 (Alkyl), 2855
(Alkyl), 1227, 1054.

Example 7 Synthesis of Sodium 1-Perfluoroheptylnonane Sulfonate (Step 1-1) Perfluorooctanoic Acid (100 m
mol, 41.4 g) was dissolved in anhydrous ether (100 ml), and octyl magnesium bromide (100 mm)
ol) was added and refluxed for 4 hours to react. 0
After cooling to -10 ° C, 1N HCl was added to stop the reaction. After liquid separation, the organic layer was washed with pure water, dried over anhydrous magnesium sulfate, and filtered. Then, the solvent was distilled off with an evaporator to obtain 26.1 g of crude perfluoroheptyl octyl ketone in a yield of 51.2%.

(Step 1-2) The above-mentioned perfluoroheptyl octyl ketone (26.13 g) was added dropwise to a solution of sodium borohydride (15 mmol, 0.567 g) in ethanol (100 ml), and the mixture was reacted for 3 hours. The reaction was stopped by adding 1N HCl (100 ml) below 10 ° C. After liquid separation, the aqueous layer was extracted again with ethyl acetate, and the organic layers were combined. The obtained organic layer was washed with pure water, dried over anhydrous magnesium sulfate, and filtered. The solvent was distilled off with an evaporator to obtain 21.8 g of crude. Recrystallization from hexane gave 12.9 g of 1-perfluoroheptylnonanol in a yield of 49.1%.

(Step1-3) Step1 of the fifth embodiment
1-perfluoroheptylnonanyl by changing 1,1,1-trifluoroheptan-2-ol to the above alcohol compound (20 mmol scale) by the method described in -3.
Trifluoromethanesulfonate (7.71 g) was obtained with a yield of 59.8%.

(Step 2) By the method described in Step 2 of Example 1, 3-cyclohexyl-1,1,1-trifluoropropan-2-yl trifluoromethanesulfonate was changed to the above ester form (10 mmol scale), and 1 -Perfluoroheptylnonanyl thiocyanate (2.67 g) was obtained with a yield of 48.3%.

(Step 3) By the method described in Step 3 of Example 1, 3-cyclohexyl-1,1,1-trifluoropropan-2-yl thiocyanate was changed to the above thiocyanate compound (2 mmol scale) to give 1-perm. Fluoroheptylnonanethiol (2.0 g) was obtained with a yield of 78.2%.

(Step 4) The 1,1,1-trifluoroheptane-2-thiol was changed to the above-mentioned thiol compound (3 mmol scale) by the method described in Step 4 of Example 5 to give 1-perfluoroheptylnonanesulfonic acid. Sodium (1.23 g) was obtained with a yield of 68.72%.

[Application Example 1] 2 parts by weight of triphenylsulfonium 3-cyclohexyl-1,1,1-trifluoropropane-2-sulfonate described in Example 2 and polyhydroxystyrene having a hydroxyl group of 1-ethoxyethyl group. Polymer 10 having a weight average molecular weight of 15,000 protected by 15 mol% and tert-butoxycarbonyl group 15 mol%
0 parts by weight and 0.2 parts by weight of isopropanolamine were added to propylene glycol monomethyl ether acetate 600.
A resist was prepared by dissolving in parts by weight.

[Application Example 2] 2 parts by weight of triphenylsulfonium 3-cyclohexyl-1,1,1-trifluoropropane-2-sulfonate described in Example 2 and polyhydroxystyrene having a hydroxyl group of 1-ethoxyethyl group. A resist was prepared by dissolving 100 parts by weight of a polymer having a weight average molecular weight of 15,000 protected by 35 mol% and 0.2 parts by weight of isopropanolamine in 600 parts by weight of propylene glycol monomethyl ether acetate.

[Application Example 3] Triphenylsulfonium 1,1,1-trifluorononane-2 described in Example 4
2 parts by weight of sulfonate, hydroxyl group of polyhydroxystyrene is 15 mol% of 1-ethoxyethyl group, tert-
A resist was prepared by dissolving 100 parts by weight of a polymer having a weight average molecular weight of 15,000 protected with 15 mol% of butoxycarbonyl groups and 0.2 parts by weight of isopropanolamine in 600 parts by weight of propylene glycol monomethyl ether acetate.

[Comparative Example 1] Triphenylsulfonium
2 parts by weight of trifluoromethanesulfonate, 100 parts by weight of a polymer having a weight average molecular weight of 15,000 in which hydroxyl groups of polyhydroxystyrene are protected with 15 mol% of 1-ethoxyethyl groups and 15 mol% of tert-butoxycarbonyl groups, and isopropanolamine 0 0.2 part by weight was dissolved in 600 parts by weight of propylene glycol monomethyl ether acetate to prepare a resist.

[Comparative Example 2] Triphenylsulfonium
Polymer 10 having a weight average molecular weight of 15,000, in which 2 parts by weight of 10-camphor sulfonate and hydroxyl groups of polyhydroxystyrene are protected with 35 mol% of 1-ethoxyethyl groups.
0 parts by weight and 0.2 parts by weight of isopropanolamine were added to propylene glycol monomethyl ether acetate 600.
A resist was prepared by dissolving in parts by weight.

[Test Example] Application Examples 1 to 3 and Comparative Examples 1 and 2.
The resist was filtered through a 0.2 μm membrane filter to prepare a radiation sensitive resin composition solution. Then, the composition solution was spin coated on a silicon wafer and dried on a hot plate at 100 ° C. for 90 seconds to give a film thickness of 0.7 μm.
m resist film was formed. The film obtained was uniform and good.

This resist film was exposed using a KrF excimer laser stepper (NA = 0.5). After the exposure, the film was heated on a hot plate at 100 ° C. for 90 seconds, developed in a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds, and rinsed with pure water for 30 seconds.

As a result, in Application Examples 1 to 3, a rectangular positive type good pattern having no edge roughness was obtained. As a result of observing the exposed pattern and the peeled silicon substrate with a scanning electron microscope, almost no foreign matter was found. In Comparative Example 1, there were many foreign matters on the pattern after exposure and on the silicon substrate after peeling, and in Comparative Example 2, the exposure sensitivity was low and the edge roughness was large.

[0098]

As described above, according to the present invention,
It has two kinds of groups, an alkyl group and a perfluoroalkyl group, on the α carbon atom, exhibits a surface active effect of reducing surface tension and interfacial tension, and is a strong acid, and is useful as an acid catalyst and a surfactant. A novel sulfonic acid derivative can be provided. When the photoacid generator that generates the sulfonic acid of the present invention is used in a semiconductor manufacturing process or the like, it has excellent solubility in a resist solvent of the photoacid generator and compatibility with a resin,
It is possible to obtain a resist material that does not generate foreign matter during pattern formation after development and during resist stripping, is less affected by edge roughness, has an excellent pattern shape, and has excellent PED stability.

Claims (2)

[Claims] 1. A sulfonic acid derivative represented by the following general formula (1). [Chemical 1] (In the formula, R represents a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylalkyl group. Rf represents a linear alkyl group having 1 to 20 carbon atoms. Represents a branched or cyclic perfluoroalkyl group, M ^{m +} is a counter cation, and m is an integer.) 2. The sulfonic acid derivative according to claim 1, wherein the M ^{m +} is a hydrogen ion, a metal ion or an onium ion.