JP2009179565A - Benzyl cyanide-based compound, photoacid generator and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new compound producing a resist achieving high sensitivity and high transparency in the case of using it as a photoacid generator in a resist composition. <P>SOLUTION: This aryl-substituted benzyl cyanide-based oximesulfonate compound is expressed by formula [1] [wherein, R<SP>1</SP>is a substituted or a non-substituted aryl; R<SP>2</SP>is H, a halogen atom, CN, NO<SB>2</SB>, a 1-10C alkyl or alkoxy, or a 1-5C haloalkyl or haloalkoxy; R<SP>3</SP>is a 1-10C alkyl or alkoxy, a 1-5C haloalkyl or haloalkoxy, or phenyl, naphthyl or anthranyl, which may be substituted by W; and the W is a halogen atom, CN, NO<SB>2</SB>, a 1-10C alkyl or alkoxy, or a 1-5C haloalkyl or haloalkoxy]. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a benzylcyanide compound, a photoacid generator using the compound, and a method for producing the compound, and in particular, light corresponding to i-line (365 nm), h-line (405 nm), and g-line (435 nm). It relates to an acid generator.

In recent years, various oximes as photoacid generators (photosensitive acid donors) having excellent extinction coefficients (photosensitivity) for g-line, h-line and i-line and having excellent solubility in solvents. A sulfonate compound has been proposed (see, for example, Patent Document 1).
For example, a dye-containing resist composition using a thiophene-based oxime sulfonate compound as a photoacid generator has been proposed to cope with the reduction in color filter thickness (for example, Patent Document 2).
Further, various benzyl cyanide oxime sulfonate compounds have been proposed as high-sensitivity and high-resolution photoacid generators for i-line resists (for example, Patent Documents 3 and 4). 3, α- (n-propylsulfonyloxyimino) -4-methoxybenzyl cyanide, an analog of α- (4-tosyloxyimino) -4-methoxybenzyl cyanide described in Example 1 Name: PAI-1003 (Midori Chemical Co., Ltd.) is marketed and widely used. The benzyl cyanide oxime sulfonate compound is also known as a curing agent for baking finish materials (for example, Patent Document 5).

In addition to the above-described applications such as color filters, optical materials such as TFT substrate planarization films, semiconductor element insulation films, optical waveguide cores and cladding materials in organic electroluminescent elements and liquid crystal display elements are transparent and heat resistant. There is a need for a permanent film having excellent properties and sensitivity (for example, Patent Document 6), and a material capable of realizing excellent transparency, heat resistance, and sensitivity for the photoacid generator used therein is required. .
JP-T-2002-508774 International Publication No. 2006/046398 Pamphlet JP-A-6-67433 JP-A-9-95479 JP-A-60-65072 JP 2006-154037 A

The thiophene oxime sulfonate compound proposed as a photoacid generator for reducing the thickness of the color filter described above has been problematic in that coloring occurs after exposure.
Further, benzyl cyanide oxime sulfonate compounds such as α- (n-propylsulfonyloxyimino) -4-methoxybenzyl cyanide have room for improvement in terms of light transmittance.
A cycloalkenyl-substituted oxime sulfonate compound has also been proposed for the purpose of improving this light transmittance (Patent Document 4), but these have no light absorption in the i-line, h-line and g-line regions, and are sensitive. There was a problem.

The present invention has been made in view of such circumstances, and when used as an acid generator for a resist, the sensitivity to active light used for exposure, particularly i-line (365 nm), h-line (405 nm) and An object of the present invention is to provide a novel compound useful as a photoacid generator that is excellent in sensitivity to g-line (435 nm), is less colored by exposure and subsequent heat treatment, and can produce a resist that realizes high transparency.

  As a result of intensive studies to achieve the above object, the present inventors have found that a resist composition containing an aryl-substituted benzyl cyanide oxime sulfonate compound as a photoacid generator is visible from i-line (365 nm) after firing. The present invention has been completed by finding that film formation in which coloring in the region is suppressed is provided.

  That is, the present invention relates to an aryl-substituted benzyl cyanide oxime sulfonate compound represented by the formula [1] as a first aspect.

(Where
R ¹ represents an aryl group which may be substituted with a substituent which may contain an oxygen atom, a nitrogen atom and a sulfur atom,
R ² represents a hydrogen atom, a halogen atom, CN groups, NO ₂ groups, alkyl groups having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group or a number of carbon atoms of 1 to 5 carbon atoms Represents 1 to 5 haloalkoxy groups,
R ³ is substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, or W. An optionally substituted phenyl group, a naphthyl group optionally substituted with W, or an anthranyl group optionally substituted with W;
W is a halogen atom, CN group, NO ₂ group, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, haloalkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a haloalkoxy group. )
As a second aspect, the present invention relates to an aryl-substituted benzyl cyanide oxime sulfonate compound represented by the formula [2].

(Where
R ² and R ⁴ are hydrogen atom, halogen atom, CN groups, NO ₂ groups, alkyl groups having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms Represents a haloalkoxy group having 1 to 5 carbon atoms,
R ³ is substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, or W. An optionally substituted phenyl group, a naphthyl group optionally substituted with W, or an anthranyl group optionally substituted with W;
W is a halogen atom, CN group, NO ₂ group, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, haloalkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a haloalkoxy group. )
As a third aspect, the present invention relates to a phenyl-substituted benzyl cyanide oxime sulfonate compound according to the ^{second aspect} , wherein R ² and R ⁴ are hydrogen atoms.
As a fourth aspect, the present invention relates to a photoacid generator comprising the aryl-substituted benzyl cyanide oxime sulfonate compound according to any one of the first aspect to the third aspect.
As a fifth aspect, the present invention relates to a photoacid generator for i-line, h-line, and g-line comprising the aryl-substituted benzyl cyanide oxime sulfonate compound according to any one of the first to third aspects.
A sixth aspect is a method for producing an aryl-substituted benzyl cyanide oxime sulfonate compound represented by the formula [1],
Formula [3]

(Where
R ¹ represents an aryl group which may be substituted with a substituent which may contain an oxygen atom, a nitrogen atom and a sulfur atom,
R ² is a hydrogen atom, a halogen atom, a CN group, a NO ₂ group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or the number of carbon atoms 1 to 5 haloalkoxy groups are represented. )
Is reacted with amyl nitrate in the presence of a base to give a compound of formula [4]

(In the formula, R ¹ and R ² represent the same meaning as described above.)
A process for producing an α-hydroxyiminoaryl-substituted benzylcyanide compound represented by formula (5), and the α-hydroxyiminoaryl-substituted benzylcyanide compound in the presence of a base:

Wherein R ³ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, W A phenyl group which may be substituted with, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W;
W is a halogen atom, CN group, NO ₂ group, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, haloalkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a haloalkoxy group. )
It relates to a method comprising a step of reacting with a sulfonyl chloride compound represented by the formula:

  By using the compound of the present invention as a photoacid generator in a resist composition, sensitivity to active light used for exposure, particularly sensitivity to i-line (365 nm), h-line (405 nm) and g-line (435 nm) can be obtained. A resist having excellent transparency and little transparency can be produced by exposure and subsequent heat treatment.

Hereinafter, the present invention will be described in more detail.
The present invention relates to an aryl-substituted benzyl cyanide oxime sulfonate compound represented by the formula [1], a photoacid generator containing the compound, and a method for producing the compound.

(In the formula, R ¹ represents an aryl group which may be substituted with a substituent which may contain an oxygen atom, a nitrogen atom and a sulfur atom, and R ² represents a hydrogen atom, a halogen atom, a CN group or a NO ₂ group. Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or a haloalkoxy group having 1 to 5 carbon atoms, and R ³ represents a carbon atom An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, a phenyl group optionally substituted with W, A naphthyl group which may be substituted with W or an anthranyl group which may be substituted with W; W represents a halogen atom, a CN group, a NO ₂ group, an alkyl group having 1 to 10 carbon atoms, or the number of carbon atoms 1 to 1 Represents an alkoxy group having 0, a haloalkyl group having 1 to 5 carbon atoms, or a haloalkoxy group having 1 to 5 carbon atoms.)

Specific examples of the R ^1, an unsubstituted or halogen atom, CN groups, NO ₂ groups, alkyl groups having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, from 1 to 5 carbon atoms An aryl group substituted with a haloalkyl group or a haloalkoxy group having 1 to 5 carbon atoms, for example, a phenyl group, a naphthyl group, an anthranyl group, a pyridyl group, a quinolyl group, a quinoxalyl group, a furyl group, a thienyl group, a thiazolyl group, a pyrazolyl group Groups, imidazolyl groups and triazolyl groups.

Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, and t-butyl. Group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.
Specific examples of the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group, n-octyloxy group, n-decyloxy group. Groups and the like.

Specific examples of the haloalkyl group having 1 to 5 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoro-n-butyl group, and a perfluoro-n-amyl group. Can be mentioned.
Specific examples of the haloalkoxy group having 1 to 5 carbon atoms include a trifluoromethoxy group,
Examples include a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group, and a perfluoro-n-amyloxy group.

Specific examples of the phenyl group optionally substituted with W include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, p -(N-propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s-butyl) phenyl group, p -(T-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group, m-methoxyphenyl group , P-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group, p- (n- Butoxy) Enyl group, p- (i-butoxy) phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (i-amyloxy) Phenyl group, p- (t-amyloxy) phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2, 4-difluorophenyl group, 2,4,6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-trifluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentafluoro A phenyl group, p-biphenylyl group, etc. are mentioned.

  Specific examples of the naphthyl group optionally substituted with W include 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, and 5-methyl-1-naphthyl group. Group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl Examples include 2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group and the like.

  Specific examples of the anthranyl group which may be substituted with W include 2-methyl-1-anthranyl group, 3-methyl-1-anthranyl group, 4-methyl-1-anthranyl group, 5-methyl-1-anthranyl. Group, 6-methyl-1-anthranyl group, 7-methyl-1-anthranyl group, 8-methyl-1-anthranyl group, 9-methyl-1-anthranyl group, 10-methyl-1-anthranyl group, 1-methyl 2-anthranyl group, 3-methyl-2-anthranyl group, 4-methyl-2-anthranyl group, 5-methyl-2-anthranyl group, 6-methyl-2-anthranyl group, 7-methyl-2-anthranyl group , 8-methyl-2-anthranyl group, 9-methyl-2-anthranyl group, 10-methyl-2-anthranyl group and the like.

Among the aryl-substituted benzyl cyanide oxime sulfonate compounds represented by the above formula [1], the sensitivity to active light used for exposure, particularly for i-line (365 nm), h-line (405 nm) and g-line (435 nm). R ¹ is unsubstituted or is a halogen atom, CN group, NO ₂ group, carbon, because it is suitable as an acid generator that is excellent in sensitivity and can produce a highly transparent resist with little coloration by exposure and subsequent heat treatment. alkyl group of atoms 1 to 10, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group or phenyl group substituted with a haloalkoxy group having 1 to 5 carbon atoms with 1 to 5 carbon atoms, R ² is hydrogen atom, an alkyl group and alkoxy group having 1 to 10 carbon atom having 1 to 10 carbon atoms, R ³ is a methyl group, an ethyl group, n- propyl group, - octyl group, preferably a compound which is p- tolyl or pentafluorophenyl group, or more preferably R ³ is a methyl group, an ethyl group, n- propyl or n- octyl group.

Specific examples of the aryl-substituted benzyl cyanide oxime sulfonate compound represented by the formula [1] include, for example, compounds represented by the following chemical formula.

[Method for producing aryl-substituted benzyl cyanide-based oxime sulfonate compound]
The aryl-substituted benzyl cyanide oxime sulfonate compound represented by the formula [1] can be produced by the following production method.

（式中、Ｒ¹乃至Ｒ³は上記と同じ意味を表す。）

(Wherein R ^{1 to} R ³ represent the same meaning as described above.)

That is, in the first step, an aryl-substituted benzylcyanide compound ([3]) is reacted with amyl nitrate in the presence of a base, and then the reaction system is acidified to produce an intermediate oxime compound ([4] , Α-hydroxyiminoaryl substituted benzyl cyanide compound).
Subsequently, in the second step, the intermediate oxime compound ([4]) is reacted with the sulfonyl chloride compound ([5]) in the presence of a base to obtain the target aryl-substituted benzyl cyanide oxime sulfonate compound ([1 ]).

[First step]
Specific examples of the aryl-substituted benzylcyanide compound ([3]) used in the first step include compounds represented by the following chemical formula.

  Among these, 4-biphenylacetonitrile compound is particularly preferable.

As the amyl nitrate used in the first step, commercially available i-amyl nitrate and n-amyl nitrate can be used as they are.
The amount of amyl nitrate used is preferably 0.8 to 1.5 times equivalent to the aryl-substituted benzyl cyanide compound ([3]).

  As the base to be used, alkali metal or alkaline earth metal hydroxides, carbonates, organic acid salts and the like can be used, but sodium hydroxide and potassium hydroxide are preferable from the viewpoint of reactivity and economy. The amount of the base used is preferably 2 to 5 times equivalent to the aryl-substituted benzylcyanide compound ([3]).

As the reaction solvent, lower aliphatic alcohols such as methanol and ethanol are preferred.
The reaction temperature is preferably -20 to 150 ° C, particularly preferably 0 to 100 ° C.
After the reaction, add water to the reaction solution, acidify with an inorganic or organic acid, extract with ethyl acetate, and then concentrate the resulting crude product through recrystallization or column chromatography. The desired intermediate oxime compound ([4]) is obtained. Examples of the inorganic acid and organic acid used here include hydrochloric acid and acetic acid.

[Second step]
Specific examples of the sulfonyl chloride compound ([5]) used in the second step include methanesulfonyl chloride, ethanesulfonyl chloride, n-propylsulfonyl chloride, i-propylsulfonyl chloride, n-butylsulfonyl chloride, n-amyl. Sulfonyl chloride, n-hexylsulfonyl chloride, n-heptylsulfonyl chloride, n-octylsulfonyl chloride, n-nonylsulfonyl chloride, n-decylsulfonyl chloride, phenylsulfonyl chloride, p-tosylsulfonyl chloride, p-ethylphenylsulfonyl chloride, p- (n-propyl) phenylsulfonyl chloride, p- (n-butyl) phenylsulfonyl chloride, p- (n-amyl) phenylsulfonyl chloride Ride, trifluoromethylsulfonyl chloride, pentafluoroethylsulfonyl chloride, perfluoro n-propylsulfonyl chloride, perfluoro i-propylsulfonyl chloride, perfluoro n-butylsulfonyl chloride, perfluoro n-amylsulfonyl chloride, pentafluorophenylsulfonyl Examples include chloride, 1-naphthylsulfonyl chloride, 2-naphthylsulfonyl chloride, 1-anthranylsulfonyl chloride, and the like. The amount used is preferably 1 to 1.2 equivalent times the OC intermediate oxime compound ([4]).

  As the base to be used, an organic base such as triethylamine, pyridine, 4-N, N-dimethylaminopyridine (DMAP) is preferable. The amount used is preferably 1 to 1.1 times equivalent to the intermediate oxime compound ([4]).

As the reaction solvent, lower alkylbenzenes such as toluene, xylene, ethylbenzene and cumene are preferable.
The reaction temperature is preferably -20 to 100 ° C, particularly preferably 0 to 80 ° C.
After completion of the reaction, the crude product of brown solid obtained through concentration is purified by recrystallization or column chromatography using silica gel to obtain the desired cyclohexadiene oxime sulfonate compound ([1]).

  Each of the above reactions (the first step and the second step) can be carried out batchwise or flow-through, and can be carried out at normal pressure or under pressure.

[Photoacid generator]
The aryl-substituted benzyl cyanide-based oxime sulfonate compound represented by the above formula [1] is useful as a photoacid generator, particularly as a photoacid generator for i-line, h-line, and g-line. A photosensitive resin composition can be prepared by mixing with the above.
In this case, the blending amount is 0.5 to 80 parts by mass, preferably 1 to 30 parts by mass with respect to 100 parts by mass of the film-forming substance.
In the photosensitive resin composition, the photoacid generator composed of the aryl-substituted benzyl cyanide oxime sulfonate compound represented by the formula [1] may be used alone, or in addition to the compound, Conventionally known or conventionally used photoacid generators such as diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzoin tosylate compounds, iron arene complexes , A halogen-containing triazine compound, an acetophenone derivative compound, or the like.

  In this specification, “n” is normal, “i” is iso, “s” is secondary, “t” is tertiary, “c” is cyclo, “o” is ortho, “m” "Represents meta, and" p "represents para.

The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
The measuring devices and measuring conditions for each physical property in the examples are as follows.
[1] [Mass spectrometry (MASS)]
Model: LX-1000 (manufactured by JEOL (JEOL)),
Detection method: Ionization method: DEP (EI ⁺ ) m / z = 50 to 1000
[2] ^[1 H NMR]
Model: Apparatus: JNM-LA400 type FT-NMR system (manufactured by JEOL (JEOL))
Measuring solvent: DMSO-d ₆
[3] [ ¹³ C NMR]
Model: Apparatus: JNM-LA400 type FT-NMR system (manufactured by JEOL (JEOL))
Measuring solvent: DMSO-d ₆
[4] [Melting point (mp.)]
Measuring instrument: Automatic melting point measuring device, FP62 (Meteller Toledo)
[5] UV-Vis spectrum apparatus: UV-VIS-NIR SCANNING SPECTROTOPOMETER (self-recording spectrophotometer) (manufactured by Shimadzu Corporation)
[6] Ultraviolet irradiation device Model: PLA-600FA (manufactured by Canon Inc.)
[7] Interferometric film thickness meter Model: F20-EXR (manufactured by Filmmetrics)

[Synthesis of aryl-substituted benzyl cyanide oxime sulfonate compound ([1])]
Example 1: Synthesis of HBPA (α-hydroxyimino-4-biphenylacetonitrile)

A 100 ml four-necked reaction flask was charged with 1.92 g (48 mmol) of NaOH and 40 g of methanol and dissolved by heating. Subsequently, 4.87 g (20 mmol) of 4-biphenylacetonitrile (BPAN) was added at 40 ° C., and then 4.41 g (30 mmol) of isoamyl nitrate (AN) was added dropwise. When the mixture was further stirred at 60 ° C. for 3 hours, crystals were precipitated. Therefore, 25 g of methanol was further added, and stirring was further continued for 3 hours to complete the reaction.
Thereafter, the reaction solution was concentrated under reduced pressure, 30 ml of water was added to the resulting residue, and 4.8 g of concentrated hydrochloric acid was added dropwise under ice cooling to make the solution acidic. Furthermore, after extracting with ethyl acetate, it concentrated and dried and obtained skin color crystal | crystallization 4.57g (LC purity 93.0%: Yield 95.6%). The crystals were recrystallized with ethyl acetate: n-heptane = 1: 1 to obtain 3.52 g of skin color crystals (yield 79.2%).

The skin color crystals were confirmed to be α-hydroxyimino-4-biphenylacetonitrile (HBPA) from the following analysis results.
It was also confirmed by ¹³ C NMR that the mixture was a mixture of two isomers (4 to 1).
MASS (ES +, m / e (%)): 223.0 ([M + H] ⁺ , 100)
MASS (ES−, m / e (%)): 221.0 ([M−H] ⁺ , 100)
_{^{13 C NMR (DMSO-d 6}} , δppm): 110.1254 (115.6805), 126.0887 [2], 126.7297 [2], 126.8900,127.0197,127.4775 [2], 128.1719 (128.3550), 125.5153,129.0494 [2], 129.5302, 130.9800, 138.8167 (138.6870), 142.3420 (142.6320).
mp. 195-196 ° C

<Example 2: Synthesis of PSBC (α- (n-propylsulfonyloxyimino) -4-phenylbenzyl cyanide)>

The following operation was performed under a yellow fluorescent lamp.
Into a 50 ml four-necked reaction flask under nitrogen flow, 3.0 g (13 mmol) of HBPA obtained in Example 1 and 25 ml of toluene dried with molecular sieve 4A were charged at 15 ° C., and stirred with a magnetic stirrer at 3 ° C. under ice cooling. Then, 1.7 ml (15 mmol) of n-propylsulfonyl chloride was added dropwise to the reaction solution.
After stirring for 5 minutes, 2.5 g (20 mmol) of 4-N, N-dimethylaminopyridine (DMAP) was subsequently added. The viscosity of the slurry increased, so 5 ml of toluene was added again, and the temperature was returned to 15 ° C. for 2 hours. Stir. When this reaction solution was analyzed by thin layer chromatography, it was confirmed that the raw materials disappeared and the compounds were produced. The reaction solution was directly concentrated under reduced pressure to obtain 7.3 g of a crude product.
Further, this crude product was purified by column chromatography (eluent: chloroform only) using 40 g of silica gel, and the fraction was concentrated at 30 ° C. and then dried under reduced pressure for 4 hours. 3.7 g (yield 84%) of crystals were obtained.

The results of analysis of the ¹ H NMR, it was confirmed that the solid is alpha-(n-propylsulfonyl) -4-phenyl cyanide (PSBC).
1H NMR (DMSO-d ₆ , δ ppm): 1.10-1.167 (m, 3H), 1.929-2.084 (m, 2H), 3.406-3.496 (m, 2H), 7.422-7.519 (m, 3H), 7.604-7.640 (M, 3H), 7.714-7.769 (m, 2H
), 7.916-7.986 (m, 2H), 7.922-8.104 (m, 2H)

[Colorability evaluation by exposure and heating as a photoacid generator]
<Example 3>
In a 50 mL eggplant-shaped flask, 3.4 g of NH108 (polyvinylphenol (manufactured by Gunei Chemical Industry Co., Ltd.), weight average molecular weight 8000 (polystyrene conversion)), and PSBC produced in Example 2 as a photoacid generator were added in an amount of 0.00 g. 17 g, 0.031 g of Megafac R-30 (manufactured by Dainippon Ink & Chemicals, Inc.) as a surfactant and 20 g of propylene glycol monomethyl ether as a solvent were added and stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform.

The composition was filtered using a 0.2 μm PTFE (polytetrafluoroethylene) filter, and the composition was applied onto a glass substrate using a spin coater. Baking was performed on a hot plate at 110 ° C. for 1 minute (soft baking (SB)) to form a resist film (measured with an interference film thickness meter) having a thickness of 1.02 μm.
For this resist film, the ultraviolet irradiation apparatus, the irradiation amount of 365nm was irradiated with ultraviolet rays is 400 mJ / cm ^2. Then P on hot plate for 1 minute at 110 ° C.
EB (post-exposure bake) was performed. Thereafter, post-baking (PB) was performed on a hot plate at 230 ° C. for 5 minutes, and the transmittance (transmittance at 350 to 750 nm) of the glass substrate on which the resist film was formed was measured with a spectrophotometer.

<Comparative Example 1>
In a 50 mL eggplant-shaped flask, 3.4 g of NH108 (polyvinylphenol (manufactured by Gunei Chemical Industry Co., Ltd.), weight average molecular weight 8000 (polystyrene conversion)), PAI-1003 (α- (n-propylsulfonyloxyimino)- As described in Example 1 of JP-A-6-67433 as 4-methoxybenzylcyanide (manufactured by Midori Chemical Co., Ltd.), “(α- (4-tosyloxyimino) -4-methoxybenzylcyanide) analog” ) 0.17 g, 0.031 g of Megafac R-30 (Dainippon Ink Chemical Co., Ltd.) as a surfactant, and 20 g of propylene glycol monomethyl ether as a solvent were stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform.
In the same manner as in Example 3, the obtained composition was subjected to resist film formation, ultraviolet irradiation, PEB, and post-baking, and the transmittance of the glass substrate on which the resist film was formed was measured.

  The results of Example 3 and Comparative Example 1 are shown in Table 1.

As shown in Table 1, the result that the transmittance of Example 3 at 365 nm, 405 nm, and 435 nm after post-baking is equal to or higher than that of Comparative Example 1 was obtained.
That is, a resist film (Example 3) using the phenyl-substituted benzyl cyanide oxime sulfonate compound of the present invention as a photoacid generator is a p-methoxybenzyl cyanide oxime sulfonate described in JP-A-6-67433. When the coloring by exposure and heating in the i-line (365 nm), h-line (405 nm) and g-line (435 nm) regions is smaller than that of a resist film (Comparative Example 1) produced using a photoacid generator composed of a compound The result to be obtained.

[Evaluation of photosensitivity as a photoacid generator]
<Example 4>
In a 50 mL eggplant-shaped flask, 3.4 g of NH108, 0.17 g of PSBC produced in Example 2 as a photoacid generator, 0.34 g of MW-390 (manufactured by Sanwa Chemical Co., Ltd.) as a crosslinking agent, interface 0.031 g of Megafac R-30 as an activator and 20 g of propylene glycol monomethyl ether as a solvent were added and stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform.

The resist composition was filtered using a 0.2 μm PTFE (polytetrafluoroethylene) filter, and the composition was applied onto a Bare Si substrate using a spin coater. Baking was performed (SB) on a hot plate at 110 ° C. for 1 minute to form a 1.02 μm-thick resist film (measured with an interference film thickness meter).
The resist film is irradiated with ultraviolet light having a light intensity of 365 mW / nm ^{2 at} a wavelength of 365 m for a predetermined time by an ultraviolet irradiation device, and then subjected to post-exposure heating (PEB) on a hot plate at a temperature of 120 ° C. for 1 minute. It was.
Thereafter, development was performed by immersing in a 2.38 mass% aqueous tetramethylammonium hydroxide (TMAH) solution for 1 minute, and then washed with running ultrapure water for 20 seconds.
When the film thickness at an exposure amount of 25 mJ / cm ² was measured, the residual film rate was 100%.

<Comparative example 2>
After preparing a composition in the same procedure as in Example 4 except that PAI-1003 (α- (n-propylsulfonyloxyimino) -4-methoxybenzylcyanide) was used as a photoacid generator, a resist film Preparation, UV irradiation, PEB, and development.
When the film thickness at an exposure amount of 25 mJ / cm ² was measured, the residual film rate was 96%.

  As described above, the results were obtained that the remaining film ratios of Example 4 and Comparative Example 2 were almost equal.

The aryl-substituted benzyl cyanide oxime sulfonate compound represented by the formula [1] of the present invention is a photoacid generator, particularly photoacid generator for i-line (365 nm), h-line (405 nm) and g-line (435 nm). By using the compound as a photoacid generator in a resist composition, it is possible to prepare a resist that realizes high transparency with high sensitivity and little coloration by exposure and subsequent heat treatment.
The photoacid generator of the present invention is used as a photoacid generator in optical materials such as TFT substrate planarization films in semiconductor electroluminescent devices and liquid crystal display devices, insulating films in semiconductor devices, and cores and cladding materials in optical waveguides. Is also useful.

Claims (6)

An aryl-substituted benzyl cyanide oxime sulfonate compound represented by the formula [1].

(Where
R ¹ represents an aryl group which may be substituted with a substituent which may contain an oxygen atom, a nitrogen atom and a sulfur atom,
R ² is a hydrogen atom, a halogen atom, a CN group, a NO ₂ group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or the number of carbon atoms Represents 1 to 5 haloalkoxy groups,
R ³ is substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, or W. An optionally substituted phenyl group, a naphthyl group optionally substituted with W, or an anthranyl group optionally substituted with W;
W is a halogen atom, CN group, NO ₂ group, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, haloalkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a haloalkoxy group. ) An aryl-substituted benzyl cyanide oxime sulfonate compound represented by the formula [2].

(Where
R ² and R ⁴ are each a hydrogen atom, a halogen atom, a CN group, a NO ₂ group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or Represents a haloalkoxy group having 1 to 5 carbon atoms,
R ³ is substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, or W. An optionally substituted phenyl group, a naphthyl group optionally substituted with W, or an anthranyl group optionally substituted with W;
W is a halogen atom, CN group, NO ₂ group, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, haloalkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a haloalkoxy group. ) The phenyl-substituted benzyl cyanide-based oxime sulfonate compound according to claim 2, wherein R ² and R ⁴ are hydrogen atoms. A photoacid generator comprising the aryl-substituted benzyl cyanide oxime sulfonate compound according to any one of claims 1 to 3. A photoacid generator for i-line, h-line and g-line comprising the aryl-substituted benzylcyanide-based oxime sulfonate compound according to any one of claims 1 to 3. A method for producing an aryl-substituted benzyl cyanide oxime sulfonate compound represented by the formula [1],
Formula [3]

(Where
R ¹ represents an aryl group which may be substituted with a substituent which may contain an oxygen atom, a nitrogen atom and a sulfur atom,
R ² represents a hydrogen atom, a halogen atom, CN groups, NO ₂ groups, alkyl groups having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group or a number of carbon atoms of 1 to 5 carbon atoms 1 to 5 haloalkoxy groups are represented. )
Is reacted with amyl nitrate in the presence of a base to give a compound of formula [4]

(In the formula, R ¹ and R ² represent the same meaning as described above.)
A process for producing an α-hydroxyiminoaryl-substituted benzylcyanide compound represented by formula (5), and the α-hydroxyiminoaryl-substituted benzylcyanide compound in the presence of a base:

Wherein R ³ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, W A phenyl group which may be substituted with, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W;
W is a halogen atom, CN group, NO ₂ group, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, haloalkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a haloalkoxy group. )
The method which consists of the process made to react with the sulfonyl chloride compound represented by these.