JP6605820B2 - Oxime sulfonate compound, photoacid generator, resist composition, cationic polymerization initiator, and cationic polymerizable composition - Google Patents

Description

  The present invention relates to an oxime sulfonate compound, a photoacid generator, a resist composition, a cationic polymerization initiator, and a cationic polymerizable composition, and more specifically, an oxime sulfonate compound useful as a photoacid generator and a cationic polymerization initiator, photo The present invention relates to an acid generator, a resist composition, a cationic polymerization initiator, and a cationic polymerizable composition.

  An oxime sulfonate compound is a substance that generates an acid upon irradiation with energy rays such as light. A photoacid generator in a resist composition for photolithography used for forming an electronic circuit such as a semiconductor, or a resin composition for optical modeling It is used as a cationic polymerization initiator in photopolymerizable compositions such as paints, coatings, adhesives and inks.

  Patent Document 1 discloses a highly sensitive, high resolution, chemically amplified positive and negative functional photoresist containing an oxime sulfonate having a predetermined structure. Patent Document 2 discloses an oxime sulfonate compound that is excellent in transparency to active light used for exposure, has high acid strength, and has good solubility in a resist solvent. Further, Patent Document 3 discloses a benzyl cyanide oxime sulfonate compound capable of producing a resist that realizes high sensitivity and high transparency.

Japanese Patent No. 3486850 Japanese Patent No. 3830183 Japanese Patent No. 5339028

However, the oxime sulfonate compound of Patent Document 1 is a compound represented by the general formula (I) in Patent Document 1, in which R ¹ -X, which is a substituent when R is a benzene ring, has R ¹ as a hydrogen atom and the number of carbon atoms Although it is disclosed that 1 to 4 alkyl groups, or phenyl groups, and X is an oxygen atom or a sulfur atom, the difference in properties and performance depending on the type of substitution, the number of substitutions, the position of substitution, etc. Not considered. Moreover, in the oxime sulfonate compound in Patent Document 2, in the general formula in Patent Document 2, it is only disclosed that R ¹ is a non-aromatic hydrocarbon group.

Further, the benzyl cyanide oxime sulfonate compound of Patent Document 3 is an alkoxy group having 1 to 10 carbon atoms as R ₁ and R ₂ which are substituents of the benzene ring in General Formula (I) of Patent Document 3. However, differences in properties and performance due to the type of substitution, the number of substitutions, the position of substitution, and the like have not been studied.

As a light source of a photo-acid generator used for a photoresist or a resin composition for stereolithography, an adhesive, an ink, and a cationic polymerization initiator, EUV (Extreme Ultra-Violet), X-ray, F ₂ , ArF Far ultraviolet rays such as KrF, I-line, H-line, and G-line, electron beam, and radiation are often used. When these light sources are used, those having low i-line (365 nm) absorption are advantageous because they have high deep-part curability and are useful in thick films. In addition, from the viewpoint of supporting high-definition patterning and shortening of the process, the photoresist or the cationic polymerization system contains a sufficient amount of acid generator or an acid generator with a good acid generation rate. It is desirable to use Accordingly, there is a demand for an acid generator having high solubility in an organic solvent and a sufficient acid generation rate.

  Accordingly, an object of the present invention is to provide an oxime sulfonate compound that has low absorption with respect to light having a wavelength of 365 nm, exhibits sufficient acid generation ability even in a film having a high depth curable property and a large film thickness, and has high solubility in an organic solvent. The object is to provide a photoacid generator, a resist composition, a cationic polymerization initiator, and a cationically polymerizable composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the oxime sulfonate compound having a predetermined structure is sufficiently acidic even in a film having a low absorption with respect to light having a wavelength of 365 nm, a high deep curability, and a large film thickness. The inventors have found that the developmental ability is expressed, and have completed the present invention.

That is, the oxime sulfonate compound of the present invention has the following general formula (I),
(In Formula (I), R ¹ is a linear, cyclic or branched alkyl group having 4 or more carbon atoms, and R ² is an aliphatic hydrocarbon group having 1 to 18 carbon atoms, 6 to 6 carbon atoms. 20 aryl groups, arylalkyl groups having 7 to 20 carbon atoms, aryl groups having 7 to 20 carbon atoms substituted with acyl groups, alicyclic hydrocarbon groups having 3 to 12 carbon atoms, and 10-camphoryl Group or the following general formula (II),
(In General Formula (II), Y ¹ represents a single bond or an alkanediyl group having 1 to 4 carbon atoms, and R ³ and R ⁴ are each independently an alkanediyl group having 2 to 6 carbon atoms, carbon Represents a halogenated alkanediyl group having 2 to 6 atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms, and R ⁵ is a straight chain having 1 to 18 carbon atoms or A branched alkyl group, a halogenated linear or branched alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 carbon atoms Represents a halogenated aryl group of -20, an arylalkyl group of 7-20 carbon atoms or a halogenated arylalkyl group of 7-20 carbon atoms, a and b represent 0 or 1, Either one is 1 And the aliphatic hydrocarbon group, aryl group, arylalkyl group, and alicyclic hydrocarbon group represented by R ² have no substituent, a halogen atom, or 1 to 1 carbon atoms. Substituted with a group selected from 4 halogenated alkyl groups, alkoxy groups having 1 to 18 carbon atoms and alkylthio groups having 1 to 18 carbon atoms. ).

In the oxime sulfonate compound of the present invention, R ¹ is preferably a linear, cyclic or branched alkyl group having 4 to 8 carbon atoms. In the oxime sulfonate compound of the present invention, R ² is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or 10-camphoryl. What is group is preferable. Furthermore, it is preferable that the oxime sulfonate compound of the present invention has a geometric isomer ratio of E: Z = 10: 90 or more in the general formula (I).

  The photoacid generator of the present invention comprises the oxime sulfonate compound of the present invention.

  The resist composition of the present invention comprises the photoacid generator of the present invention.

  The resist composition of the present invention is preferably an i-ray chemically amplified positive or negative resist composition. The resist composition of the present invention is suitable for forming a resist layer having a thickness of 10 to 200 μm.

  The cationic polymerization initiator of the present invention is characterized by comprising the oxime sulfonate compound of the present invention.

  The cationically polymerizable composition of the present invention comprises the cationic polymerization initiator of the present invention.

  Since the oxime sulfonate compound of the present invention has low absorption with respect to light having a wavelength of 365 nm and a good acid generation rate, according to the present invention, an oxime sulfonate compound useful as a photoacid generator and a cationic polymerization initiator, A photoacid generator, a resist composition, a cationic polymerization initiator, and a cationic polymerizable composition can be provided.

Compound no. FIG. 6 is a diagram showing the results of X-ray crystal structure analysis of Compound 6;

Hereinafter, the present invention will be described in detail based on embodiments.
The oxime sulfonate compound of the present invention has the following general formula (I),
Or have a structure. Here, in formula (I), R ¹ is a linear, cyclic or branched alkyl group having 4 or more carbon atoms, and R ² is an aliphatic hydrocarbon group having 1 to 18 carbon atoms, the number of carbon atoms An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 7 to 20 carbon atoms substituted with an acyl group, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, 10- Camphoryl group or the following general formula (II),
And the aliphatic hydrocarbon group, aryl group, arylalkyl group, and alicyclic hydrocarbon group represented by R ² have no substituent, are a halogen atom, or a halogen atom having 1 to 4 carbon atoms. And a group selected from an alkyl group having 1 to 18 carbon atoms and an alkylthio group having 1 to 18 carbon atoms.

Examples of the linear, cyclic or branched alkyl group having 4 or more carbon atoms represented by R ¹ include 1-butyl, 2-butyl, isobutyl, tertiary butyl, cyclobutyl, 1-pentyl, isopentyl, tertiary pentyl and neopentyl. , Cyclopentyl, 1-hexyl, 2-hexyl, 3-hexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, cyclohexyl, cyclohexylmethyl, tertiary heptyl, cycloheptyl, 1- Examples include octyl, isooctyl, tertiary octyl, cyclooctyl, 2-ethylhexyl, 1-nonyl, isononyl, 1-decyl and 1-dodecyl. Among these, a linear, cyclic or branched alkyl group having 4 to 8 carbon atoms is preferable because both solubility and acid generation rate are good.

R ² in the general formula (I) is substituted with an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or an acyl group. And an aryl group having 7 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, a 10-camphoryl group, or a group represented by the above general formula (II). Among these, the aliphatic hydrocarbon group, aryl group, arylalkyl group, and alicyclic hydrocarbon group may not have a substituent, and are a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, a carbon atom. It may be substituted with a group selected from an alkoxy group having 1 to 18 carbon atoms and an alkylthio group having 1 to 18 carbon atoms.

  Here, examples of the halogen atom as a substituent include chlorine, bromine, iodine, and fluorine. In addition, examples of the halogenated alkyl group having 1 to 4 carbon atoms include perfluoroalkyl groups such as a trifluoromethyl group.

  Examples of the alkoxy group having 1 to 18 carbon atoms include methoxy, ethoxy, propoxy, butoxy, tertiary butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, unde, siloxy, dodecyloxy, tridecyloxy Tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy and the like.

  Examples of the alkylthio group having 1 to 18 carbon atoms include methylthio, ethylthio, propylthio, isopropylthio, butylthio, secondary butylthio, tertiary butylthio, isobutylthio, pentylthio, isopentylthio, tertiary pentylthio, hexylthio, heptylthio, iso Heptylthio, tertiary heprotylthio, octylthio, isooctylthio, tertiary octylthio, 2-ethylhexylthio, nonylthio, decylthio, undecylthio, dodecylthio, tridecylthio, tetradecylthio, pentadecylthio, hexadecylthio, heptadecylthio, octadecylthio, etc. Can be mentioned.

Examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms that R ² can take include an alkenyl group, an alkyl group, a group in which a methylene group in the alkyl group is substituted with an alicyclic hydrocarbon group, and a methylene group in the alkyl group. Examples include a group in which the proton of the group is substituted with an alicyclic hydrocarbon group or a group in which an alicyclic hydrocarbon group is present at the end of an alkyl group.

  Examples of the alkenyl group include allyl and 2-methyl-2-propenyl, and examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, isobutyl, pentyl, isopentyl, and tertiary pentyl. , Hexyl, 2-hexyl, 3-hexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl , Dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hebrotadecyl, and octadecyl. Examples of the alicyclic hydrocarbon group include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and the like.

  Examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms substituted with a halogen atom include trifluoromethyl, pentafluoroethyl, 2-chloroethyl, 2-bromoethyl, heptafluoropropyl, 3-bromopropyl, and nonafluoro. Butyl, tridecafluorohexyl, heptadecafluorooctyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 1,1-difluoropropyl, 1,1,2,2-tetrafluoropropyl, 3 , 3,3-tripleopropyl, 2,2,3,3,3-pentafluoropropyl, norbornyl-1,1-difluoroethyl, norbornyltetrafluoroethyl, adamantane-1,1,2,2-tetra Halogens such as fluoropropyl and bicyclo [2.2.1] heptane-tetrafluoromethyl Include alkyl groups.

  Examples of the aliphatic hydrocarbon having 1 to 18 carbon atoms substituted with an alkoxy group having 1 to 18 carbon atoms include methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, butoxymethyl group, ethoxyethyl group Ethoxypropyl group, propoxybutyl group and the like.

  Examples of the aliphatic hydrocarbon having 1 to 18 carbon atoms substituted with an alkylthio group having 1 to 18 carbon atoms include 2-methylthioethyl, 4-methylthiobutyl, 4-butylthioethyl, and the like. Examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms substituted with an alkylthio group having 1 to 18 carbon atoms include 1,1,2,2-tetrafluoro-3-methylthiopropyl.

  Examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-pinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, and 4-butylphenyl. 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl 2,5-dimethylphenyl, 2,6-dimethylphenyl 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2, 6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5-di-tertiary Mill phenyl, 2,5-di-tert-octylphenyl, phenyl, biphenyl, 2,4,5-trimethylphenyl, 2,4,6-trimethylphenyl, 2,4,6-isopropylphenyl and the like.

  Examples of the aryl group having 6 to 20 carbon atoms substituted with a halogen atom include pentafluorophenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, 2,4-bis (trifluoromethyl) phenyl, 4-trifluoromethylphenyl, and bromoethyl. And phenyl.

  Examples of the aryl group having 6 to 20 carbon atoms substituted with an alkylthio group having 1 to 18 carbon atoms include 4-methylthiophenyl, 4-butylthiophenyl, 4-octylthiophenyl, and 4-dodecylthiophenyl. .

  Examples of the aryl group having 6 to 20 carbon atoms substituted by a halogen atom and an alkylthio group having 1 to 18 carbon atoms include 1,2,5,6-tetrafluoro-4-methylthiophenyl, 1,2,5, Examples include 6-tetrafluoro-4-butylthiophenyl and 1,2,5,6-tetrafluoro-4-dodecylthiophenyl.

  Examples of the arylalkyl group having 7 to 20 carbon atoms include benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl and the like.

  Examples of the arylalkyl group having 7 to 20 carbon atoms substituted with a halogen atom include pentafluorophenylmethyl, phenyldifluoromethyl, 2-phenyl-tetrafluoroethyl, 2- (pentafluorophenyl) ethyl and the like. .

  Examples of the arylalkyl group having 7 to 20 carbon atoms substituted with the alkylthio group having 1 to 18 carbon atoms include p-methylthiobenzyl.

  Examples of the arylalkyl group having 7 to 20 carbon atoms substituted with a halogen atom and an alkylthio group having 1 to 18 carbon atoms include 2,3,5,6-tetrafluoro-4-methylthiophenylethyl and the like.

  The number of carbon atoms of the aryl group having 7 to 20 carbon atoms substituted with an acyl group includes an acyl group. Examples include acetylphenyl, acetylnaphthyl, benzoylphenyl, 1-anthraquinolyl, and 2-anthraquinolyl.

  Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, and bicyclo [2. 1.1] hexane, bicyclo [2.2.1] heptane, bicyclo [3.2.1] octane, bicyclo [2.2.2] octane, and adamantane.

In the general formula (II), Y ¹ represents a single bond or an alkanediyl group having 1 to 4 carbon atoms, and R ³ and R ⁴ are each independently an alkanediyl group having 2 to 6 carbon atoms. Represents a halogenated alkanediyl group having 2 to 6 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms, and R ⁵ is a straight chain having 1 to 18 carbon atoms. Chain or branched alkyl group, halogenated linear or branched alkyl group having 1 to 18 carbon atoms, alicyclic hydrocarbon group having 3 to 12 carbon atoms, aryl group having 6 to 20 carbon atoms, carbon atom Represents a halogenated aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a halogenated arylalkyl group having 7 to 20 carbon atoms, a and b each represents 0 or 1; Either one of Is one.

General formula (II) is an ether group. In the general formula (II), the alkanediyl group having 1 to 4 carbon atoms represented by Y ¹ includes methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butylene, butane- 1,3-diyl, butane-2,3-diyl, butane-1,2-diyl may be mentioned.

Examples of the alkanediyl group having 2 to 6 carbon atoms represented by R ³ and R ⁴ include ethylene, propane-1,3-diyl, propane-1,2-diyl, butylene, butane-1,3-diyl, Butane-2,3-diyl, butane-1,2-diyl, pentane-1,5-diyl, pentane-1,3-diyl, pentane-1,4-diyl, pentane-2,3-diyl, hexane -1,6-diyl, hexane-1,2-diyl, hexane-1,3-diyl, hexane-1,4-diyl, hexane-2,5-diyl, hexane-2,4-diyl, hexane-3 , 4-diyl and the like.

  As the halogenated alkanediyl group having 2 to 6 carbon atoms, at least one proton in the above alkanediyl group having 2 to 6 carbon atoms is substituted with a halogen atom. Examples of the halogen atom include chlorine, bromine, iodine, and fluorine. For example, tetrafluoroethylene, 1,1-difluoroethylene, 1-fluoroethylene, 1,2-difluoroethylene, hexafluoropropane 1,3 diyl, 1,1,2,2-tetrafluoropropane-1,3 diyl, 1,1,2,2-tetrafluoropentane-1,5 diyl and the like.

In the general formula (II), the arylene group having 6 to 20 carbon atoms represented by R ³ and R ⁴ includes 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,5- Dimethyl-1,4-phenylene, 4,4′-biphenylene, diphenylmethane-4,4′-diyl 2,2-diphenylpropane-4,4′-diyl, naphthalene-1,2-diyl, naphthalene-1,3 -Diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl , Naphthalene-2,6-diyl, naphthalene-2,7-diyl and the like.

  As the halogenated arylene group having 6 to 20 carbon atoms, at least one proton in the above-described arylene group having 6 to 20 carbon atoms is substituted with a halogen atom. Examples of the halogen atom include chlorine, bromine, iodine, and fluorine. An example is tetrafluorophenylene.

In the general formula (II), the alkyl group having 1 to 18 carbon atoms represented by R ⁵ includes methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, sec-butyl, isobutyl, pentyl, isopentyl, 3-pentyl, hexyl, 2-hexyl, 3-hexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl , Dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl.

  The halogenated alkyl group having 1 to 18 carbon atoms is obtained by substituting at least one proton in the above alkyl group having 1 to 18 carbon atoms with a halogen atom. Examples of the halogen atom include chlorine, bromine, iodine, and fluorine. For example, triple chloromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, tridecafluorohexyl, heptadecafluorooctyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 1,1 -Difluoropropyl, 1,1,2,2-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1,1,2,2-tetrafluoro Examples include halogenated alkyl groups such as tetradecyl.

In the general formula (II), examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms represented by R ⁵ include cyclopropane, cyclobutane, cyclopentane, cyclohexane, Cycloheptane, cyclooctane, cyclodecane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane, bicyclo [3.2.1] octane, bicyclo [2.2.2] octane, adamantane Etc.

In the general formula (II), an aryl group having 6 to 20 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or 7 carbon atoms represented by R ⁵ Examples of the halogenated arylalkyl group of ˜20 include the groups exemplified as R ² .

As R ⁵ , an arylene group having 6 to 20 carbon atoms, an arylalkylene group having 7 to 20 carbon atoms or an alkylene group having 1 to 8 carbon atoms has a high acid generation ability and gives high sensitivity. Therefore, it is preferable.

  In the above general formula (I), it is preferable that the geometric isomer ratio of the oxime moiety is E: Z = 10: 90 or more because the acid generation ability is high and high sensitivity is imparted.

  Specific examples of the oxime sulfonate compound of the present invention include the following compound Nos. 1-No. 20 is mentioned.

R ² in the general formula (I) may be selected so as to release an appropriate organic sulfonic acid according to the application. For patterning with high sensitivity and high definition, arylsulfonic acid having strong acid strength and giving high sensitivity is most useful. Accordingly, R ² in the compound of the present invention is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a 10-camphoryl group. is there.

  The method for producing the oxime sulfonate compound of the present invention is not particularly limited, and can be synthesized by applying a known chemical reaction. For example, the method of synthesizing as follows is mentioned.

Here, in the above reaction formula, R ¹ and R ² represent the same group as in the general formula (1), and X and X ′ represent a halogen atom.

The oxime sulfonate compound of the present invention is an active energy ray such as EUV (Extreme Ultra-Violet), X-ray, F ₂ , ArF, KrF, i-ray, h-ray, g-ray, etc. It has the property of releasing a Lewis acid upon irradiation of, and can be decomposed or polymerized by acting on an acid-reactive organic substance. The oxime sulfonate compound of the present invention is used as a photoacid generator for a positive or negative photoresist, or for the production of flat plates, relief printing plates, printed circuit boards, ICs, LSIs, relief images and image duplications. It is useful as a wide range of cationic polymerization initiators such as image forming, photocurable ink, paint, adhesive and the like.

  When the oxime sulfonate compound of the present invention is used for an acid-reactive organic substance, the amount used is not particularly limited, but is preferably 0.05 with respect to 100 parts by mass of the acid-reactive organic substance. -100 mass parts, More preferably, it is a ratio of 0.5-20 mass parts. However, the blending amount can be increased or decreased from the above range depending on factors such as the nature of the acid-reactive organic substance, the light irradiation intensity, the time required for the reaction, the physical properties, and the cost.

  The resist composition of the present invention is particularly useful as a chemically amplified resist. Chemically amplified resists have a polarity change induced by the deprotection reaction of the resist base resin side chain, such as the cleavage of a chemical bond such as an ester group or an acetal group, by the action of an acid generated from a photoacid generator upon exposure. A positive resist to be solubilized in the developer and a chemical chain reaction such as polymerization or cross-linking occur, and the resist base resin is insolubilized in the developer by the cross-linking reaction or polarity change, and only the unexposed areas are selectively used during development. There are two types of negative resist to be removed.

  The resist base resin includes polyhydroxystyrene and derivatives thereof; polyacrylic acid and derivatives thereof; polymethacrylic acid and derivatives thereof; and two or more co-polymers formed from hydroxystyrene, acrylic acid, methacrylic acid and derivatives thereof Two or more copolymers selected from hydroxystyrene, styrene and derivatives thereof; three or more selected from polyolefins and derivatives thereof, cycloolefins and derivatives thereof, maleic anhydride, and acrylic acid and derivatives thereof Three or more copolymers selected from cycloolefin and derivatives thereof, maleimide, and acrylic acid and derivatives thereof; polynorbornene; one or more selected from the group consisting of metathesis ring-opening polymers Molecular polymer; Recone resins.

  The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the resist base resin is usually 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 100. , 000. In this case, when the Mw of the resist base resin is less than 1,000, the heat resistance as a resist tends to decrease. On the other hand, when the resist base resin exceeds 500,000, the developability and applicability as a resist tend to decrease.

  In the positive resist, a high molecular polymer in which a protective group that is decomposed by the action of an acid is introduced into the resist base resin is used. Protecting groups include tertiary alkyl groups, trialkylsilyl groups, oxoalkyl groups, aryl-substituted alkyl groups, heteroalicyclic groups such as tetrahydropyran-2-yl groups, tertiary alkylcarbonyl groups, tertiary alkylcarbonylalkyls And acetal groups such as a group, tertiary alkyloxycarbonyl group, tertiary alkyloxycarbonylalkyl group, alkoxyalkyl group, tetrahydropyranyl group, tetrahydrofuranyl, thiofuranyl group, and the like.

  In the negative resist, a resin obtained by reacting the resist base resin with a crosslinking agent is used. The crosslinking agent can be arbitrarily selected from those conventionally used as a crosslinking agent. For example, an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, a guanamine resin, or a glycoluril. -Formaldehyde resin, succinylamide-formaldehyde resin, ethylene urea-formaldehyde resin, etc. can be mentioned. These may be those obtained by reacting melamine, urea, guanamine, glycoluril, succinylamide, or ethyleneurea with formalin in boiling water to form methylol, or further reacting it with a lower alcohol to produce alkoxylation.

  A commercially available thing can also be used as said crosslinking agent, For example, Nicarak MX-750, Nicarac MW-30, Nicarac MX-290 (made by Sanwa Chemical Co., Ltd.) is mentioned.

  As long as the photoacid generator in the resist composition of the present invention contains the oxime sulfonate compound of the present invention as an essential component, other photoacid generators may be used as optional components. The use amount of the photoacid generator is usually 0.05 to 100 parts by mass, preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the resist base resin, from the viewpoint of ensuring sensitivity and developability as a resist. Part. When the amount of the photoacid generator used is less than 0.05 parts by mass, sensitivity and developability may be deteriorated.

  When using the oxime sulfonate compound of this invention as a photo-acid generator, you may use together with other photo-acid generators, such as an iodonium salt compound and a sulfonium compound. The amount used in combination is preferably 10 to 200 parts by mass with respect to 100 parts by mass of the oxime sulfonate compound of the present invention.

  Various additives may be added to the photoresist using the oxime sulfonate compound of the present invention as a photoacid generator. Various additives include base quenchers, acid multipliers, acid diffusing agents, base generators, inorganic fillers, organic fillers, pigments, dyes and other colorants, antifoaming agents, thickeners, flame retardants, and antioxidants. And various resin additives such as stabilizers and leveling agents. The use amount of these various additives is preferably 50% by mass or less in the resist composition of the present invention.

  The resist composition of the present invention is usually dissolved in a solvent so that the total solid content is usually 5 to 80% by mass, preferably 10 to 50% by mass, and then, for example, the pore size is 0.2 μm. Adjust by filtering through a degree filter. The resist composition of the present invention is prepared by a method such as mixing, dissolving or kneading a photoacid generator comprising the oxime sulfonate compound of the present invention, other photoacid generator, resist base resin and other optional components. Can do.

  As a light source used for exposure of the resist composition, g-line (436 nm), h-line (405 nm), i-line (365 nm), visible light, ultraviolet light, far-field, depending on the type of photoacid generator used. The oxime sulfonate compound of the present invention is appropriately selected from ultraviolet rays, X-rays, charged particle beams and the like. The far-ultraviolet rays such as ArF excimer laser (wavelength 193 nm) and KrF excimer laser (wavelength 248 nm), and synchrotron radiation are used. It can be suitably used in resists that use various types of radiation, such as X-rays such as X-rays, electron beams, and charged particle beams such as EUV.

  The resist composition of the present invention is coated on a substrate such as a glass substrate by an appropriate coating method such as a spinner or a coater, then exposed through a predetermined mask, and post-baked to improve the apparent sensitivity of the resist, A good resist pattern can be obtained by development. The thickness of the resist layer obtained by applying the resist composition of the present invention on a substrate and exposing and developing is preferably 0.1 to 250 μm, and more preferably 10 to 200 μm. Since the oxime sulfonate compound of the present invention has low absorption at i-line (365 nm), it has high deep-part curability and is useful in thick films.

  When the oxime sulfonate compound of the present invention is used as a cationic polymerization initiator in a cationic polymerizable composition, the cationic polymerizable composition is polymerized or crosslinked by a cationic polymerization initiator activated by light irradiation. One type or two or more types of cationically polymerizable compounds are mixed and used.

  Typical examples of the cationically polymerizable compound are epoxy compounds, oxetane compounds, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, spiro orthoester compounds, vinyl compounds, and the like, and one or more of these are used. be able to. Among them, epoxy compounds and oxetane compounds that are easy to obtain and convenient for handling are suitable.

  Of these, alicyclic epoxy compounds, aromatic epoxy compounds, aliphatic epoxy compounds, and the like are suitable as the epoxy compounds.

  Specific examples of the alicyclic epoxy compound include cyclohexene oxide and cyclopentene obtained by epoxidizing a polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. An oxide containing compound is mentioned. For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane Meta Oxane, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene bis (3,4 Epoxycyclohexanecarboxylate), epoxyhexahydrophthalate dioctyl, epoxyhexahydrophthalate di-2-ethylhexyl and the like.

  Commercially available products that can be suitably used as the alicyclic epoxy resin include UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200 (manufactured by Union Carbide), Celoxide 2021, Celoxide 2021P, Celoxide. 2081, Celoxide 2083, Celoxide 2085, Celoxide 2000, Celoxide 3000, Cyclomer A200, Cyclomer M100, Cyclomer M101, Eporide GT-301, Epolide GT-302, Eporide 401, Eporide 403, ETHB, Epolide HD300 (and above, Daicel) Chemical Industry Co., Ltd.), KRM-2110, KRM-2199 (manufactured by ADEKA Corporation) and the like.

  Among the alicyclic epoxy resins, an epoxy resin having a cyclohexene oxide structure is preferable in terms of curability (curing speed).

  Specific examples of the aromatic epoxy resin include polyhydric phenol having at least one aromatic ring or polyglycidyl ether of an alkylene oxide adduct thereof such as bisphenol A, bisphenol F, or further alkylene oxide. Examples thereof include glycidyl ether and epoxy novolac resin of the added compound.

  Furthermore, specific examples of the aliphatic epoxy resin were synthesized by vinyl polymerization of a polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof, a polyglycidyl ester of an aliphatic long-chain polybasic acid, glycidyl acrylate or glycidyl methacrylate. Examples thereof include homopolymers, copolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate and other vinyl monomers. As typical compounds, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, dipentaerythritol One or two or more kinds of glycidyl ethers of polyhydric alcohols such as hexaglycidyl ether, diglycidyl ether of polyethylene glycol and diglycidyl ether of polypropylene glycol, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerin Polyglycidyl ether of polyether polyol and diglycidyl ester of aliphatic long-chain dibasic acid obtained by adding alkylene oxide. It is. In addition, monoglycidyl ethers of higher aliphatic alcohols, phenols, cresols, butylphenols, monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy Examples include octyl stearate, butyl epoxy stearate, and epoxidized polybutadiene.

  Examples of commercially available products that can be suitably used as aromatic and aliphatic epoxy resins include Epicoat 801, Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd.), PY-306, 0163, DY-022 (and so forth, Ciba Specialty Chemicals). ), KRM-2720, EP-4100, EP-4000, EP-4080, EP-4900, ED-505, ED-506 (above, manufactured by ADEKA Corporation), Epolite M-1230, Epolite EHDG-L , Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF, Epolite 4000, Epolite 3002 Epolite FR-1500 (above, manufactured by Kyoeisha Chemical Co., Ltd.), Santo Tote ST0000, YD-716, YH-300, PG-202, PG-207, YD-172, YDPN638 (above, manufactured by Tohto Kasei Co., Ltd.), etc. Can be mentioned.

  Specific examples of the oxetane compound include the following compounds. 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-ethyl-3 -Oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl- 3-Oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl ( 3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3- Ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl) -3- Xetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromo Phenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1 , 3- (2-Methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-Ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bi [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol Bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane Tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-Echi -3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3- Oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl- 3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3- Til-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis Examples include (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, and the like. be able to. These oxetane compounds are particularly effective when used when flexibility is required.

  Specific examples of other compounds of the cationic polymerizable compound include cyclic lactone compounds such as β-propiolactone and ε-caprolactone; cyclic acetals such as trioxane, 1,3-dioxolane, and 1,3,6-trioxane cyclooctane. Compound; Cyclic thioether compound such as tetrahydrothiophene derivative; Spiro ortho ester compound obtained by reaction of the above-mentioned epoxy compound and lactone; ethylene glycol divinyl ether, alkyl vinyl ether, 2-chloroethyl vinyl ether, 2-hydroxyethyl vinyl ether, triethylene glycol Vinyl ether compounds such as divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, hydroxybutyl vinyl ether, propylene ether of propylene glycol, etc. , Vinyl compounds such as ethylenically unsaturated compounds such as styrene, vinylcyclohexene, isobutylene and polybutadiene; oxolane compounds such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran; thiirane compounds such as ethylene sulfide and thioepichlorohydrin; 1,3-pro Examples thereof include thietane compounds such as pin sulfide and 3,3-dimethylthietane; and well-known compounds such as silicones.

  The amount used when the oxime sulfonate compound of the present invention is used as a cationic polymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 100 parts by mass of the cationic polymerizable compound. Parts by mass to 5 parts by mass. If the amount used is less than 0.01 parts by mass, curing may be insufficient. On the other hand, if the amount exceeds 10 parts by mass, an increase in the effect of use is not obtained, and the physical properties of the cured product are adversely affected. May give.

  The oxime sulfonate compound of the present invention is used as a cationic polymerizable composition by blending various additives with the cationic polymerizable compound. Various additives include: crosslinking agents; organic solvents; photoradical initiators; thermal cation initiators; benzotriazole, triazine, and benzoate UV absorbers; phenol, phosphorus, and sulfur antioxidants; cationic Antistatic agent composed of surfactant, anionic surfactant, nonionic surfactant, amphoteric surfactant, etc .; halogen compound, phosphate ester compound, phosphate amide compound, melamine compound, fluororesin or Flame retardants such as metal oxides, (poly) phosphate melamine, (poly) phosphate piperazine; hydrocarbon-based, fatty acid-based, aliphatic alcohol-based, aliphatic ester-based, aliphatic amide-based or metal soap-based lubricants; Colorants such as dyes, pigments, carbon black; fumed silica, fine particle silica, silica, diatomaceous earth, clay, kaolin, diatomaceous earth Silica-based inorganic additives such as silica gel, calcium silicate, sericite, kaolinite, flint, feldspar powder, aragonite, attapulgite, talc, mica, minnesotite, pyrophyllite, silica and the like; fillers such as glass fiber and calcium carbonate; Examples include nucleating agents, crystallization agents such as crystallization accelerators, silane coupling agents, rubber elasticity imparting agents such as flexible polymers, basic compounds, acid proliferating agents, acid diffusing agents, and sensitizers. The total use amount of these various additives is 50% by mass or less in the cationically polymerizable composition of the present invention.

  Further, in order to facilitate the dissolution of the oxime sulfonate compound of the present invention in the cationically polymerizable compound, a suitable solvent (for example, propylene carbonate, carbitol, carbitol acetate, butyrolactone, propylene glycol-1-monomethyl ether-2) is used in advance. -Acetate etc.) can be dissolved and used.

  The above cationic polymerizable composition can be cured to a dry-to-touch state or a solvent-insoluble state usually after 0.1 seconds to several minutes by irradiation with energy rays such as ultraviolet rays. Any suitable energy ray may be used as long as it induces decomposition of the cationic polymerization initiator, but preferably an ultra-high, high, medium, low-pressure mercury lamp, xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, 2,000 obtained from tungsten lamp, excimer lamp, germicidal lamp, excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light emitting diode, CRT light source, etc. High energy rays such as electromagnetic wave energy having a wavelength of angstrom to 7,000 angstrom, electron beam, X-ray, and radiation are used.

  The exposure time to the energy rays depends on the strength of the energy rays, the coating thickness and the cationically polymerizable organic compound, but usually about 0.1 seconds to 10 seconds is sufficient. However, it is preferable to take a longer irradiation time for a relatively thick coating. From 0.1 seconds to several minutes after irradiation with energy rays, most compositions are dry to the touch by cationic polymerization. However, in some cases, heat energy from heating or a thermal head may be used in combination to promote cationic polymerization. preferable.

  Specific applications of the resist composition and cationic polymerizable composition of the present invention include optical filters, paints, coating agents, lining agents, adhesives, printing plates, insulating varnishes, insulating sheets, laminates, printed boards, and semiconductors. Sealant, molding material, putty, glass fiber impregnating agent, sealing agent for equipment, LED package, liquid crystal inlet, organic EL, optical element, electrical insulation, electronic parts, separation membrane, etc. Passivation films for semiconductors, solar cells, etc., thin film transistors (TFTs), liquid crystal display devices, organic EL display devices, interlayer insulation films used for printed circuit boards, surface protective films, guide pattern formations, base materials, printed circuit boards Or color TV, PC monitor, portable information terminal, color filter of CCD image sensor, electrode material for plasma display panel, printing ink, Medical composition, resin for optical modeling, both liquid and dry film, micro mechanical parts, glass fiber cable coating, holographic recording material, magnetic recording material, optical switch, plating mask, etching mask, stencil for screen printing, Touch panels such as transparent conductive films, MEMS elements, nanoimprint materials, two-dimensional and three-dimensional high-density mounting of semiconductor packages, decorative sheets, artificial nails, glass replacement optical films, electronic paper, optical disks, projectors and light Lens parts of lens sheets such as microlens arrays used for communication lasers, prism lens sheets used for backlights of liquid crystal display devices, Fresnel lens sheets used for screens of projection televisions, lenticular lens sheets, etc. Or a backlight using such a sheet, an optical lens such as a microlens / imaging lens, an optical element, an optical connector, an optical waveguide, an insulating packing, a heat shrink rubber tube, an O-ring, a sealant for a display device , Protective material, optical fiber protective material, adhesive, die bonding agent, high heat dissipation material, high heat-resistant seal material, solar cell / fuel cell / secondary battery material, battery solid electrolyte, insulation coating material, photocopier photosensitivity Drums, gas separation membranes, concrete protective materials, linings, soil injection agents, sealing agents, regenerator materials, glass coatings, foams and other civil engineering and building materials, tubes, sealing materials, coating materials, sterilization equipment sealing materials, It can be used for various applications such as contact lenses, oxygen-enriched membranes, biochips and other medical materials, automobile parts, and various machine parts. There is no particular limitation on its use.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, this invention is not limited to these.

<Synthesis of Oxumsulfonate Compound>
Compound No. 6, no. 10. No. 12, no. 13 and no. Preparation of 14 <Step 1> Preparation of alkylated compound To a 200 mL solution of 4-hydroxyphenylacetonitrile 0.19 mol dimethylacetamide 0.38 mol potassium carbonate and 0.22 mol alkyl halide were added at room temperature and stirred at 70 ° C. for 5 hours. did. The reaction solution was filtered to remove insolubles, washed with toluene / water, and then the solvent was distilled off from the organic layer under reduced pressure to obtain an alkylated product.

<Step 2> Production of oxime compound To a suspension of 0.37 mol of sodium hydroxide and 82 g of methanol, the alkylated product obtained in Step 1 and 0.22 mol of isobutyl nitrite were added dropwise over 30 minutes under ice cooling. And stirred for 2 hours under ice-cooling. Further, 0.14 mol of isobutyl nitrite was added dropwise, the temperature was raised to room temperature, and the mixture was stirred at 40 ° C. for 0.5 hour. The reaction solution was cooled to ice cooling, acidified with 35% hydrochloric acid, and extracted with toluene. The organic layer was washed with water three times, neutralized and then washed with saturated brine. The solvent was distilled off under reduced pressure to obtain an oxime product.

<Step 3> Production of target product To a 120 mL toluene solution of the oxime obtained in Step 2, 0.28 mol of triethylamine was added under ice cooling, 0.19 mol of various sulfonic acid chlorides were added, and the temperature was raised to room temperature. Water was added to the reaction solution stirred for a period of time, and the organic layer was separated, washed with water, and the solvent was distilled off under reduced pressure. Recrystallization was performed twice from acetonitrile / isopropanol and dried at 40 ° C. under reduced pressure to obtain the desired product. Various analyzes were performed to confirm that it was the target product. The results of analysis are shown in Tables 1 to 3.

<Examples 1-1 to 1-3 and Comparative Examples 1-1 and 1-2>
Preparation of Positive Resist Composition and Patterning Evaluation According to the composition shown in Table 4 below, resist solutions having a solid content of 20% were prepared so that the compound concentrations as acid generators were 3%, 5%, and 10%. After filtering with a 0.1 μm microfilter, this was coated on a glass substrate with a spin coater, dried at 90 ° C. for 90 seconds, and then exposed to 0 to 100 mJ / cm ² through a mask having a 20 μm pattern opening. The light was irradiated. The film was baked at 120 ° C. for 90 seconds, developed by immersing in an aqueous 2.38% tetramethylammonium hydroxide solution for 30 seconds, washed with ion-exchanged water, and the remaining film ratio for each exposure amount was measured. The results are shown in Table 5.
In addition, the remaining film rate was calculated | required by the following formula.
(Film thickness (μm)) / (initial film thickness (μm)) × 100 = (remaining film ratio)

* 1: Resin having a structure in which 50 mol% of poly (p-hydroxystyrene) is substituted with a t-butoxycarbonyl group (Mw = 18,000)

  From Table 5 above, it was confirmed that the compound of the present invention functions sufficiently as an acid generator even when the exposure amount is low as compared with the comparative compound.

Example 2 Preparation and Evaluation of Negative Resist Composition 20 g of Nippon Kayaku EPPN-201 and 0.4 g of a cross-linking agent (tetramethoxymethyl glycouril) were dissolved in 100 g of methyl ethyl ketone (MEK) to prepare a resin solution. , Compound No. 6 was dissolved in 8.00 g of this resin solution to prepare a resist solution. This was coated on a glass substrate with a spin coater, dried at 90 ° C. for 90 seconds, and then exposed to light having a wavelength of 365 nm. The film was baked at 110 ° C. for 90 seconds, developed by immersing in a 2.38% tetramethylammonium hydroxide aqueous solution for 30 seconds, and washed with pure water. After leaving at room temperature for 24 hours, the coating film was rubbed with a cotton swab to which methyl ethyl ketone was attached. As a result, even after 200 reciprocations, the coating film was not attacked, and it was confirmed that curing was sufficiently advanced.

Example 3 Production and Evaluation of Cationic Polymerizable Composition Compound No. was mixed with 80 g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and 20 g of 1,4-butanediol diglycidyl ether. . 4 mmol of 6 was added and stirred well to make uniform. This was coated on aluminum coated paper with a # 3 bar coater. This was irradiated with light from an 80 W / cm high-pressure mercury lamp using a light irradiation device with a belt conveyor. The distance from the ramp to the belt conveyor was 10 cm, and the line speed of the belt conveyor was 8 m / min. After leaving at room temperature for 24 hours after curing, the coating film was rubbed with a cotton swab to which methyl ethyl ketone was attached. As a result, the coating film was not affected even after 200 reciprocations, and it was confirmed that the curing had progressed sufficiently.

[Examples 4-1 to 4-5 and Comparative Examples 4-1 to 4-3] Evaluation of UV absorption spectrum 6, no. 10, no. 12, no. 13 and no. 14 was dissolved in acetonitrile, and the absorption spectrum was measured with a sunlight photometer U-3010. The values of λmax and ε (molar extinction coefficient) in the range of 300 nm to 400 nm and ε at 365 nm were shown. The results are shown in Table 6.

[Examples 5-1 to 5-4 and Comparative Examples 5-1 to 5-4] Solubility Evaluation The solubility of propylene glycol monomethyl ether acetate (PGMEA), cyclopentanone and gamma butyrolactone at 25 ° C. was evaluated. . The solubility was expressed as the concentration at which no undissolved residue was generated, with the concentration increasing in increments of 1% by mass. The results are shown in Table 7.

[Examples 6-1 to 6-5 and Comparative Examples 6-1 to 6-4] Acid generation rate 6, no. 10, no. 12, no. 13 and no. 14 and comparative compound no. 1-No. A 1.5 × 10 ⁻⁴ mol / L acetonitrile / water mixed solution (acetonitrile / water = 9/1: volume ratio) was prepared for No. 4, and 5.0 mL was accurately placed in a petri dish with an inner diameter of 50 mm, and HOYA CANDEO With a UV lamp manufactured by OPTRONICS, 100 mW / cm ² of UV was irradiated using a cut filter that transmits only a wavelength around 365 nm. The irradiation time was set to 3 points of 1 second, 3 seconds, and 5 seconds, respectively. After the exposure, the photodecomposition rate (%) was calculated using HPLC to obtain the acid generation rate. The results are shown in Table 8. In addition, Compound No. 6, no. 10, no. 12, no. 13 and no. 14 and comparative compound no. 1-No. The optical purity of 4 is 100%.

  As is apparent from Tables 6 to 8, the compound of the present invention has a high transmittance at 365 nm, sufficiently expresses acid generating ability even in a film having a large film thickness, and all have high solubility in various solvents. In addition, it was confirmed that the acid generation ability was large.

[Example 7] Acid generation rate of geometric isomer Compound No. 10 and compound no. The acid generation rate was measured in the same manner as in Example 3 for 14 (E + Z) body and Z body. The results are shown in Table 9. The geometric isomer ratio was confirmed by ¹ H-NMR. In addition, Compound No. It was confirmed by X-ray crystal structure analysis that 6 is a Z body. The results are shown in the figure below.

From Table 9 above, compound no. The (E + Z) isomer and the Z isomer of No. 10 have a high acid generating ability because the geometrical isomer ratio at the oxime position is E: Z = 10: 90 or more. It is clear that the 14 Z-form has higher acid generating ability than the (E + Z) -form in which the geometric isomer ratio at the oxime position is less than E: Z = 10: 90.

Claims (9)

The following general formula (I),
(In formula (I), R ¹ is a linear, cyclic or branched alkyl group having 4 or more carbon atoms, and R ² is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted. An oxime sulfonate compound represented by a substituted alkyl group having 1 to 8 carbon atoms or a 10-camphoryl group . The oxime sulfonate compound according to claim 1, wherein R ¹ is a linear, cyclic or branched alkyl group having 4 to 8 carbon atoms. The oxime sulfonate compound according to claim 1 or 2, wherein, in the general formula (I), the geometric isomer ratio of the oxime moiety is E: Z = 10: 90 or more. A photoacid generator comprising the oxime sulfonate compound according to any one of claims 1 to 3 . A resist composition comprising the photoacid generator according to claim 4 . 6. The resist composition according to claim 5 , which is a chemical amplification type positive type or negative type resist composition for i-line. The resist composition according to claim 6 , wherein a resist layer having a thickness of 10 to 200 μm is formed. A cationic polymerization initiator comprising the oxime sulfonate compound according to any one of claims 1 to 3 . A cationically polymerizable composition comprising the cationic polymerization initiator according to claim 8 .