JP5517658B2 - Sulfonium salt, photoacid generator, curable composition, and positive photoresist composition - Google Patents

Description

  The present invention relates firstly to a sulfonium salt, and secondly to a photoacid generator, more specifically, when an active energy ray such as light, electron beam or X-ray is applied to cure a cationically polymerizable compound. The present invention relates to a photoacid generator containing a suitable specific sulfonium salt. Thirdly, the present invention relates to a curable composition containing the photoacid generator and a cured product obtained by curing the composition. Fourthly, the present invention relates to a chemically amplified positive photoresist composition containing the photoacid generator and a method for producing a resist pattern using the same.

  Photofabrication, which is currently the mainstream of precision microfabrication technology, is the application of a photosensitive resin composition to the surface of a workpiece to form a coating film, which is then patterned using photolithography technology. A generic term for technologies for manufacturing various precision parts such as semiconductor packages by performing chemical forming, electrolytic etching, and / or electroforming mainly composed of electroplating as a mask.

  Conventionally, as a photoacid generator for use in curing a cationically polymerizable compound such as an epoxy compound by applying an active energy ray such as light, electron beam or X-ray, a triarylsulfonium salt (Patent Document 1), naphthalene A phenacylsulfonium salt having a skeleton (Patent Document 2), a dialkylbenzylsulfonium salt (Patent Document 3), and a sulfonium salt having a thioxanthone skeleton introduced (Patent Document 4) are known.

  In a photolithography process using a photoresist, i-line having a wavelength of 365 nm is currently widely used as exposure light. For this reason, an inexpensive medium-pressure / high-pressure mercury lamp that exhibits good emission intensity can be used as an irradiation light source, and LED lamps having an emission wavelength in the i-line region (360 nm to 390 nm) have recently become widespread. It can also be mentioned. Therefore, the need for a photoacid generator exhibiting high sensitivity to i-line is expected to increase further in the future.

  However, among existing photoacid generators, triarylsulfonium salts (Patent Document 1), phenacylsulfonium salts having a naphthalene skeleton (Patent Document 2) and dialkylbenzylsulfonium salts (Patent Document 3) are sensitive to i-line. Because of its low nature, it is necessary to use a sensitizer together to increase sensitivity. In addition, the sulfonium salt having a thioxanthone skeleton introduced therein (Patent Document 4) has a problem that the absorption rate is too large for i-line, and therefore, light curing does not pass to the deep part during thick film curing, resulting in a problem of poor curing.

  Furthermore, in recent years, with the further miniaturization of electronic devices, high-density mounting of semiconductor packages has progressed. Multi-pin thin-film mounting and downsizing of packages, mounting based on flip-chip 2D and 3D mounting technology The density is improved. As connection terminals for such high-density mounting technology, for example, protruding electrodes (mounting terminals) such as bumps protruding on the package, metal posts that connect the rewiring extending from the peripheral terminals on the wafer and the mounting terminals, etc. It is arranged with high accuracy on the substrate.

  As a material used for such high-precision photofabrication, there is a positive photosensitive resin composition having a naphthoquinonediazide group-containing compound (see Patent Document 5). However, this material has a problem of low sensitivity to i-line (365 nm) which is an exposure light source generally used in the photolithography process.

  A chemically amplified positive resist composition using an oxime sulfonate compound as an acid generator (see Patent Document 6) has been proposed as a photosensitive resin composition that has improved the above problems. This is because the acid is generated from the photoacid generator by irradiation (exposure), and the diffusion of the acid and the acid catalytic reaction are promoted by the heat treatment after the exposure, thereby improving the solubility of the base resin in the resin composition in the alkali. The base resin that was insoluble in alkali before exposure is solubilized in alkali, and is called a positive photoresist. However, since this resist composition has poor storage stability, the management of the storage temperature of the resist composition is complicated and has practical problems.

  Further, a chemically amplified positive resist composition using a triarylsulfonium salt compound as a photoacid generator is also known (Non-patent Documents 1 and 2, Patent Documents 7 and 8), but has good storage stability. However, the sensitivity to i-line is not sufficient.

Japanese Patent Laid-Open No. 50-151997 JP-A-9-118663 JP-A-2-178303 JP-A-8-165290 JP 2002-258479 A JP 2000-66385 A JP 2003-231673 A JP 2002-193925 A

M.J.O'Brien, J.V.Crivello, SPIE Vol. 920, Advances in Resist Technology and Processing, p42 (1988). H.ITO, SPIE Vol.920, Advances in Resist Technology and Processing, p33, (1988).

In the above background, the first object of the present invention is to provide a new sulfonium salt having high photosensitivity to i-line.
The second object of the present invention is to be stored in a blend with a cationically polymerizable compound such as an epoxy compound having high photosensitivity to i-line and high compatibility with a cationically polymerizable compound such as an epoxy compound. A new acid generator comprising a sulfonium salt having excellent stability is provided.
The third object of the present invention is to provide an energy ray curable composition such as a negative resist composition and a cured product using the acid generator.
A fourth object of the present invention is to provide a chemically amplified positive photoresist composition and a method for producing a resist pattern, which can obtain a resist having good storage stability and high sensitivity to i-line. It is to be.

The inventor has synthesized a sulfonium salt represented by the following formula (1) and found that it is suitable for each of the above purposes.
That is, the present invention provides a sulfonium salt represented by the formula (1).

[In the formula (1), R ^{1 to} R ⁴ each independently represent an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, Acyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, substituted Represents an amino group, a cyano group, a nitro group or a halogen atom, and Ra, Rb and Rc each independently represent a phenyl group which may be substituted or an alkyl group which may be substituted; m ¹ ˜m ⁴ represents the number of R ^{1 to} R ⁴ , respectively. M ¹ , m ² and m ⁴ are integers from 0 to 4, and m ³ is an integer from 0 to 5. X ⁻ represents a monovalent polyatomic anion. ]

The present invention also provides a photoacid generator characterized by containing the sulfonium salt.

  Moreover, this invention is an energy beam curable composition characterized by containing the said photo-acid generator and a cationically polymerizable compound.

  Furthermore, the present invention is a cured product obtained by curing the energy beam curable composition.

  Furthermore, the present invention provides a chemically amplified positive photoresist composition comprising the photoacid generator and a component (B) which is a resin whose solubility in alkali is increased by the action of an acid. is there.

  Furthermore, the present invention provides a laminating step of laminating a photoresist layer having a thickness of 5 to 150 μm made of any one of the above chemically amplified positive photoresist compositions to obtain a photoresist laminate, A method for producing a resist pattern, comprising: an exposure step of selectively irradiating light or radiation with a site; and a development step of developing a photoresist laminate to obtain a resist pattern after the exposure step.

The sulfonium salt of the present invention has excellent photosensitivity to active energy rays such as visible light, ultraviolet rays, electron beams and X-rays, has high compatibility with cationically polymerizable compounds such as epoxy compounds, and cationic polymerization of epoxy compounds and the like. Storage stability is excellent in a blend with a functional compound.
The photoacid generator of the present invention is excellent in curability by the action of ultraviolet light, particularly i-ray, when used for curing a cationically polymerizable compound, and cures a cationically polymerizable compound without using a sensitizer. Can be made. The photoacid generator of the present invention is also excellent in thick film curability.
Since the energy beam curable composition of the present invention contains the above-mentioned photoacid generator, it can be cured with ultraviolet light. In addition, the energy ray-curable composition of the present invention has high storage stability and does not require the use of a sensitizer, and thus is excellent in cost and workability.
Since the cured product of the present invention can be obtained without using a sensitizer, there is no problem of coloring or deterioration caused by the remaining sensitizer.

  Hereinafter, embodiments of the present invention will be described in detail. In the present specification, the term “alkyl group” includes a cycloalkyl group.

In the formula (1), among R ^{1 to} R ⁴ , the alkyl group is a linear alkyl group having 1 to 18 carbon atoms (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.), C3-C18 branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl and isooctadecyl), and cycloalkyl groups having 3 to 18 carbon atoms (such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and 4-decylcyclohexyl).

In the formula (1), among R ^{1 to} R ⁴ , the alkoxy group is a linear alkoxy group having 1 to 18 carbon atoms or a branched alkoxy group having 3 to 18 carbon atoms (methoxy, ethoxy, propoxy, iso Propoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy, octadecyloxy, etc.).

In the formula (1), among R ^{1 to} R ⁴ , the alkylcarbonyl group is a linear alkylcarbonyl group having 2 to 18 carbon atoms or a branched alkylcarbonyl group having 4 to 18 carbon atoms (acetyl, propionyl, butanoyl). , 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl and octadecanoyl).

In Formula (1), among R ^{1 to} R ⁴ , examples of the arylcarbonyl group include arylcarbonyl groups having 7 to 11 carbon atoms (such as benzoyl and naphthoyl).

In the formula (1), among R ^{1 to} R ⁴ , the alkoxycarbonyl group is a linear alkoxycarbonyl group having 2 to 19 carbon atoms or a branched alkoxycarbonyl group having 4 to 19 carbon atoms (methoxycarbonyl, ethoxycarbonyl, Propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, octadecyloxycarbonyl, etc.).

In formula (1), among R ^{1 to} R ⁴ , examples of the aryloxycarbonyl group include aryloxycarbonyl groups having 7 to 11 carbon atoms (such as phenoxycarbonyl and naphthoxycarbonyl).

In Formula (1), among R ^{1 to} R ⁴ , examples of the arylthiocarbonyl group include arylthiocarbonyl groups having 7 to 11 carbon atoms (such as phenylthiocarbonyl and naphthoxythiocarbonyl).

In the formula (1), among R ^{1 to} R ⁴ , as the acyloxy group, a linear acyloxy group having 2 to 19 carbon atoms or a branched acyloxy group having 4 to 19 carbon atoms (acetoxy, ethylcarbonyloxy, propylcarbonyl) Oxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, octadecylcarbonyloxy and the like.

In Formula (1), among R ^{1 to} R ⁴ , the arylthio group is an arylthio group having 6 to 20 carbon atoms (phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2- Chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2 -Hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4- [4- (phenylthio) benzoyl] phenylthio, 4- [4- (phenylthio) ) Phenoxy] phenylthio, 4- [4- (phen Ruthio) phenyl] phenylthio, 4- (phenylthio) phenylthio, 4-benzoylphenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl 2-methylthiophenylthio, 4- (4-methylthiobenzoyl) phenylthio, 4- (2-methylthiobenzoyl) phenylthio, 4- (p-methylbenzoyl) phenylthio, 4- (p-ethylbenzoyl) phenylthio 4- (p -Isopropylbenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) phenylthio and the like.

In formula (1), among R ^{1 to} R ⁴ , the alkylthio group is a linear alkylthio group having 1 to 18 carbon atoms or a branched alkylthio group having 3 to 18 carbon atoms (methylthio, ethylthio, propylthio, isopropylthio). , Butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio and isooctadecylthio).

In Formula (1), among R ^{1 to} R ⁴ , examples of the aryl group include aryl groups having 6 to 10 carbon atoms (such as phenyl, tolyl, dimethylphenyl, and naphthyl).

In the formula (1), among R ^{1 to} R ⁴ , the heterocyclic hydrocarbon group is a heterocyclic hydrocarbon group having 4 to 20 carbon atoms (thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, Pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thiantenyl, phenoxazinyl, phenoxathinyl, chromanyl, isochromonyl, dibenzothionyl, dibenzothienyl Dibenzofuranyl and the like).

In Formula (1), among R ^{1 to} R ⁴ , examples of the aryloxy group include aryloxy groups having 6 to 10 carbon atoms (such as phenoxy and naphthyloxy).

In the formula (1), among R ^{1 to} R ⁴ , the alkylsulfinyl group is a linear alkylsulfinyl group having 1 to 18 carbon atoms or a branched sulfinyl group having 3 to 18 carbon atoms (methylsulfinyl, ethylsulfinyl, Propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, isooctadecylsulfinyl, etc.) .

In Formula (1), among R ^{1 to} R ⁴ , examples of the arylsulfinyl group include arylsulfinyl groups having 6 to 10 carbon atoms (such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl).

In formula (1), among R ^{1 to} R ⁴ , the alkylsulfonyl group is a linear alkylsulfonyl group having 1 to 18 carbon atoms or a branched alkylsulfonyl group having 3 to 18 carbon atoms (methylsulfonyl, ethylsulfonyl). , Propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl, octadecylsulfonyl, etc.) .

In formula (1), among R ^{1 to} R ⁴ , examples of the arylsulfonyl group include arylsulfonyl groups having 6 to 10 carbon atoms (phenylsulfonyl, tolylsulfonyl (tosyl group), naphthylsulfonyl, etc.) and the like.

In formula (1), among R ^{1 to} R ⁴ , examples of the hydroxy (poly) alkyleneoxy group include a hydroxy (poly) alkyleneoxy group represented by formula (2).
HO (-AO) q- (2)
[AO represents an ethyleneoxy group and / or a propyleneoxy group, and q represents an integer of 1 to 5. ]

In formula (1), among R ^{1 to} R ⁴ , the amino group which may be substituted includes an amino group (—NH ₂ ) and a substituted amino group having 1 to 15 carbon atoms (methylamino, dimethylamino, ethylamino). , Methylethylamino, diethylamino, n-propylamino, methyl-n-propylamino, ethyl-n-propylamino, n-propylamino, isopropylamino, isopropylmethylamino, isopropylethylamino, diisopropylamino, phenylamino, diphenylamino , Methylphenylamino, ethylphenylamino, n-propylphenylamino, isopropylphenylamino, etc.).

In Formula (1), among R ^{1 to} R ⁴ , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the formula (1), R ^{1 to} R ⁴ are independent of each other, and therefore may be the same as or different from each other.

Of R ^{1 to} R ⁴ , an alkyl group, an alkoxy group, an alkylcarbonyl group, and a halogen atom are preferable, and a methyl group, a methoxy group, and an acetyl group are particularly preferable.

In the formula (1), Ra, Rb and Rc represent a phenyl group which may be substituted or an alkyl group which may be substituted. Examples of the substituent include an alkyl group, a hydroxyl group, an alkoxy group, a cyano group, a nitro group, and a halogen atom, and the definitions of these substituents are the same as those for R ^{1 to} R ⁴ . Of these, a phenyl group and a methyl group are particularly preferable.

In formula (1), m ^{1 to} m ⁴ represent the number of R ^{1 to} R ⁴ , respectively, m ¹ , m ² and m ⁴ are integers of 0 to 4, preferably 0 to 3, more preferably 0 to 2, particularly preferably 0 or 1. M ³ is an integer of 0 to 5, preferably 0 to 3, more preferably 0 to 2, and particularly preferably 0 or 1. When m ^{1 to} m ⁴ are in these preferable ranges, the photosensitivity of the sulfonium salt is further improved.

In the formula (1), X ⁻ represents an acid generated by irradiating the sulfonium salt of the present invention with an active energy ray such as light (visible light, ultraviolet ray, far ultraviolet ray) or radiation (electron beam, X ray, etc.) ( An anion corresponding to HX). X ⁻ is not limited except that it is a monovalent polyatomic anion, but MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ⁵ _c BY _4-c ⁻ , R ⁵ _c GaY _{4 ^{-c -, R 6 SO 3 -}} , (R 6 SO 2) 3 C - or _{^{(R 6 SO 2) 2 N}} - anion represented by are preferred.

M represents a phosphorus atom, a boron atom, or an antimony atom.
Y represents a halogen atom (a fluorine atom is preferred).

Rf represents an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms) in which 80 mol% or more of hydrogen atoms are substituted with fluorine atoms. Examples of the alkyl group to be Rf by fluorine substitution include linear alkyl groups (such as methyl, ethyl, propyl, butyl, pentyl and octyl), branched chain alkyl groups (such as isopropyl, isobutyl, sec-butyl and tert-butyl) and And cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and the like. The ratio of hydrogen atoms of these alkyl groups substituted by fluorine atoms in Rf is preferably 80 mol% or more based on the number of moles of hydrogen atoms that the original alkyl group had, more preferably 90%. % Or more, particularly preferably 100%. When the ratio of substitution by fluorine atoms is within these preferred ranges, the photosensitivity of the sulfonium salt is further improved. As particularly preferred Rf, CF ₃ −, CF ₃ CF ₂ —, (CF ₃ ) ₂ CF—, CF ₃ CF ₂ CF ₂ —, CF ₃ CF ₂ CF ₂ CF ₂ —, (CF ₃ ) ₂ CFCF ₂ — , CF ₃ CF ₂ (CF ₃ ) CF— and (CF ₃ ) ₃ C—. The b Rf's are independent of each other, and therefore may be the same as or different from each other.

  P represents a phosphorus atom, and F represents a fluorine atom.

R ⁵ represents a phenyl group in which a part of hydrogen atoms is substituted with at least one element or electron withdrawing group. Examples of such one element include a halogen atom, and include a fluorine atom, a chlorine atom and a bromine atom. Examples of the electron withdrawing group include a trifluoromethyl group, a nitro group, and a cyano group. Of these, a phenyl group in which one hydrogen atom is substituted with a fluorine atom or a trifluoromethyl group is preferable. The c R ^{5 s} are independent of each other, and therefore may be the same as or different from each other.

  B represents a boron atom, and Ga represents a gallium atom.

R ⁶ represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and the alkyl group and the perfluoroalkyl group are linear or branched. Alternatively, the aryl group may be unsubstituted or may have a substituent.

  S represents a sulfur atom, O represents an oxygen atom, C represents a carbon atom, and N represents a nitrogen atom. a represents an integer of 4 to 6. b is preferably an integer of 1 to 5, more preferably 2 to 4, and particularly preferably 2 to 3. c is preferably an integer of 1 to 4, more preferably 4.

Examples of the anion represented by MY _a ⁻ include SbF ₆ ⁻ , PF ₆ ⁻ and BF ₄ ⁻ .

Examples of the anion represented by (Rf) _b PF _6-b ^— include (CF ₃ CF ₂ ) ₂ PF ₄ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ CF) ₂ PF ₄ ⁻ , ((CF ₃ ) ₂ CF) ₃ PF ₃ ⁻ , (CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ⁻ , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ⁻ , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ⁻ , (CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ^— and (CF ₃ CF ₂ CF ₂ CF ₂ ) ₃ PF ₃ ^— It is done. Of these, (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ CF) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ CF) ₂ PF ₄ ⁻ , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ^— and ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ^— are preferred.

Examples of the anion represented ^{_{by, (C 6 F 5) 4}} B - - R 5 c BY 4-c, ((CF 3) 2 C 6 H 3) 4 B -, (CF 3 C 6 H 4) 4 B _{^{-, (C 6 F 5)}} 2 BF 2 -, C 6 F 5 BF 3 - and _{(C 6 H 3 F 2)} 4 B - , and the like. Of _{these, (C 6 F 5) 4} B - , and _{((CF 3) 2 C 6} H 3) 4 B - are preferred.

Examples of the anion represented ^{_{by, (C 6 F 5) 4}} Ga - - R 5 c GaY 4-c, ((CF 3) 2 C 6 H 3) 4 Ga -, (CF 3 C 6 H 4) 4 Ga _{^{-, (C 6 F 5)}} 2 GaF 2 -, C 6 F 5 GaF 3 - and _{(C 6 H 3 F 2)} 4 Ga - , and the like. Of _{these, (C 6 F 5) 4} Ga - and _{((CF 3) 2 C 6} H 3) 4 Ga - are preferred.

Examples of the anion represented by R ⁶ SO ₃ ^— include trifluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, heptafluoropropanesulfonic acid anion, nonafluorobutanesulfonic acid anion, pentafluorophenylsulfonic acid anion, p-toluenesulfone. Examples include an acid anion, benzenesulfonate anion, camphorsulfonate anion, methanesulfonate anion, ethanesulfonate anion, propanesulfonate anion and butanesulfonate anion. Of these, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, benzenesulfonate anion and p-toluenesulfonate anion are preferred.

Examples of the anion represented by (R ⁶ SO ₂ ) ₃ C ⁻ include (CF ₃ SO ₂ ) ₃ C ⁻ , (C ₂ F ₅ SO ₂ ) ₃ C ⁻ , (C ₃ F ₇ SO ₂ ) ₃ C ⁻ and _{(C 4 F 9 SO 2)} 3 C - , and the like.

Examples of the anion represented by (R ⁶ SO ₂ ) ₂ N ⁻ include (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , (C ₃ F ₇ SO ₂ ) ₂ N ⁻ and _{(C 4 F 9 SO 2)} 2 N - , and the like.

Examples of the monovalent polyatomic anion include MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ⁵ _c BY _4-c ⁻ , R ⁵ _c GaY _4-c ⁻ , R ⁶ SO ₃ ⁻ , (R ⁶ In addition to the anion represented by SO ₂ ) ₃ C ⁻ or (R ⁶ SO ₂ ) ₂ N ⁻ , perhalogenate ions (ClO ₄ ⁻ , BrO ₄ ⁻ etc.), halogenated sulfonate ions (FSO ₃ ⁻ , ClSO ₃ ⁻ etc.), sulfate ions (CH ₃ SO ₄ ⁻ , CF ₃ SO ₄ ⁻ , HSO ₄ ⁻ etc.), carbonate ions (HCO ₃ ⁻ , CH ₃ CO ₃ ⁻ etc.), aluminate ions (AlCl ₄ ⁻ , AlF ₄ ^-, etc.), hexafluoro bismuthate ions (BiF ₆ ^-), carboxylate ion ^{_{(CH 3 COO -, CF 3}} COO -, C 6 H 5 COO -, CH 3 C 6 H 4 COO -, C 6 F 5 CO ^{_{-, CF 3 C 6 H 4}} COO - , etc.), an aryl boronic acid ions ^{_{(B (C 6 H 5)}} 4 -, CH 3 CH 2 CH 2 CH 2 B (C 6 H 5) 3 - , etc.), thiocyanate ion (SCN ⁻ ), nitrate ion (NO ₃ ⁻ ) and the like can be used.

These X ^- of, in terms of cationic polymerization _{^{performance, MY a -, (Rf)}} b PF 6-b -, R 5 c BY 4-c -, R 5 c GaY 4-c -, R 6 SO 3 _{^{-, (R 6 SO 2)}} 3 C - and _{^{(R 6 SO 2) 2 N}} - anion is preferably represented _{^{by, MY a -, (Rf)}} b PF 6-b -, R 5 c bY 4-c - _{^{, R 5 c GaY 4-c}} - and _{^{(R 6 SO 2) 3 C}} - more _{^{preferably, SbF 6 -, PF 6 -}} , (CF 3 CF 2) 3 PF 3 -, (C 6 F 5) 4 B _{^{-, ((CF 3) 2}} C 6 H 3) 4 B -, (C 6 F 5) 4 Ga -, ((CF 3) 2 C 6 H 3) 4 Ga - and _{(CF 3} SO ₂₎ 3 C ^- is particularly preferred.
For use in a chemically amplified positive photoresist composition, SbF ₆ ⁻ , PF ₆ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ⁻ , trifluoromethanesulfonic acid anion, nonafluorobutanesulfonic acid anion, benzene A sulfonate anion, a p-toluenesulfonate anion, (CF ₃ SO ₂ ) ₃ C ⁻ and (CF ₃ SO ₂ ) ₂ N ⁻ are preferable in terms of improving the resolution and pattern shape of the resist, and (CF ₃ CF ₂ ). ₃ PF ₃ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ and ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ⁻ are particularly preferred because they are more compatible with the resist composition.

Preferred examples of the sulfonium salt represented by the formula (1) include the following, but are not limited thereto.
(A) R ² and R ³ are a methyl group or a methoxy group, m ² and m ³ are 1, and m ¹ and m ⁴ are 0.
(B) All of m ^{1 to} m ⁴ are 0.
(C) Ra, Rb and Rc are all methyl groups or phenyl groups.

  Among the cations of the sulfonium salt in the present invention, preferred specific examples are shown below.

The sulfonium salt of the present invention can be produced, for example, by the production method (1) described below.
<Manufacturing method (1)>
Methods represented by the following reaction formulas (for example, 4th edition, Experimental Chemistry Course Vol. 24, 1992, published by Maruzen Co., Ltd., page 376, JP-A-7-329399, JP-A-8-165290, JP-A-10- And the method described in JP-A No. 212286 or JP-A-10-7680).

In the above reaction formulas, R ^{1 to} R ⁴ represent substituents, m ^{1 to} m ⁴ represent the number of each substituent, and S, O, Si, Ra to Rc, and X ⁻ are the definitions in the formula (1). Is the same. H represents a hydrogen atom.
HX ′ represents a conjugate acid of a monovalent polyatomic anion. HX ′ is preferably methanesulfonic acid, perfluoromethanesulfonic acid and sulfuric acid from the viewpoints of availability, acid stability and reaction yield.
The dehydrating agent represents, for example, phosphoric anhydride, acetic anhydride, concentrated sulfuric acid, and the like.
The monovalent polyatomic anion (X ′ ⁻ ) can be exchanged for another anion (X ⁻ ) of the present invention by, for example, a metathesis reaction as described above.
DX represents an alkali metal (lithium, sodium, potassium, etc.) cation and another anion of the present invention (for example, MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ⁵ _c BY _4-c ⁻ , R ⁵ _{c ^{GaY 4-c -, R 6}} SO 3 - represents a salt of an anion represented by _{^{like) -, (R 6 SO 2}} ) 3 C -, R 6 SO 2) 2 N.
DX ′ represents a salt of an alkali metal (lithium, sodium, potassium, etc.) cation and a monovalent polyatomic anion (methanesulfonic acid anion, perfluoromethanesulfonic acid anion, hydrogen sulfate anion, etc.).

  In the above reaction formula, the first stage reaction may be carried out in the absence of a solvent, or may be carried out in an organic solvent (acetonitrile, tetrahydrofuran, dioxane, ethanol, acetone, etc.) if necessary. The reaction temperature is about 20 to 105 ° C. The reaction time is about 1 to several tens of hours.

  The reaction in the second stage may be performed subsequent to the reaction in the first stage, or may be performed after the reaction intermediate <G3> is isolated (purified as necessary). The reaction intermediate <G3> and an aqueous solution of a salt (DX) of an alkali metal cation and an anion used in the present invention were mixed and stirred to perform a metathesis reaction, and the precipitated solid was filtered or separated. The sulfonium salt of the present invention can be obtained as a solid or viscous liquid by extracting the oil with an organic solvent and removing the organic solvent. The obtained solid or viscous liquid can be washed with an appropriate organic solvent, if necessary, or purified by recrystallization or column chromatography (the same applies hereinafter).

<Manufacturing method (2)>
The above <G2> can be synthesized by the oxidation reaction described in the 4th edition, Experimental Chemistry Course Vol. 23 (1991, Maruzen), pages 276 to 277, as shown in the following reaction formula.

In the reaction formula, R ^{1 to} R ⁴ , S, O, Si, and m ^{1 to} m ⁴ are the same as defined in the formula (1).
“Oxidizing agent” represents an oxidizing agent such as hydrogen peroxide.

The chemical structure of the sulfonium salt of the present invention is determined by a general analytical method (for example, ¹ H-, ¹¹ B-, ¹³ C-, ¹⁹ F-, ³¹ P-nuclear magnetic resonance spectrum, infrared absorption spectrum and / or element). Analysis).

The sulfonium salt of the present invention is suitable as a photoacid generator.
A photoacid generator is an acid generator that decomposes its chemical structure when irradiated with light. The generated acid can be used as a catalyst for an epoxide curing reaction or the like, and for making a chemically amplified positive photoresist composition soluble in an alkali developer.

  The photoacid generator of the present invention may be used as it is, or may be used by containing another photoacid generator.

  When other photoacid generator is contained, the content (mol%) of the other photoacid generator is preferably 1 to 100, more preferably 5 to the total number of moles of the sulfonium salt of the present invention. 50.

  Other photoacid generators include onium ions (sulfonium, iodonium, selenium, ammonium, phosphonium, etc.) and conventionally known ones such as salts of transition metal complex ions and anions.

Examples of the _{^{anionic, MY a -, (Rf)}} b PF 6-b -, R 10 c BY 4-c -, R 10 c GaY 4-c -, R 11 SO 3 -, (R 11 SO 2) 3 C ^- or _{^{(R 11 SO 2) 2 N}} - except anion represented by the, perhalogenated acid ion ^_(ClO 4 -, BrO ₄ ^-, etc.), halogenated sulfonic acid ion ^_(FSO 3 -, ClSO ₃ ^-, etc.), sulfuric acid Ions (CH ₃ SO ₄ ⁻ , CF ₃ SO ₄ ⁻ , HSO ₄ ⁻ etc.), carbonate ions (HCO ₃ ⁻ , CH ₃ CO ₃ ⁻ etc.), aluminate ions (AlCl ₄ ⁻ , AlF ₄ ⁻ etc.), hexa Fluorobismate ion (BiF ₆ ⁻ ), carboxylate ion (CH ₃ COO ⁻ , CF ₃ COO ⁻ , C ₆ H ₅ COO ⁻ , CH ₃ C ₆ H ₄ COO ⁻ , C ₆ F ₅ COO _{^{-, CF 3 C 6 H 4}} COO - , etc.), an aryl boronic acid ions _{^{(B (C 6 H 5)}} 4 -, CH 3 CH 2 CH 2 CH 2 B (C 6 H 5) 3 - , etc.), thiocyanate ion (SCN ⁻ ), nitrate ion (NO ₃ ⁻ ) and the like can be used. Here, M represents a phosphorus atom, a boron atom, or an antimony atom.

  Examples of the sulfonium ions include triarylsulfonium, diarylsulfonium, monoarylsulfonium, and trialkylsulfonium.

  Examples of triarylsulfonium include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris (4-methoxyphenyl) sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris (4-fluoro Phenyl) sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris (4-hydroxyphenyl) sulfonium, 4- (phenylthio) phenyldiphenylsulfonium, 4- (p-tolylthio) phenyldi-p-tolylsulfonium, 4- (4-methoxyphenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (phenyl) E) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenyldi-p-tolylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- {bis [4- (2-hydroxy) Ethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, bis {4- [bis (4-methylphenyl) sulfonio] phenyl} sulfide, bis {4- [Bis (4-methoxyphenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenyldiphenyl Sulfonium, 4- (4-be Zoylphenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi- p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) Sulfonio] thioxanthone, 2-{[4- (phenylthio) phenyl] phenylsulfonio} thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- [4- (4 -Tert-butylbenzoyl) Phenylthio] phenyldiphenylsulfonium, 4- [4- (benzoylphenylthio)] phenyldi-p-tolylsulfonium, 4- [4- (benzoylphenylthio)] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrhenium , 5-phenylthiaanthrhenium, 5-tolylthiaanthrhenium, 5- (4-ethoxyphenyl) thiaanthrhenium, 5- (2,4,6-trimethylphenyl) thiaanthrhenium, etc. No. 4,231,951, U.S. Pat. No. 4,256,828, JP-A-61-100557, JP-A-7-61964, JP-A-7-10914, JP-A-7-25922, JP-A-8-27208, JP-A-8-27209. No. 1, JP-A-8-165290, JP-A-8-301 91, JP-A-9-143212, JP-A-9-278813, JP-A-10-7680, JP-A-10-212286, JP-A-10-287463, JP-A-10-245378, JP-A-8-157510. JP-A-10-204083, JP-A-8-245656, JP-A-8-157451, JP-A-7-324069, JP-A-9-268205, JP-A-9-278935, JP-A-2001-288205. JP-A-11-80118, JP-A-10-182825, JP-A-10-330353, JP-A-10-152249, JP-A-5-239213, JP-A-7-333834, JP-A-9-12537, JP-A-9-12537. No. 8-325259, JP-A-8-160606, JP-A-2000-186071 (US Pat. No. 6,368). No. 69), JP-T-2005-501040, JP 2005-530698, JP 2006-104185, JP-T-2006-518332 and JP 2007-254454 No., etc.).

  Examples of the diarylsulfonium include diphenylphenacylsulfonium, diphenyl4-nitrophenacylsulfonium, diphenylbenzylsulfonium and diphenylmethylsulfonium (Japanese Patent Laid-Open Nos. 7-300504, 64-45357 and 64-64). 29419 etc.).

  Examples of monoarylsulfonium include phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl (1 -Ethoxycarbonyl) ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium and 9-anthracenylmethylphenacils Examples include Honium (JP-A-6-345726, JP-A-8-325225, JP-A-9-118663 (US Pat. No. 6093753), JP-A-2-196812, JP-A2-1470, 2-196812, JP-A-3-237107, JP-A-3-17101, JP-A-6-228086, JP-A-10-152469, JP-A-7-300505, JP-A-2000-39706, JP-A-2003. -277353 and JP-A-2003-277352).

  Examples of the trialkylsulfonium include dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, octadecylmethylphenacylsulfonium, and the like (JP-A-4-308563, JP-A-5-140210). JP, 5-140209, JP 5-230189, JP 6-271532, JP 58-37003, JP 2-178303, JP 10-338688, JP 9-328506. No. 11, JP-A-11-228534, JP-A-8-27102, JP-A-7-333834, JP-A-5-222167, JP-A-11-21307, JP-A-11-35613, US Pat. No. 6,031,014, etc. ).

  Examples of the iodonium ion include diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxyphenyl). ) Iodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, isobutylphenyl (p-tolyl) iodonium, etc. (Macromolecules, 10, 1307 (1977), JP-A-6-184170, U.S. Pat. No. 4,256,828, U.S. Pat. No. 4,351,708, JP-A-56-135519, JP-A-58-38350, JP-A-10-195117 JP 2001-139539, JP 2000-510516 and JP 2000-119306 No., etc.).

  Selenium ions include triaryl selenium {triphenyl selenium, tri-p-tolyl selenium, tri-o-tolyl selenium, tris (4-methoxyphenyl) selenium, 1-naphthyldiphenyl selenium, tris (4-fluorophenyl) selenium , Tri-1-naphthyl selenium, tri-2-naphthyl selenium, tris (4-hydroxyphenyl) selenium, 4- (phenylthio) phenyldiphenyl selenium and 4- (p-tolylthio) phenyl di-p-tolyl selenium}} diaryl Selenium {diphenylphenacyl selenium, diphenylbenzyl selenium, diphenylmethyl selenium, etc.}; monoaryl selenium {phenylmethylbenzyl selenium, 4-hydroxyphenylmethy Benzyl selenium, phenylmethyl phenacyl selenium, 4-hydroxyphenyl methyl phenacyl selenium, 4-methoxyphenyl methyl phenacyl selenium, etc.} and trialkyl selenium {dimethylphenacyl selenium, phenacyl tetrahydroselenophenium, dimethyl benzyl selenium, benzyl Tetrahydroselenophenium, octadecylmethylphenacyl selenium, etc.} (Japanese Patent Laid-Open Nos. 50-151997, 50-151976, 53-22597, etc.).

  Examples of ammonium ions include tetraalkylammonium (tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, tetraethylammonium, trimethyl-n-propylammonium, trimethylisopropylammonium, trimethyl-n-butylammonium, trimethylisobutylammonium, Trimethyl-t-butylammonium, trimethyl-n-hexylammonium, dimethyldi-n-propylammonium, dimethyldiisopropylammonium, dimethyl-n-propylisopropylammonium, methyltri-n-propylammonium and methyltriisopropylammonium); pyrrolidinium (N , N-dimethylpyrrolidinium, -Ethyl-N-methylpyrrolidinium and N, N-diethylpyrrolidinium, etc.); imidazolinium (N, N'-dimethylimidazolinium, N, N'-diethylimidazolinium, N-ethyl-N '-Methylimidazolinium, 1,2,3-trimethylimidazolinium, 1,3,4-trimethylimidazolinium, 1,3-diethyl-2-methylimidazolinium, 1,3-diethyl-4- Methyl imidazolinium and 1,2,3,4-tetramethylimidazolinium, etc.); tetrahydropyrimidinium (N, N'-dimethyltetrahydropyrimidinium, N, N'-diethyltetrahydropyrimidinium, N- Ethyl-N′-methyltetrahydropyrimidinium and 1,2,3-trimethyltetrahydropyrimidinium); Ni (N, N'-dimethylmorpholinium, N-ethyl-N-methylmorpholinium, N, N-diethylmorpholinium, etc.); piperidinium (N, N-dimethylpiperidinium, N-ethyl-N) '-Methylpiperidinium and N, N'-diethylpiperidinium, etc.); pyridinium (N-methylpyridinium, N-ethylpyridinium, Nn-propylpyridinium, N-isopropylpyridinium, Nn-butylpyridinium, N-benzylpyridinium and N-phenacylpyridium, etc.); imidazolium (N, N'-dimethylimidazolium, N-ethyl-N-methylimidazolium, N, N'-diethylimidazolium, 1,2-diethyl) -3-methylimidazolium, 1,3-diethyl-2-methylimidazolium and 1-methyl-3-n-propyl-2,4-dimethylimidazolium, etc.); quinolium (N-methylquinolium, N-ethylquinolium, Nn-propylquinolium, N-isopropylquinolium, N- n-butyl quinolium, N-benzyl quinolium, N-phenacyl quinolium, etc.); isoquinolium (N-methylisoquinolium, N-ethylisoquinolium, Nn-propylisoquinolium, N-isopropyliso Quinolium, Nn-butylisoquinolium, N-benzylisoquinolium, N-phenacylisoquinolium, etc.); thiazonium (benzylbenzothiazonium, phenacylbenzothiazonium, etc.) and arridinium (benzylacrylic) (U.S. Pat. No. 4069) and the like. No. 55, Japanese Patent Publication No. 2519480, Japanese Patent Application Laid-Open No. 5-222112, Japanese Patent Application Laid-Open No. 5-222111, Japanese Patent Application Laid-Open No. 5-262613, Japanese Patent Application Laid-Open No. 5-255256, Japanese Patent Application Laid-Open No. 7-109303, Japanese Patent Application Laid-Open No. 10-101718. JP-A-2-268173, JP-A-9-328507, JP-A-5-132461, JP-A-9-216552, JP-A-7-43854, JP-A-7-43901, JP-A-5-262813, JP-A-4-327574, JP-A-2-43202, JP-A-60-203628, JP-A-57-209931, and JP-A-9-221651).

  Examples of phosphonium ions include tetraarylphosphonium {tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis (2-methoxyphenyl) phosphonium, tetrakis (3-methoxyphenyl) phosphonium, tetrakis (4-methoxyphenyl) phosphonium, etc.}; tria Reel phosphonium (triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, triphenylbutylphosphonium, etc.) and tetraalkylphosphonium (triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethyl) Phenacylphosphonium and tributylphenacylphos Honiumu etc.) and the like (JP-A-6-157624, JP-A-5-105692, JP-A-7-82283 and JP-A 9-202873 Patent etc.).

Transition metal complex ions include chromium complex cations {(η5-cyclopentadienyl) (η6-toluene) Cr ⁺ , (η5-cyclopentadienyl) (η6-xylene) Cr ⁺ , (η5-cyclopentadienyl). ) (Η6-1-methylnaphthalene) Cr ⁺ , (η5-cyclopentadienyl) (η6-cumene) Cr ⁺ , (η5-cyclopentadienyl) (η6-mesitylene) Cr ⁺ , (η5-cyclopentadiene) Enyl) (η6-pyrene) Cr ⁺ , (η5-fluorenyl) (η6-cumene) Cr ⁺ , (η5-indenyl) (η6-cumene) Cr ⁺ , bis (η6-mesitylene) Cr ²⁺ , bis (η6-xylene) ) ^{Cr 2+,} bis (Ita6- cumene) ^{Cr 2+,} bis (Ita6- toluene) ^{Cr 2+,} (η6- toluene) (η6- xylene) ^{Cr 2+,} (η6 Cumene) (η6- naphthalene) ^{Cr 2+,} bis (eta. @ 5-cyclopentadienyl) Cr ^+, bis (eta. @ 5-indenyl) ^Cr +, (η5- cyclopentadienyl) (eta. @ 5 fluorenyl) Cr ⁺ and (eta. @ 5 Cyclopentadienyl) (η5-indenyl) Cr ⁺ etc}, and iron complex cation {(η5-cyclopentadienyl) (η6-toluene) Fe ⁺ , (η5-cyclopentadienyl) (η6-xylene) Fe ⁺ , (Η5-cyclopentadienyl) (η6-1-methylnaphthalene) Fe ⁺ , (η5-cyclopentadienyl) (η6-cumene) Fe ⁺ , (η5-cyclopentadienyl) (η6-mesitylene) Fe ^+, (η5- cyclopentadienyl) (η6- pyrene) ^Fe +, ^(η5- fluorenyl) (η6- cumene) ^Fe +, ^(η5- Indeni ) (Ita6- cumene) Fe ^+, bis (Ita6- mesitylene) ^{Fe 2+,} bis (Ita6- xylene) ^{Fe 2+,} bis (Ita6- cumene) ^{Fe 2+,} bis (Ita6- toluene) ^{Fe 2+,} (η6- toluene) (Η6-xylene) Fe ²⁺ , (η6-cumene) (η6-naphthalene) Fe ²⁺ , bis (η5-cyclopentadienyl) Fe ⁺ , bis (η5-indenyl) Fe ⁺ , (η5-cyclopentadienyl) (Η5-fluorenyl) Fe ⁺ and (η5-cyclopentadienyl) (η5-indenyl) Fe ⁺ etc.} (wherein Cr represents a chromium atom and Fe represents an iron atom) (Macromol. Chem. 81,86 (1965), Angew. Makromol.
Chem., 50, 9 (1976), Macromol. Chem., 153, 229 (1972), J. Polym. Sci., Polym. Chem. Edn., 14, 1547 (1976), Chem. Ztg., 108, 345 (1984), J. Imaging. Sci.,
30, 174 (1986), J. Photochem. Photobiol. A: Chem., 77 (1994), J. Rad. Curing., 26 (1986), Adv. Polym. Sci., 78,
61 (1986), U.S. Pat. Nos. 4,973,722, 4,992,572, 3,895,954, European Patent Publication Nos. 203829, 354181, 94914, 109851, 94949 Kaihei 58-210904 (US Pat. No. 4,868,288), JP-A-59-108003, JP-A-2000-226396, JP-A-2-284903, and the like.

  The photoacid generator of the present invention may be dissolved in advance in a solvent that does not inhibit cationic polymerization in order to facilitate dissolution in the cationic polymerizable compound.

  Solvents include carbonates (propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, and diethyl carbonate); esters (ethyl acetate, ethyl lactate, β-propiolactone, β-butyrolactone, γ-butyrolactone, δ Ether (ethylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol dibutyl ether, etc.); and ether esters ( Ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Fine diethylene glycol monobutyl ether acetate, etc.) and the like.

  When using a solvent, the proportion of the solvent used is preferably 15 to 1000 parts by weight, more preferably 30 to 500 parts by weight, with respect to 100 parts by weight of the photoacid generator of the present invention. The solvent to be used may be used independently or may use 2 or more types together.

  The energy beam curable composition of the present invention comprises the above-mentioned photoacid generator and a cationically polymerizable compound.

  Examples of the cationic polymerizable compound include cyclic ethers (epoxides and oxetanes), ethylenically unsaturated compounds (vinyl ether and styrene, etc.), bicycloorthoesters, spiroorthocarbonates and spiroorthoesters (Japanese Patent Laid-Open No. 11-060996). JP-A 09-302269, JP-A 2003-026993, JP-A 2002-206017, JP-A 11-349895, JP-A 10-212343, JP-A 2000-119306, JP-A 10-67812, JP 2000-186071, JP 08-85775, JP 08-134405, JP 2008-20838, JP 2008-20839, JP 2008-20841, JP 2008-26660, JP 2008-26644. , JP 2 07-277327, Photopolymer social gathering “Photopolymer Handbook” (1989, Industrial Research Committee), General Technology Center “UV / EB Curing Technology” (1982, General Technology Center), Radtech Study Group “UV. "EB Curing Material" (1992, CMC), Technical Information Association, "Hardening Failure / Inhibition Causes in UV Curing and Countermeasures" (2003, Technical Information Association), Coloring Materials, 68, (5), 286-293 (1995), fine chemical, 29, (19), 5-14 (2000), etc.).

  Known epoxides can be used and include aromatic epoxides, alicyclic epoxides and aliphatic epoxides.

  Aromatic epoxides include mono- or polyhydric phenols having at least one aromatic ring (phenol, biphenol, bisphenol A, bisphenol F, phenol novolac, cresol novolac, brominated products thereof, and alkylene oxide adducts thereof). And glycidyl esters (such as diglycidyl phthalate and diglycidyl-3-methyl phthalate) of monovalent or polyvalent carboxylic acids (such as phthalic acid and 3-methylphthalic acid) having at least one aromatic ring. .

  As alicyclic epoxides, compounds obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3, 4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 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) cyclohexanemetadioxane, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylenebis (3,4 Epoxycyclohexane), dicyclopentadiene diepoxide, ethylene bis (3,4-epoxycyclohexanecarboxylate) and the like.

  Examples of the aliphatic epoxide include aliphatic polyhydric alcohol or polyglycidyl ether of this alkylene oxide adduct (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, Triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol and hexaglycidyl ether of dipentaerythritol), polyglycidyl ester of aliphatic polybasic acid (diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate) And diglycidyl hexahydro-3-methylphthalate, etc.), epoxidized products of long chain unsaturated compounds (epoxidized soybean oil, epoxidized polybutadiene, etc.) Glycidyl group-containing polymers (such as homopolymers of glycidyl (meth) acrylate or copolymers thereof with other unsaturated monomers) and polyfunctional epoxides having a dimethylsiloxane skeleton (Journal of Polym. Sci., Part A, Polym. Chem) ., Vol. 28, 497 (1990) etc.)

  As oxetane, known ones can be used, such as 3-ethyl-3-hydroxymethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, [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, 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-oxetanylmethyl) Ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pen Bromophenyl (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-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether , Dicyclopentenyl bis (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-ethyl -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, dipentaerythritoltetrakis (3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3-phenoxymethyloxetane, 3-ethyl-3- (4-methylphenoxy) methyloxetane, 3-ethyl-3- (4-fluorophenoxy) methyloxetane, 3-ethyl-3- (1-naphthoxy) methyloxetane, 3-ethyl-3- (2-Naphoxy) methyloxetane, 3-ethyl-3-{[3- (ethoxysilyl) propoxy] methyl} oxetane, oxetanylsilsesquioxetane, phenol novolac oxetane and the like.

  As the ethylenically unsaturated compound, known cationically polymerizable monomers can be used, and examples thereof include aliphatic monovinyl ether, aromatic monovinyl ether, polyfunctional vinyl ether, styrene, and cationically polymerizable nitrogen-containing monomers.

  Aliphatic monovinyl ethers include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, 2-chloroethyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, 2-acetoxyethyl vinyl ether, diethylene glycol Examples thereof include monovinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, allyl vinyl ether, 2-methacryloyloxyethyl vinyl ether, and 2-acryloyloxyethyl vinyl ether.

  Examples of the aromatic monovinyl ether include 2-phenoxyethyl vinyl ether, phenyl vinyl ether, and p-methoxyphenyl vinyl ether.

  Polyfunctional vinyl ethers include butanediol-1,4-divinyl ether, triethylene glycol divinyl ether, 1,4-benzene divinyl ether, hydroquinone divinyl ether, cyclohexanedimethanol divinyl ether (1,4-bis [(vinyloxy) methyl Cyclohexane), diethylene glycol divinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether, and the like.

  Examples of styrene include styrene, α-methylstyrene, p-methoxystyrene, and p-tert-butoxystyrene.

  Examples of the cationic polymerizable nitrogen-containing monomer include N-vinylcarbazole and N-vinylpyrrolidone.

  Bicycloorthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2.2.2] octane and 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo. -[2.2.2] octane and the like.

  Examples of the spiro ortho carbonate include 1,5,7,11-tetraoxaspiro [5.5] undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro [5.5] undecane. It is done.

  Spiro orthoesters include 1,4,6-trioxaspiro [4.4] nonane, 2-methyl-1,4,6-trioxaspiro [4.4] nonane and 1,4,6-trioxas. Examples include pyro [4.5] decane.

  Of these cationically polymerizable compounds, epoxide, oxetane and vinyl ether are preferable, epoxide and oxetane are more preferable, and alicyclic epoxide and oxetane are particularly preferable. In addition, these cationically polymerizable compounds may be used alone or in combination of two or more.

  The content of the photoacid generator of the present invention in the energy ray curable composition is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts of the cationic polymerizable compound. is there. Within this range, the polymerization of the cationically polymerizable compound is further sufficient, and the physical properties of the cured product are further improved. This content is determined by considering various factors such as the nature of the cationic polymerizable compound, the type and energy dose of the energy ray, temperature, curing time, humidity, and coating thickness, and is limited to the above range. Not.

  In the energy ray curable composition of the present invention, a known additive (sensitizer, pigment, filler, antistatic agent, flame retardant, antifoaming agent, flow control agent, light stabilizer, An antioxidant, an adhesion-imparting agent, an ion scavenger, a coloring inhibitor, a solvent, a non-reactive resin, a radical polymerizable compound, and the like).

  The energy beam curable composition of the present invention basically does not require a sensitizer, but can contain a sensitizer as necessary to supplement the curability. As such a sensitizer, known sensitizers (JP-A-11-279212 and JP-A-09-183960) can be used, and anthracene {anthracene, 9,10-dibutoxyanthracene, 9,10 -Dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-tert-butyl-9,10-dimethoxyanthracene, 2,3-dimethyl-9,10-dimethoxyanthracene, 9 -Methoxy-10-methylanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-tert-butyl-9,10-diethoxyanthracene, 2,3-dimethyl-9, 10-diethoxyanthracene, 9-ethoxy-10-methylanthracene, , 10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dipropoxyanthracene, 2-tert-butyl-9,10-dipropoxyanthracene, 2,3-dimethyl-9,10-dipropoxyanthracene, 9-isopropoxy-10-methylanthracene, 9,10-dibenzyloxyanthracene, 2-ethyl-9,10-dibenzyloxyanthracene, 2-tert- 9,10-dibenzyloxyanthracene, 2,3-dimethyl-9,10-dibenzyloxyanthracene, 9-benzyloxy-10-methylanthracene, 9,10-di-α-methylbenzyloxyanthracene, 2-ethyl -9,10-di-α-methylbenzyloxy Nthracene, 2-tert-9,10-di-α-methylbenzyloxyanthracene, 2,3-dimethyl-9,10-di-α-methylbenzyloxyanthracene, 9- (α-methylbenzyloxy) -10- Methylanthracene, 9,10-diphenylanthracene, 9-methoxyanthracene, 9-ethoxyanthracene, 9-methylanthracene, 9-bromoanthracene, 9-methylthioanthracene, 9-ethylthioanthracene, etc.}; pyrene; 1,2-benz Anthracene; perylene; tetracene; coronene; thioxanthone {thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, etc.}; phenothiazine Phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, N-phenylphenothiazine, etc.}; xanthone; naphthalene {1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,7-dimethoxynaphthalene, 1,1'-thiobis (2-naphthol), 1,1'-bi- (2-naphthol) And 4-methoxy-1-naphthol and the like}; ketone {dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpro Piophenone, 2-hydroxy Cymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p- Azidobenzalacetophenone, 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, 1- [4- (2-hydroxyethoxy) phenyl]- 2-hydroxy-2-methyl-1-propan-1-one, benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4 -Dichlorobenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide and the like}; carbazole {N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole and N-glycidylcarbazole and the like}; chrysene {1,4-dimethoxy Chrysene, 1,4-diethoxychrysene, 1,4-dipropoxychrysene, 1,4-dibenzyloxychrysene, 1,4-di-α-methylbenzyloxychrysene, etc.}; phenanthrene {9-hydroxyphenanthrene, 9 -Methoxyphenanthrene, 9-ethoxyphenanthrene, 9-benzyloxyphenanthrene, 9,10-dimethoxyphenanthrene, 9,10-diethoxyphenanthrene, 9,10-dipropoxyphenanthrene, 9,10-dibenzyloxy Enanthrene, 9,10-di-α-methylbenzyloxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene and 9-hydroxy-10-ethoxyphenanthrene}, and the like.

  When the sensitizer is contained, the content of the sensitizer is preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight, with respect to 100 parts of the photoacid generator.

  Known pigments can be used as the pigment, and examples include inorganic pigments (such as titanium oxide, iron oxide, and carbon black) and organic pigments (such as azo pigments, cyanine pigments, phthalocyanine pigments, and quinacridone pigments).

  When the pigment is contained, the content of the pigment is preferably 0.5 to 400,000 parts by weight, more preferably 10 to 150,000 parts by weight with respect to 100 parts of the photoacid generator.

  Known fillers can be used as fillers, such as fused silica, crystalline silica, calcium carbonate, aluminum oxide, aluminum hydroxide, zirconium oxide, magnesium carbonate, mica, talc, calcium silicate and lithium aluminum silicate. Can be mentioned.

  When it contains a filler, the content of the filler is preferably 50 to 600,000 parts by weight, more preferably 300 to 200,000 parts by weight with respect to 100 parts of the photoacid generator.

  As the antistatic agent, a known antistatic agent can be used, and a nonionic antistatic agent {glycerin fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, N, N-bis (2-hydroxyethyl) ) Alkylamine, polyoxyethylene alkylamine, polyoxyethylene alkylamine fatty acid ester, alkyldiethanolamide, etc.}; anionic antistatic agent {alkyl sulfonate, alkylbenzene sulfonate, alkyl phosphate, etc.}; cationic charge Inhibitors {tetraalkylammonium salts and trialkylbenzylammonium salts, etc.}; amphoteric antistatic agents {alkylbetaines and alkylimidazolium betaines, etc.}; polymeric antistatic agents {quaternary ammo-containing styrene- (meta Acrylate copolymer, quaternary ammonio-containing styrene-acrylonitrile-maleimide copolymer, polyoxyethylene glycol, polyether ester amide, polyether amide imide, ethylene oxide-epichlorohydrin copolymer and methoxy polyoxyethylene glycol ( Meth) acrylate copolymer, etc.}.

  When the antistatic agent is contained, the content of the antistatic agent is preferably 0.1 to 20000 parts by weight, more preferably 0.6 to 5000 parts by weight with respect to 100 parts of the photoacid generator.

  As the flame retardant, known flame retardants can be used. Inorganic flame retardant {antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide , Magnesium hydroxide, calcium aluminate, etc.}; bromine flame retardant {tetrabromophthalic anhydride, hexabromobenzene, decabromobiphenyl ether, etc.}; and phosphate ester flame retardant {tris (tribromophenyl) phosphate, etc.} It is done.

  When the flame retardant is contained, the content of the flame retardant is preferably 0.5 to 40000 parts by weight, more preferably 5 to 10000 parts by weight with respect to 100 parts of the photoacid generator.

  As the antifoaming agent, known antifoaming agents can be used, alcohol defoaming agents {isopropanol, n-butanol, octaethyl alcohol, hexadecyl alcohol, etc.}; metal soap defoaming agents {calcium stearate, aluminum stearate, etc. }; Phosphate ester defoamers {tributyl phosphate, etc.}; Fatty acid ester defoamers {glycerin monolaurate, etc.}; Polyether defoamers {polyalkylene glycol, etc.}; Silicone defoamers {dimethylsilicone oil and silica Silicone compound and the like}; and mineral oil defoaming agent {mineral oil in which silica powder is dispersed} and the like.

  When the antifoaming agent is contained, the content of the antifoaming agent is preferably 0.1 to 20000 parts by weight, more preferably 0.5 to 5000 parts by weight with respect to 100 parts of the photoacid generator.

  As the flow control agent, known flow control agents can be used, and examples thereof include hydrogenated castor oil, polyethylene oxide, organic bentonite, colloidal silica, amide wax, metal soap, and acrylate polymer.

  When the fluidity modifier is contained, the content of the fluidity modifier is preferably 0.1 to 20000 parts by weight, more preferably 0.5 to 5000 parts by weight with respect to 100 parts of the photoacid generator. .

  As the light stabilizer, known light stabilizers and the like can be used. Ultraviolet absorbing stabilizers {benzotriazole, benzophenone, salicylate, cyanoacrylate and derivatives thereof}; radical scavenging stabilizers {hindered amine, etc.}; and quenching And a type stabilizer {nickel complex etc.}.

  When the light stabilizer is contained, the content of the light stabilizer is preferably 0.05 to 40,000 parts by weight, more preferably 0.5 to 10,000 parts by weight with respect to 100 parts of the photoacid generator.

  As antioxidants, known antioxidants can be used, such as phenolic antioxidants (monophenolic, bisphenolic and polymeric phenolic), sulfur antioxidants and phosphorus antioxidants. It is done.

  When the antioxidant is contained, the content of the antioxidant is preferably 0.1 to 20000 parts by weight, more preferably 0.6 to 5000 parts by weight with respect to 100 parts of the photoacid generator.

  As the adhesion-imparting agent, a known adhesion-imparting agent can be used, and examples thereof include a coupling agent, a silane coupling agent, and a titanium coupling agent.

  When the adhesiveness-imparting agent is contained, the content of the adhesiveness-imparting agent is preferably 0.1 to 20000 parts by weight, more preferably 0.6 to 5000 parts by weight with respect to 100 parts of the adhesiveness-imparting agent. .

As the ion scavenger, known ion scavengers can be used, and organic aluminum (alkoxyaluminum, phenoxyaluminum, etc.) and the like can be mentioned.
When the ion scavenger is contained, the content of the ion scavenger is preferably 0.1 to 20000 parts by weight, more preferably 0.6 to 5000 parts by weight with respect to 100 parts of the photoacid generator.

Known anti-coloring agents can be used as the anti-coloring agent. In general, antioxidants are effective. Phenol type antioxidants (monophenol type, bisphenol type and high molecular phenol type, etc.), sulfur type oxidation Examples thereof include an inhibitor and a phosphorus-based antioxidant.
When the anti-coloring agent is contained, the content of the anti-coloring agent is preferably 0.1 to 20000 parts by weight, more preferably 0.6 to 5000 parts by weight with respect to 100 parts of the photoacid generator.

  The solvent is not limited as long as it can be used for dissolving a cationically polymerizable compound or adjusting the viscosity of an energy ray-curable composition. In addition to those that can be used as a solvent for the photoacid generator, for example, ether {anisole, diethyl Ether, tetrahydrofuran, 1,4-dioxane and ethyl-tert-butyl ether etc.}; aromatic hydrocarbon {toluene, xylene, cumene, ethylbenzene and mesitylene etc.}; ketone {acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone etc.}; alcohol { Methanol, ethanol, isopropyl alcohol, tert-butanol and the like}; nitrile {acetonitrile and the like} and the like.

  When the solvent is contained, the content of the solvent is preferably 50 to 2,000,000 parts by weight, more preferably 200 to 500,000 parts by weight with respect to 100 parts of the photoacid generator.

  Non-reactive resins include polyester, polyvinyl acetate, polyvinyl chloride, polybutadiene, polycarbonate, polystyrene, polyvinyl ether, polyvinyl butyral, polybutene, hydrogenated styrene butadiene block copolymer, and (meth) acrylic ester co-polymer. Examples include coalescence and polyurethane. The number average molecular weight of these resins is preferably from 1,000 to 500,000, more preferably from 5,000 to 100,000 (the number average molecular weight is a value measured by a general method such as GPC).

  When the non-reactive resin is contained, the content of the non-reactive resin is preferably 5 to 400000 parts by weight, more preferably 50 to 150,000 parts by weight with respect to 100 parts of the photoacid generator.

  When a non-reactive resin is contained, it is desirable to dissolve the non-reactive resin in a solvent in advance so that the non-reactive resin can be easily dissolved with the cationic polymerizable compound.

  As radically polymerizable compounds, known {photopolymer social gathering edition “Photopolymer Handbook” (1989, Industrial Research Committee), General Technology Center “UV / EB Curing Technology” (1982, General Technology Center), Radtech Research The radical-polymerizable compounds in the “UV / EB Curing Materials” edition (1992, CMC) and the “Technical Information Association”, “Hardening Failure / Inhibition Causes in UV Curing and Countermeasures” (2003, Technical Information Association)} Monofunctional monomers, bifunctional monomers, polyfunctional monomers, epoxy (meth) acrylates, polyester (meth) acrylates and urethane (meth) acrylates can be used.

  Monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 1,6-hexanediol mono (meth) ) Acrylate, styrene, vinylcyclohexene, isobutylene and butadiene.

  Bifunctional monomers include dihydric alcohols or di (meth) acrylates of these alkylene oxide adducts {dihydric alcohols (ethylene hydride, propylene glycol, bisphenol A, bisphenol A hydrides and their alkylene oxide adducts, etc.) Di (meth) acrylate} and divinylbenzene.

  As the polyfunctional monomer, a monomer other than the bifunctional monomer can be used, and examples thereof include (meth) acrylates of polyhydric alcohols (trimethylolpropane, glycerin, pentaerythritol, and alkylene oxide adducts thereof).

  Examples of the epoxy (meth) acrylate include epoxy (meth) acrylate obtained by reacting epoxide {aromatic epoxide, alicyclic epoxide, aliphatic epoxide, etc.} with (meth) acrylic acid.

As the polyester (meth) acrylate, a polyester (meta) obtained by esterifying a hydroxy-terminated polyester obtained from an aromatic polybasic acid or aliphatic polybasic acid and a polyhydric alcohol with (meth) acrylic acid. ) Acrylate and the like.
Aromatic polybasic acids include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid, and aliphatic polybasic acids include succinic acid, adipic acid, and sebacic acid. As alcohol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, polytetramethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol , Trimethylolpropane, glycerin, pentaerythritol, bisphenol and their alkylene oxide adducts.

Examples of urethane (meth) acrylates include urethane (meth) acrylates obtained by urethanation reaction of isocyanate-terminated prepolymers obtained from polyfunctional isocyanates and polyhydric alcohols with hydroxyl group-containing (meth) acrylates. .
Polyfunctional isocyanates include cycloaliphatic isocyanates (isophorone diisocyanate and dicyclohexylmethane diisocyanate, etc.); aliphatic isocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, etc.) and aromatic isocyanates (toluene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, etc.)} Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, neopentyl glycol, polytetramethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6 -Hexanediol, trimethylolpropane, glycerin, pentaerythris Tol, bisphenol, hydrogenated bisphenol, polycaprolactone diol, polyester diol, polycarbonate diol, and the like. Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Examples thereof include 4-hydroxybutyl (meth) acrylate and penta (erythritol) tri (meth) acrylate.

  When the radically polymerizable compound is contained, the content of the radically polymerizable compound is preferably 5 to 400000 parts by weight, more preferably 50 to 150,000 parts by weight with respect to 100 parts of the photoacid generator.

  When radically polymerizable compounds are contained, a radical polymerization initiator that initiates polymerization by heat or light is preferably used in order to increase the molecular weight by radical polymerization.

  As the radical polymerization initiator, a known radical polymerization initiator or the like can be used, and a thermal radical polymerization initiator and a photo radical polymerization initiator are included.

  As thermal radical polymerization initiators, organic peroxides {ketone peroxides (such as methyl ethyl ketone peroxide and cyclohexanone peroxide), peroxyketals (2,2-bis (tert-butylperoxy) butane and 1,1-bis (Tert-butylperoxy) cyclohexane, etc.), hydroperoxide (such as tert-butylhydroperoxide and cumene hydroperoxide), dialkyl peroxide (such as di-tert-butylperoxide), diacyl peroxide (isobutyryl peroxide) Oxide, lauroyl peroxide and benzoyl peroxide), peroxydicarbonate (diisopropyl peroxydicarbonate, etc.), peroxyester (tert-butylperoxyisobutyrate and 2,5-dimethyl) -2,5-di (benzoylperoxy) hexane, etc.)}, and azo compounds {1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobisisobutyronitrile, 2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis [2-methyl-N- (2- Propenyl) propionamidine] dihydrochloride, 2,2′-azobis (2-methylpropionamide), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′- Azobis (2-methylpropane), 2,2'-azobis (2,4,4-trimethylpentane) and dimethyl 2,2'-azobis (2-methylpro Onato) and the like}.

  As photo radical polymerization initiators, acetophenone initiators {acetophenone, p-tert-butyltrichloroacetophenone and 2,2-diethoxyacetophenone, etc.}, benzophenone initiators {benzophenone, methyl o-benzoylbenzoate and 4-benzoyl-4 '-Methyldiphenyl sulfide, etc.}, Michler's ketone initiator {4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone, etc.}, benzoin initiator {benzoin, benzoin methyl ether, etc.}, thioxanthone Initiators {thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, etc.} and acylphosphine Such initiator {mono acyl phosphine oxides and bisacylphosphine oxides and the like} and the like.

  When the radical polymerization initiator is contained, the content of the radical polymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, relative to 100 parts of the radical polymerizable compound. .

  The energy ray-curable composition of the present invention comprises a cationically polymerizable compound, a photoacid generator, and optionally an additive, uniformly at room temperature (about 20 to 30 ° C.) or optionally heated (about 40 to 90 ° C.). Can be mixed and dissolved, or further kneaded with a three-roll or the like.

The energy ray-curable composition of the present invention can be cured by irradiating energy rays to obtain a cured product.
As the energy ray, any energy ray may be used as long as it has energy that induces the decomposition of the sulfonium salt of the present invention, but low pressure, medium pressure, high pressure or ultrahigh pressure mercury lamp, metal halide lamp, LED lamp, xenon lamp, carbon arc lamp, Energy rays in the ultraviolet to visible light region (wavelength: about 100 to about 800 nm) obtained from a fluorescent lamp, a semiconductor solid state laser, an argon laser, a He—Cd laser, a KrF excimer laser, an ArF excimer laser, an F ₂ laser, or the like are preferable. In addition, the radiation which has high energy, such as an electron beam or an X-ray, can also be used for an energy beam.

  The irradiation time of the energy beam is affected by the energy beam intensity and the energy beam permeability to the energy beam curable composition, but about 0.1 to 10 seconds is sufficient at room temperature (about 20 to 30 ° C). It is. However, it may be preferable to spend more time when energy beam permeability is low or when the energy beam curable composition is thick. From 0.1 seconds to several minutes after irradiation with energy rays, most energy ray curable compositions are cured by cationic polymerization. If necessary, after irradiation with energy rays, room temperature (about 20 to 30 ° C.) to 150 It is also possible to heat and cure at a temperature of several seconds to several hours.

  Specific applications of the energy beam curable composition of the present invention include paints, coating agents, inks, inkjet inks, positive resists, resist films, liquid resists, negative resists, MEMS resists, positive photosensitive materials. , Negative photosensitive materials, various adhesives, molding materials, casting materials, putty, glass fiber impregnating agents, sealing materials, sealing materials, sealing materials, optical semiconductor (LED) sealing materials, optical waveguide materials, nanoimprints Examples include materials, photofabrication, and micro stereolithography materials.

  Since the sulfonium salt of the present invention generates a strong acid upon irradiation with light, light for chemically amplified resist materials known in the art (Japanese Patent Application Laid-Open Nos. 2003-267968, 2003-261529, 2002-193925, etc.) is used. It can also be used as an acid generator.

  Chemically amplified resist materials include: (1) a two-component chemically amplified positive resist containing, as essential components, a resin that is soluble in an alkali developer by the action of an acid and a photoacid generator; and (2) an alkali developer. Soluble resin, a three-component chemical amplification type positive resist containing, as essential components, a dissolution inhibitor and a photoacid generator that are soluble in an alkali developer by the action of an acid, and (3) suitable for an alkali developer. A chemically amplified negative resist containing a crosslinking agent that crosslinks the resin by heat treatment in the presence of a soluble resin and an acid and makes the resin insoluble in an alkaline developer and a photoacid generator as an essential component is included.

  Further, the chemically amplified positive photoresist composition of the present invention comprises a component (A) comprising the photoacid generator of the present invention, which is a compound that generates acid upon irradiation with light or radiation, and an alkali by the action of the acid. It contains a resin component (B) whose solubility is increased.

  In the chemically amplified positive photoresist composition of the present invention, the component (A) may be used in combination with another conventionally known photoacid generator. Other acid generators include, for example, onium salt compounds, sulfone compounds, sulfonate ester compounds, sulfonimide compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, triazine compounds, nitrobenzyl compounds. , Organic halides and disulfone.

Examples of the onium salt compounds include iodonium salts, sulfonium salts other than the sulfonium salts represented by the general formula (1) of the present invention, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts, and the like.
Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof.
Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.
Moreover, as said imide sulfonate compound, the compound represented by following General formula (3) can be mentioned, for example.

[In General Formula (3), R ¹² represents a monovalent organic group, and R ¹³ represents a divalent organic group. ]

  Moreover, as said disulfonyl diazomethane, the compound represented by following General formula (4) can be mentioned, for example.

[In the general formula (4), each R ¹⁴ is independently a linear or branched monovalent aliphatic hydrocarbon group, a cycloalkyl group, a linear or branched monovalent monovalent group. A halogen-substituted aliphatic hydrocarbon group, a halogen-substituted cycloalkyl group, an aryl group, a halogenated aryl group and the like are shown. ]

  Moreover, as said disulfonylmethane compound, the compound represented by following General formula (5) can be mentioned, for example.

[In the general formula (5), each R ¹⁵ is independently a linear or branched monovalent aliphatic hydrocarbon group, cycloalkyl group, aryl group, aralkyl group or hetero atom 1. V and W are each independently an aryl group, a hydrogen atom, a linear or branched monovalent aliphatic hydrocarbon group, or another monovalent organic group having a hetero atom And at least one of V and W is an aryl group, or V and W are connected to each other to form a monocyclic or polycyclic ring having at least one unsaturated bond, or W are connected to each other to form a group represented by the following formula (6). ]

[In Formula (6), V ′ and W ′ are independent of each other, and a plurality of V ′ and W ′ may be the same or different, and may be a hydrogen atom, a halogen atom, a straight chain Or a branched alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, or V ′ and W ′ bonded to the same or different carbon atoms are connected to each other to form a carbocyclic structure. X is an integer of 2-10. ]

  Moreover, as said oxime sulfonate compound, the compound represented by the following general formula (7-1) or general formula (7-2) can be mentioned, for example.

[In General Formula (7-1) and General Formula (7-2), R ¹⁶ and R ¹⁷ independently represent a monovalent organic group, and two R ¹⁶ in General Formula (7-2) And the two R ¹⁷ may be the same or different. ]
Specific examples of the oxime sulfonate compound include α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2. , 6-dichlorophenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (methylsulfonyloxyimino) -1-phenyl Acetonitrile, α- (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methylsulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile, [2- ( Propylsulfonyloxyimino) -2,3-dihydroxythiophene-3-ylidene] (o-tolyl) acetonitrile, and those represented by the following chemical formula.

  Moreover, as said hydrazine sulfonate compound, the compound represented by General formula (8-1) or General formula (8-2) can be mentioned, for example.

[In General Formula (8-1) and General Formula (8-2), R ¹⁸ represents a monovalent organic group, and two R ¹⁸ in General Formula (8-2) are the same or different from each other. May be. ]

  As other conventionally known photoacid generators, one or more of the group of onium compounds, sulfonimide compounds, diazomethane compounds and oxime sulfonate compounds are preferred.

  When such other conventionally known photoacid generators are used in combination, the use ratio may be arbitrary, but usually other photoacids are used with respect to 100 parts by mass of the sulfonium salt represented by the general formula (1). The generating agent is 10 to 900 parts by mass, preferably 25 to 400 parts by mass.

  The content of the component (A) is preferably 0.05 to 5% by mass in the solid content of the chemically amplified positive photoresist composition.

<Resin component (B) whose solubility in alkali is increased by the action of acid>
The aforementioned “resin (B) whose solubility in alkali is increased by the action of an acid” used in the chemically amplified positive photoresist composition for thick film of the present invention (referred to as “component (B)” in the present specification) .) Is at least one resin selected from the group consisting of novolak resin (B1), polyhydroxystyrene resin (B2), and acrylic resin (B3), or a mixed resin or copolymer thereof.

[Novolac resin (B1)]
As the novolac resin (B1), a resin represented by the following general formula (b1) can be used.

In the general formula (b1), R ^1b represents an acid dissociable, dissolution inhibiting group, R ^2b and R ^3b each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is in parentheses. Represents the number of repeating units in the structure.

Furthermore, ^examples of the acid dissociable, dissolution inhibiting group represented by R ^1b include a group represented by the following general formula (b2) or (b3), a linear alkyl group having 1 to 6 carbon atoms, and 3 to 3 carbon atoms. Preferred are 6 branched alkyl groups, cyclic alkyl groups having 3 to 6 carbon atoms, tetrahydropyranyl group, tetrahydrofuranyl group and trialkylsilyl group.

In the general formulas (b2) and (b3), R ^4b and R ^5b are each independently a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a branched chain having 3 to 6 carbon atoms. Represents an alkyl group, and R ^6b represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, and R ^7b Represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, and o is 0 or 1.

  Examples of the linear alkyl group having 1 to 6 carbon atoms or the branched alkyl group having 3 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert- Examples include a butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

  Here, specific examples of the general formula (b2) include methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, isobutoxyethyl group, tert-butoxyethyl group. , Cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group, and the like. Specific examples of the general formula (b3) include Tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group and the like. Examples of the trialkylsilyl group include a trimethylsilyl group and a tri-tert-butyldimethylsilyl group.

[Polyhydroxystyrene resin (B2)]
As the polyhydroxystyrene resin (B2), a resin represented by the following general formula (b4) can be used.

In the general formula (b4), R ^8b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ^9b represents an acid dissociable, dissolution inhibiting group, and n represents the number of repeating units in the structure in parentheses. Represent.

  The alkyl group having 1 to 6 carbon atoms is a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The cyclic alkyl group includes a cyclopentyl group and a cyclohexyl group. Etc.

As the acid dissociable, dissolution inhibiting group represented by R ^9b , the same acid dissociable, dissolution inhibiting groups as exemplified in the general formulas (b2) and (b3) can be used.

  Furthermore, the polyhydroxystyrene resin (B2) can contain other polymerizable compounds as structural units for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anionic polymerizable compounds. For example, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl Methacrylic acid derivatives having a carboxyl group and an ester bond such as phthalic acid and 2-methacryloyloxyethylhexahydrophthalic acid; (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate Alkyl esters; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) ) (Meth) acrylic acid aryl esters such as acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methyl Vinyl group-containing aromatic compounds such as hydroxystyrene and α-ethylhydroxystyrene; Vinyl group-containing aliphatic compounds such as vinyl acetate; Conjugated diolefins such as butadiene and isoprene; Nitrile groups such as acrylonitrile and methacrylonitrile Polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.

[Acrylic resin (B3)]
As the acrylic resin (B3), resins represented by the following general formulas (b5) to (b10) can be used.

In the general formulas (b5) to (b7), R ^{10b to} R ^17b each independently represent a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a branched alkyl group having 3 to 6 carbon atoms. Represents a group, a fluorine atom, or a linear fluorinated alkyl group having 1 to 6 carbon atoms or a branched fluorinated alkyl group having 3 to 6 carbon atoms, and ^Xb together with the carbon atom to which it is bonded Forming a hydrocarbon ring having 5 to 20 carbon atoms, Y ^b represents an aliphatic cyclic group or an alkyl group which may have a substituent, n represents the number of repeating units of the structure in parentheses, p is an integer of 0 to 4, and q is 0 or 1.

The linear or branched alkyl group in R ^{10b to} R ^17b is a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group. , Isopentyl group, neopentyl group and the like, and cyclic alkyl group include cyclopentyl group, cyclohexyl group and the like. Further, the fluorinated alkyl group is one in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.

R ^11b is preferably a linear alkyl group having 2 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms from the viewpoint of high contrast, good resolution, depth of focus, and the like. R ^13b , R ^14b , R ^16b and R ^17b are preferably a hydrogen atom and a methyl group.

^Xb forms an aliphatic cyclic group having 5 to 20 carbon atoms together with the carbon atom to which it is bonded. Specific examples of such aliphatic cyclic groups include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Groups. In particular, a group obtained by removing one or more hydrogen atoms from cyclohexane or adamantane (which may further have a substituent) is preferable.

Furthermore, when the aliphatic cyclic group of ^Xb has a substituent on the ring skeleton, examples of the substituent include polar groups such as a hydroxyl group, a carboxyl group, a cyano group, and an oxygen atom (= O). And a straight-chain alkyl group having 1 to 4 carbon atoms or a branched lower alkyl group having 3 to 4 carbon atoms. As the polar group, an oxygen atom (═O) is particularly preferable.

Y ^b is an optionally substituted aliphatic cyclic group or an alkyl group, and one or more hydrogen atoms from a polycycloalkane such as a monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane or the like. Examples include groups excluding atoms. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Group and the like. In particular, a group obtained by removing one or more hydrogen atoms from adamantane (which may further have a substituent) is preferable.

Furthermore, the alicyclic group of the abovementioned Y ^b is, if they have a substituent on the ring skeleton, examples of the substituent, a hydroxyl group, a carboxyl group, a cyano group, an oxygen atom (= O) polar groups such as And a linear or branched lower alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (═O) is particularly preferable.

When Y ^b is an alkyl group, it is preferably a linear alkyl group having 1 to 20 carbon atoms, more preferably 6 to 15 or a branched chain having 3 to 20 carbon atoms, more preferably 6 to 15 carbon atoms. It is an alkyl group. Such an alkyl group is particularly preferably an alkoxyalkyl group, and examples of such an alkoxyalkyl group include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxy group. Ethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1 -Ethoxy-1-methylethyl group etc. are mentioned.

In general formula (b8), general formula (b9), and general formula (b10), R ^18b , R ^20b, and R ^21b each independently represent a hydrogen atom or a methyl group, and in general formula (b8), R ^19b is independently of each other a hydrogen atom, a hydroxyl group, a cyano group, or a COOR ^23b group (where R ^23b is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched chain having 3 to 4 carbon atoms). Represents a chain alkyl group or a cycloalkyl group having 3 to 20 carbon atoms.) In the general formula (b10), each R ^22b is independently a monovalent alicyclic group having 4 to 20 carbon atoms. A hydrocarbon group or a derivative thereof, a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, and at least one of R ^22b is the alicyclic hydrocarbon group or It is a derivative thereof, or any two Two R ^22b are bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with a common carbon atom to which each R ^22b is bonded, and the remaining R ^22b is a carbon atom. A linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a derivative thereof is represented.

  Preferable specific examples of the acrylic resin represented by the general formula (b5) include those represented by the following general formulas (b5-1) to (b5-3).

In the general formulas (b5-1) to (b5-3), R ^18b represents a hydrogen atom or a methyl group, and n represents the number of repeating units in the structure in parentheses.

  Preferable specific examples of the acrylic resin represented by the general formula (b6) include those represented by the following general formulas (b6-1) to (b6-28).

    Preferable specific examples of the acrylic resin represented by the general formula (b7) include those represented by the following general formulas (b7-1) to (b7-22).

  As a preferable repeating unit of the acrylic resin represented by the general formula (b8), for example, (meth) acrylic acid 3-hydroxyadamantan-1-yl, (meth) acrylic acid 3,5-dihydroxyadamantan-1-yl , (Meth) acrylic acid 3-cyanoadamantan-1-yl, (meth) acrylic acid 3-carboxyladamantan-1-yl, (meth) acrylic acid 3,5-dicarboxyladamantan-1-yl, (meth) acrylic Examples include units in which a polymerizable unsaturated bond is cleaved, such as acid 3-carboxyl-5-hydroxyadamantan-1-yl and (meth) acrylic acid 3-methoxycarbonyl-5-hydroxyadamantan-1-yl.

  As a preferable repeating unit of the acrylic resin represented by the general formula (b10), for example, 1-methyl-1-cyclopentyl (meth) acrylate, 1-ethyl-1-cyclopentyl (meth) acrylate, (meth) 1-methyl-1-cyclohexyl acrylate, 1-ethyl-1-cyclohexyl (meth) acrylate, 2-methyladamantyl-2-yl (meth) acrylate, 2-ethyladamantyl-2-yl (meth) acrylate , (Meth) acrylic acid 2-n-propyladamantyl-2-yl, (meth) acrylic acid 2-i-propyladamantyl-2-yl, (meth) acrylic acid 1- (adamantan-1-yl) -1- Examples include units in which a polymerizable unsaturated bond such as methylethyl is cleaved.

  Further, the (B3) acrylic resin is made of a copolymer containing structural units derived from a polymerizable compound having an ether bond with respect to the structural units represented by the general formulas (b5) to (b10). A resin is preferred.

  Such a structural unit is a structural unit derived from a polymerizable compound having an ether bond. Examples of polymerizable compounds having an ether bond include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol ( Exemplified radical polymerizable compounds such as (meth) acrylic acid derivatives having ether bonds and ester bonds such as (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate Preferably, it is 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylateAny one of these compounds may be used alone, or two or more thereof may be used in combination.

  Furthermore, the (B3) acrylic resin can contain other polymerizable compounds as constituent units for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anionic polymerizable compounds. For example, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl Methacrylic acid derivatives having a carboxyl group and an ester bond such as phthalic acid and 2-methacryloyloxyethylhexahydrophthalic acid; (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate Alkyl esters; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) ) (Meth) acrylic acid aryl esters such as acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methyl Vinyl group-containing aromatic compounds such as hydroxystyrene and α-ethylhydroxystyrene; Vinyl group-containing aliphatic compounds such as vinyl acetate; Conjugated diolefins such as butadiene and isoprene; Nitrile groups such as acrylonitrile and methacrylonitrile Polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.

  Among the components (B), it is preferable to use an acrylic resin (B3).

  Among the acrylic resins (B3), structural units represented by the general formulas (b5) to (b10), a structural unit derived from a polymerizable compound having an ether bond, a (meth) acrylic acid unit, It is preferable that it is a copolymer which has a structural unit which consists of (meth) acrylic-acid alkylesters.

  The proportion of the structural units represented by the general formulas (b5) to (b10) in the copolymer is preferably 20 to 70% by mass.

  Moreover, the polystyrene conversion weight average molecular weight of a component (B) becomes like this. Preferably it is 10,000-600,000, More preferably, it is 50,000-600,000, More preferably, it is 230,000-550,000. is there. By setting it as such a weight average molecular weight, the resin physical property of a resist becomes excellent.

  Furthermore, the component (B) is preferably a resin having a dispersity of 1.05 or more. Here, the “dispersion degree” is a value obtained by dividing the weight average molecular weight by the number average molecular weight. By setting such a degree of dispersion, the resist plating resistance and resin physical properties are excellent.

  The content of the component (B) is preferably 5 to 60% by weight in the solid text of the chemically amplified positive photoresist composition.

<Alkali-soluble resin (C)>
The chemically amplified positive photoresist composition of the present invention preferably further contains an alkali-soluble resin (referred to herein as “component (C)”) in order to improve the resin physical properties of the resist. . Component (C) is preferably at least one selected from the group consisting of novolak resin (C1), polyhydroxystyrene resin (C2), acrylic resin (C3), and polyvinyl resin (C4).

[Novolac resin (C1)]
As the novolak resin (C1), those having a weight average molecular weight of 1,000 to 50,000 are preferable.

  The novolak resin (C1) can be obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as “phenols”) and an aldehyde in the presence of an acid catalyst. Examples of phenols used at this time include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p. -Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3, 4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglicinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol, etc. It is.

  Examples of aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. The catalyst for the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used as the acid catalyst.

  It is possible to further improve the flexibility of the resin by using o-cresol, substituting the hydrogen atom of the hydroxyl group in the resin with another substituent, or using bulky aldehydes. is there.

[Polyhydroxystyrene resin (C2)]
The polyhydroxystyrene resin (C2) preferably has a weight average molecular weight of 1,000 to 50,000.

  Examples of the hydroxystyrene compound constituting the polyhydroxystyrene resin (C2) include p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene, and the like. Furthermore, the polyhydroxystyrene resin (C2) is preferably a copolymer with a styrene resin, and examples of the styrene compound constituting the styrene resin include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, Examples include α-methylstyrene.

[Acrylic resin (C3)]
The acrylic resin (C3) preferably has a weight average molecular weight of 50,000 to 800,000.

  Such an acrylic resin (C3) is preferably one comprising a monomer unit derived from a polymerizable compound having an ether bond and a monomer unit derived from a polymerizable compound having a carboxyl group.

  Examples of the polymerizable compound having an ether bond include 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxypolyethylene glycol ( Examples include (meth) acrylic acid derivatives having an ether bond and an ester bond such as (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and preferably 2-methoxyethyl acrylate. And methoxytriethylene glycol acrylate. Any one of these compounds may be used alone, or two or more thereof may be used in combination.

  Examples of the polymerizable compound having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, 2-methacryloyloxyethyl succinic acid, and 2-methacryloyloxy. Examples thereof include compounds having a carboxyl group and an ester bond such as ethylmaleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid, and acrylic acid and methacrylic acid are preferable. Any one of these compounds may be used alone, or two or more thereof may be used in combination.

[Polyvinyl resin (C4)]
The polyvinyl resin (C4) preferably has a weight average molecular weight of 10,000 to 200,000, more preferably 50,000 to 100,000.

  The polyvinyl resin (C4) is poly (vinyl lower alkyl ether), and can be obtained by polymerizing any one or a mixture of two or more vinyl lower alkyl ethers represented by the following general formula (c1) ( Co) polymer.

In the above formula, R ^1c represents a linear or branched alkyl group having 1 to 6 carbon atoms.

  The polyvinyl resin (C4) is a polymer obtained from a vinyl compound, and specific examples thereof include polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, and copolymers thereof. Of these, polyvinyl methyl ether is preferred in view of the low glass transition point.

  The content of the component (C) is preferably 5 to 95 parts by weight, more preferably 10 to 90 parts by weight with respect to 100 parts by weight of the component (B). When the amount is 5 parts by weight or more, the resin physical properties of the resist can be improved, and when the amount is 95 parts by weight or less, there is a tendency that film loss during development can be prevented.

<Acid diffusion control agent (D)>
The chemical amplification type positive photoresist composition for thick film of the present invention further comprises an acid diffusion control agent (D) (in the present specification, “component ( D) ").) Is preferably included. As the component (D), a nitrogen-containing compound (D1) is preferable, and an organic carboxylic acid (D2), a phosphorus oxo acid, or a derivative thereof (D3) can be further contained as necessary.

[Nitrogen-containing compound (D1)]
Examples of the nitrogen-containing compound (D1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tribenzylamine, diethanolamine, triethanolamine, n-hexylamine, n-heptylamine, n -Octylamine, n-nonylamine, ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4, 4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propi Amide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, imidazole, benz Imidazole, 4-methylimidazole, 8-oxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tri (2-pyridyl) -S-triazine, morpholine, 4-methylmorpholine, piperazine, 1,4- Examples thereof include dimethylpiperazine and 1,4-diazabicyclo [2.2.2] octane. Of these, alkanolamines such as triethanolamine are particularly preferred. Any of these may be used alone, or two or more of these may be used in combination.

  The nitrogen-containing compound (D1) is usually used in the range of 0 to 5 parts by weight, particularly in the range of 0 to 3 parts by weight, based on 100 parts by weight of the total weight of the component (B) and the component (C). It is preferable to be used.

[Organic carboxylic acid (D2)]
Specifically, as the organic carboxylic acid (D2), malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, and the like are preferable, and salicylic acid is particularly preferable.

[Oxo acid of phosphorus or derivative thereof (D3)]
Examples of phosphorus oxo acids or derivatives thereof (D3) include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and other phosphoric acid or derivatives thereof such as phosphonic acid, phosphonic acid dimethyl Phosphonic acids such as esters, phosphonic acid-di-n-butyl esters, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester and derivatives thereof; phosphinic acids such as phosphinic acid, phenylphosphinic acid and Examples thereof include derivatives such as esters, and among these, phosphonic acid is particularly preferable. These may be used alone or in combination of two or more.

  (D2) or (D3) is usually used in the range of 0 to 5 parts by weight, particularly in the range of 0 to 3 parts by weight, based on 100 parts by weight of the total weight of the component (B) and the component (C). It is preferable to be used.

  In order to form a salt and stabilize it, (D2) or (D3) is preferably used in an amount equivalent to the nitrogen-containing compound (D1).

  The chemically amplified positive photoresist composition of the present invention may further contain an adhesion assistant in order to improve the adhesion to the substrate. As the adhesion aid used, a functional silane coupling agent is preferable. Specific functional silane coupling agents include silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, and epoxy groups. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. The content of the adhesion assistant is preferably 20 parts by weight or less with respect to 100 parts by weight of the total weight of the component (B) and the component (C).

  The chemically amplified positive photoresist composition of the present invention may further contain a surfactant in order to improve coating properties, antifoaming properties, leveling properties and the like. Examples of surfactants include BM-1000, BM-1100 (both trade names; manufactured by BM Chemie), MegaFuck F142D, MegaFuck F172, MegaFuck F173, MegaFuck F183 (both trade names; Dainippon) Ink Chemical Industry Co., Ltd.), Fluorard FC-135, Fluorard FC-170C, Fluorard FC-430, Fluorard FC-431 (all trade names; manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S -131, Surflon S-141, Surflon S-145 (all trade names; manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all trade names; Toray Silicone) Commercially available fluorosurfactants such as Not determined.

  The chemically amplified positive photoresist composition of the present invention may further contain an acid, an acid anhydride, or a high boiling point solvent in order to finely adjust the solubility in an alkali developer. Examples of acids and acid anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, cinnamic acid; lactic acid, 2-hydroxybutyric acid, 3 Hydroxy monocarboxylic acids such as hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, syringic acid Oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid , Butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid Polyvalent carboxylic acids such as butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanilic anhydride, maleic anhydride, hexa hexahydrate Hydrophthalic acid, methyltetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride And acid anhydrides such as acid, anhydrous benzophenone tetracarboxylic acid, ethylene glycol bistrimellitic anhydride, and glycerin tris anhydrous trimellitate. Examples of high-boiling solvents include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl Ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, Examples thereof include propylene carbonate and phenyl cellosolve acetate. The amount of the compound used for finely adjusting the solubility in the alkali developer as described above can be adjusted according to the application and application method, and is particularly limited as long as the composition can be mixed uniformly. Although not intended, it is 60% by weight or less, preferably 40% by weight or less, based on the total weight of the composition obtained.

  In addition, the chemically amplified positive photoresist composition of the present invention basically does not require a sensitizer, but can contain a sensitizer as necessary to supplement sensitivity. As such a sensitizer, conventionally known ones can be used. Specifically, anthracene {anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2 -Ethyl-9,10-dimethoxyanthracene, 2-tert-butyl-9,10-dimethoxyanthracene, 2,3-dimethyl-9,10-dimethoxyanthracene, 9-methoxy-10-methylanthracene, 9,10-di Ethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-tert-butyl-9,10-diethoxyanthracene, 2,3-dimethyl-9,10-diethoxyanthracene, 9-ethoxy-10-methyl Anthracene, 9,10-dipropoxyanthracene, 9,10-di Propoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dipropoxyanthracene, 2-tert-butyl-9,10-dipropoxyanthracene, 2,3-dimethyl-9,10-dipropoxyanthracene , 9-Isopropoxy-10-methylanthracene, 9,10-dibenzyloxyanthracene, 2-ethyl-9,10-dibenzyloxyanthracene, 2-tert-9,10-dibenzyloxyanthracene, 2,3- Dimethyl-9,10-dibenzyloxyanthracene, 9-benzyloxy-10-methylanthracene, 9,10-di-α-methylbenzyloxyanthracene, 2-ethyl-9,10-di-α-methylbenzyloxyanthracene , 2-tert-9,10-di-α-methyl Benzyloxyanthracene, 2,3-dimethyl-9,10-di-α-methylbenzyloxyanthracene, 9- (α-methylbenzyloxy) -10-methylanthracene, 9,10-diphenylanthracene, 9-methoxyanthracene, 9-ethoxyanthracene, 9-methylanthracene, 9-bromoanthracene, 9-methylthioanthracene, 9-ethylthioanthracene, etc.}; pyrene; 1,2-benzanthracene; perylene; tetracene; coronene; thioxanthone {thioxanthone, 2-methyl Thioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone and 2,4-diethylthioxanthone}; phenothiazine {phenothiazine, N-methylphenothiazine, N-e Ruphenothiazine, N-phenylphenothiazine, etc.}; xanthone; naphthalene {1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,7-dimethoxynaphthalene, 1,1'-thiobis (2-naphthol), 1,1'-bi- (2-naphthol), 4-methoxy-1-naphthol, etc. }; Ketone {dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2 -Methylpropiophenone, 2,2-dimethyl Toxi-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexyl phenyl ketone, benzoin , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1 -One, benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone and 4-benzoyl-4 ' Methyldiphenyl sulfide, etc.}; carbazole {N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole, N-glycidylcarbazole, etc.}; chrysene {1,4-dimethoxychrysene, 1,4-diethoxychrysene, 1 , 4-dipropoxychrysene, 1,4-dibenzyloxychrysene and 1,4-di-α-methylbenzyloxychrysene, etc.}; phenanthrene {9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-ethoxyphenanthrene, 9- Benzyloxyphenanthrene, 9,10-dimethoxyphenanthrene, 9,10-diethoxyphenanthrene, 9,10-dipropoxyphenanthrene, 9,10-dibenzyloxyphenanthrene, 9,10-di-α-methylbenzyloxy Phenanthrene, 9-hydroxy-10-methoxy-phenanthrene and 9-hydroxy-10-ethoxy phenanthrene, etc.}; coumarin and the like. Any one of these may be used alone, or two or more thereof may be mixed and used.

  The amount of these sensitizers used is 5 to 500 parts by weight, preferably 10 to 300 parts by weight, based on 100 parts by weight of the sulfonium salt represented by the general formula (1).

  The chemically amplified positive photoresist composition of the present invention can be appropriately mixed with an organic solvent for viscosity adjustment. Specific examples of organic solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, diester Polyhydric alcohols such as propylene glycol and dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; ethyl formate; Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate , Ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 2-hydroxy-3- Mention may be made of esters such as methyl methylbutanoate, 3-methoxybutyl acetate and 3-methyl-3-methoxybutyl acetate; and aromatic hydrocarbons such as toluene and xylene. Any one of these may be used alone, or two or more thereof may be mixed and used.

  The amount of these organic solvents used is such that the concentration of the solid content is 5 μm or more so that the thickness of the photoresist layer obtained by using the chemically amplified positive photoresist composition of the present invention (for example, spin coating method) is 5 μm or more. Is preferably 30% by weight or more.

  The thick film chemically amplified positive photoresist composition of the present invention can be prepared, for example, by mixing and stirring the above-mentioned components by a usual method. If necessary, a dissolver, a homogenizer, a three-roll mill, etc. You may disperse and mix using a disperser. Further, after mixing, it may be filtered using a mesh, a membrane filter or the like.

  The chemically amplified positive photoresist composition of the present invention is suitable for forming a photoresist layer having a thickness of usually 5 to 150 μm, more preferably 10 to 120 μm, and still more preferably 10 to 100 μm on a support. ing. This photoresist laminate is obtained by laminating a photoresist layer made of the chemically amplified positive photoresist composition of the present invention on a support.

  The support is not particularly limited, and a conventionally known one can be used. For example, a substrate for electronic parts or a substrate on which a predetermined wiring pattern is formed can be exemplified. Examples of the substrate include a metal substrate such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, and aluminum, and a glass substrate. In particular, the chemically amplified positive photoresist composition of the present invention can form a resist pattern satisfactorily even on a copper substrate. As a material for the wiring pattern, for example, copper, solder, chromium, aluminum, nickel, gold, or the like is used.

  The photoresist laminate can be produced, for example, as follows. That is, a desired coating film is formed by applying a solution of the chemically amplified positive photoresist composition prepared as described above onto a support and removing the solvent by heating. As a coating method on the support, methods such as a spin coating method, a slit coating method, a roll coating method, a screen printing method, and an applicator method can be employed. The pre-baking conditions of the coating film of the composition of the present invention vary depending on the type of each component in the composition, the blending ratio, the coating film thickness, etc., but usually 70 to 150 ° C., preferably 80 to 140 ° C. What is necessary is just about 60 minutes.

  The film thickness of the photoresist layer is usually 5 to 150 μm, preferably 10 to 120 μm, more preferably 10 to 100 μm.

  In order to form a resist pattern using the thus obtained photoresist laminate, light or radiation, for example, having a wavelength of 300 to 500 nm is passed through the obtained photoresist layer through a mask having a predetermined pattern. Irradiation (exposure) with ultraviolet rays or visible rays may be performed selectively.

Here, “light” may be light that activates the acid generator to generate acid, and includes ultraviolet rays, visible rays, and far ultraviolet rays, and “radiation” means X-rays, electron beams, It means an ion beam. As a light or radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, an LED lamp, or the like can be used. Further, the radiation irradiation amount varies depending on the kind of each component in the composition, the blending amount, the film thickness of the coating film, etc., but is, for example, 50 to 10,000 mJ / cm ² when using an ultrahigh pressure mercury lamp.

  Then, after the exposure, the diffusion of the acid is promoted by heating using a known method to change the alkali solubility of the photoresist layer in the exposed portion. Next, for example, using a predetermined alkaline aqueous solution as a developer, unnecessary portions are dissolved and removed to obtain a predetermined resist pattern.

  Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethyl. Ethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0 An aqueous solution of an alkali such as -5-nonane can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, isopropanol or a surfactant to the alkaline aqueous solution can also be used as a developer.

  The development time varies depending on the type of each component of the composition, the blending ratio, and the dry film thickness of the composition, but it is usually 1 to 30 minutes. Any of these may be used. After the development, washing with running water is performed for 30 to 90 seconds and dried using an air gun, oven, or the like.

  Forming connection terminals such as metal posts and bumps by embedding a conductor such as metal in the non-resist portion (the portion removed with the alkaline developer) of the resist pattern thus obtained by, for example, plating. Can do. The plating method is not particularly limited, and various conventionally known methods can be employed. As the plating solution, solder plating, copper plating, gold plating, or nickel plating solution is particularly preferably used. The remaining resist pattern is finally removed using a stripping solution or the like according to a conventional method.

  The chemically amplified positive photoresist composition of the present invention can also be used as a dry film. This dry film has a protective film formed on both sides of a layer made of the chemically amplified positive photoresist composition of the present invention. The thickness of the layer made of the chemically amplified positive photoresist composition is usually 5 to 150 μm, preferably 20 to 120 μm, more preferably 20 to 80 μm. Moreover, a protective film is not specifically limited, The resin film conventionally used for the dry film can be used. As an example, one may be a polyethylene terephthalate film and the other may be one selected from the group consisting of a polyethylene terephthalate film, a polypropylene film, and a polyethylene film.

  The chemical amplification type positive dry film as described above can be manufactured, for example, as follows. That is, a solution of a chemically amplified positive photoresist composition prepared as described above is applied on one protective film, and the solvent is removed by heating to form a desired coating film. The drying conditions vary depending on the type of each component in the composition, the blending ratio, the coating film thickness, etc., but are usually 60 to 100 ° C. and about 5 to 20 minutes.

  In order to form a resist pattern using the thus obtained chemically amplified dry film, one protective film of the chemically amplified positive dry film is peeled off and the exposed surface is directed to the support side described above. Then, after laminating on the support to obtain a photoresist layer, after prebaking to dry the resist, the other protective film may be peeled off.

  In the photoresist layer thus obtained on the support, a resist pattern can be formed in the same manner as described above with respect to the photoresist layer formed by coating directly on the support. .

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, it is not intending that this invention is limited to those Examples. In the following, “part” means part by weight and “%” means weight% unless otherwise specified.

[Production of sulfonium salt mixture-step 1]
(Production Example 1) Production of a mixture of [4- (trimethylsilyl) phenyl] phenyl sulfide and [4- (trimethylsilyl) phenyl] phenyl sulfoxide [4- (trimethylsilyl) phenyl] phenyl sulfide 10.0 parts, acetonitrile 40.0 parts Then, after 0.19 parts of sulfuric acid was charged and mixed uniformly, the temperature was raised to 50 ° C. and 2.19 parts of a 30% aqueous hydrogen peroxide solution was added dropwise over 10 minutes. Thereafter, the mixture was reacted at 65 ° C. for 3 hours. After cooling the reaction solution to room temperature (about 25 ° C.), 150 parts of dichloromethane was added and washed with 200 parts of distilled water until the pH became neutral. By transferring the dichloromethane layer to a rotary evaporator and distilling off the solvent, 48.5% of brown liquid [4- (trimethylsilyl) phenyl] phenyl sulfide and 51.5% of [4- (trimethylsilyl) phenyl] phenyl sulfoxide were obtained. 9.8 parts of a mixture containing were obtained. ¹ H-NMR data of [4- (trimethylsilyl) phenyl] phenyl sulfoxide: {d6-dimethyl sulfoxide, δ (ppm) 7.5 to 7.8 (6H, m), 7.1 to 7.4 (3H, m), 0.2 (9H, s)}. The content was calculated from the peak area ratio by HPLC analysis of the mixture.

(Production Example 2) Production of a mixture of [4- (trimethylsilyl) phenyl] 2-methylphenyl sulfide and [4- (trimethylsilyl) phenyl] 2-methylphenyl sulfoxide 10.0 parts of [4- (trimethylsilyl) phenyl] phenyl sulfide In the same manner as in Production Example 1, except that [4- (trimethylsilyl) phenyl] 2-methylphenyl sulfide is changed to 10.5 parts, % And 9.2 parts of a mixture containing 51% of [4- (trimethylsilyl) phenyl] 2-methylphenyl sulfoxide. ¹ H-NMR data of [4- (trimethylsilyl) phenyl] 2-methylphenyl sulfoxide: {d6-dimethyl sulfoxide, δ (ppm) 7.5 to 7.8 (6H, m), 7.1 to 7.4 (3H, m), 0.2 (9H, s)}. The content was calculated from the peak area ratio by HPLC analysis of the mixture.

(Production Example 3) Production of a mixture of [4- (triphenylsilyl) phenyl] phenyl sulfide and [4- (triphenylsilyl) phenyl] phenyl sulfoxide 10.0 parts of [4- (triphenylsilyl) phenyl] phenyl sulfide Then, 40.0 parts of acetonitrile and 0.11 part of sulfuric acid were charged and mixed uniformly, then the temperature was raised to 50 ° C., and 1.28 parts of 30% hydrogen peroxide aqueous solution was added dropwise over 10 minutes. Thereafter, the mixture was reacted at 65 ° C. for 3 hours. After cooling the reaction solution to room temperature (about 25 ° C.), 150 parts of dichloromethane was added and washed with 200 parts of distilled water until the pH became neutral. By transferring the dichloromethane layer to a rotary evaporator and distilling off the solvent, 49% of brown liquid [4- (triphenylsilyl) phenyl] phenyl sulfide and 51% of [4- (triphenylsilyl) phenyl] phenyl sulfoxide were obtained. 9.7 parts of a mixture containing were obtained. ¹ H-NMR data of [4- (triphenylsilyl) phenyl] phenyl sulfoxide: {d6-dimethyl sulfoxide, δ (ppm) 7.5 to 7.8 (12H, m), 7.1 to 7.4 ( 12H, m)}. The content was calculated from the peak area ratio by HPLC analysis of the mixture.

(Production Example 4) Production of a mixture of [4- (triphenylsilyl) phenyl] 2-methylphenyl sulfide and [4- (triphenylsilyl) phenyl] 2-methylphenyl sulfoxide [4- (triphenylsilyl) phenyl] A brown liquid [4- (triphenylsilyl) was prepared in the same manner as in Production Example 3 except that 10.0 parts of phenylsulfide was changed to 10.3 parts of [4- (triphenylsilyl) phenyl] 2-methylphenylsulfide. ) Phenyl] 2-methylphenyl sulfide was obtained in an amount of 10.0 parts and 49 parts of [4- (triphenylsilyl) phenyl] 2-methylphenyl sulfoxide was obtained in 10.0 parts. ¹ H-NMR data of [4- (triphenylsilyl) phenyl] 2-methylphenyl sulfoxide: {d6-dimethyl sulfoxide, δ (ppm) 7.5 to 7.8 (11H, m), 7.1 to 7 .4 (12H, m), 2.4 (3H, s)}. The content was calculated from the peak area ratio by HPLC analysis of the mixture.

[Example 1]
Preparation of [4- (4-trimethylsilyl) phenylthio] phenyl (4-trimethylsilyl) phenylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate

4.8 parts of the mixture of [4- (trimethylsilyl) phenyl] phenyl sulfide and [4- (trimethylsilyl) phenyl] phenyl sulfoxide produced in Production Example 1 was dissolved in 23.3 parts of methanesulfonic acid, and acetic anhydride 2 was dissolved at room temperature. 8 parts were added dropwise. Then, it was made to react at 60 degreeC for 6 hours, and after cooling the reaction solution to room temperature (about 25 degreeC), it injected into 200 parts of distilled water.
While stirring, 52.7 parts of a 10% aqueous solution of potassium tris (pentafluoroethyl) trifluorophosphate was added dropwise, and stirring was continued for 3 hours at room temperature (about 25 ° C.). Extracted. The organic layer (dichloromethane layer) was separated and washed 5 times with water. The organic layer was transferred to a rotary evaporator, the solvent was distilled off, and the residue was washed with a toluene / hexane solution to give [4- (4- 7.4 parts of trimethylsilyl) phenylthio] phenyl (4-trimethylsilyl) phenylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate were obtained. The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. { ¹ H-NMR: d6-dimethylsulfoxide; δ (ppm) 7.6 to 8.0 (9H, m), 7.2 to 7.6 (8H, m), 0.2 to 0.3 (18H , S). IR (KBr tablet method: CF bond characteristic absorption; around 1200 cm ^−1. LC-MS: molecular ion peak; 516.

[Example 2]
Preparation of [4- (4-trimethylsilyl) phenylthio] phenyl (4-trimethylsilyl) phenylphenylsulfonium tetrakis (pentafluorophenyl) borate

Except that “10% tris (pentafluoroethyl) potassium trifluorophosphate aqueous solution 52.7 parts” was changed to “10% tetrakis (pentafluorophenyl) lithium borate aqueous solution 74.6 parts”, the same procedure as in Example 1 was performed. Thus, 9.2 parts of [4- (4-trimethylsilyl) phenylthio] phenyl (4-trimethylsilyl) phenylphenylsulfonium tetrakis (pentafluorophenyl) borate was obtained. The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. { ¹ H-NMR: d6-dimethylsulfoxide; δ (ppm) 7.6 to 8.0 (9H, m), 7.2 to 7.6 (8H, m), 0.2 to 0.3 (18H , S). IR (KBr tablet method): B—C bond characteristic absorption; near 980 cm ⁻¹ . LC-MS: molecular ion peak; 516.

Example 3
Preparation of [4- (4-trimethylsilyl) phenylthio] phenyl (4-trimethylsilyl) phenylphenylsulfonium hexafluoroantimonate

Except that “10% tris (pentafluoroethyl) potassium trifluorophosphate aqueous solution 52.7 parts” was changed to “5% potassium hexafluoroantimonate aqueous solution 150 parts” in the same manner as in Example 1, [4- ( 5.8 parts of 4-trimethylsilyl) phenylthio] phenyl (4-trimethylsilyl) phenylphenylsulfonium hexafluoroantimonate were obtained. The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. { ¹ H-NMR: d6-dimethylsulfoxide; δ (ppm) 7.6 to 8.0 (9H, m), 7.2 to 7.6 (8H, m), 0.2 to 0.3 (18H , S). IR (KBr tablet method): Sb-F binding property absorption; around 650 cm ⁻¹ . LC-MS: molecular ion peak; 516.

Example 4
Preparation of [4- (4-trimethylsilyl) phenylthio] phenyl (4-trimethylsilyl) phenylphenylsulfonium hexafluorophosphate

In the same manner as in Example 1, except that “10% tris (pentafluoroethyl) potassium trifluorophosphate aqueous solution 52.7 parts” was changed to “5% potassium hexafluorophosphate aqueous solution 100 parts” [4- ( 5.1 parts of 4-trimethylsilyl) phenylthio] phenyl (4-trimethylsilyl) phenylphenylsulfonium hexafluorophosphate were obtained.
The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. { ¹ H-NMR: d6-dimethylsulfoxide; δ (ppm) 7.6 to 8.0 (9H, m), 7.2 to 7.6 (8H, m), 0.2 to 0.3 (18H , S). IR (KBr tablet method): PF bond characteristic absorption; around 840 cm ⁻¹ . LC-MS: molecular ion peak; 516.

Example 5
Preparation of [4- (4-trimethylsilyl) phenylthio] phenyl (4-trimethylsilyl) phenylphenylsulfonium nonafluorobutanesulfonate

Except that “10% tris (pentafluoroethyl) potassium trifluorophosphate aqueous solution 52.7 parts” was changed to “5% sodium nonafluorobutanesulfonate aqueous solution 63.1 parts”, in the same manner as in Example 1, 6.0 parts of 4- (4-trimethylsilyl) phenylthio] phenyl (4-trimethylsilyl) phenylphenylsulfonium nonafluorobutanesulfonate were obtained.
The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. { ¹ H-NMR: d6-dimethylsulfoxide; δ (ppm) 7.6 to 8.0 (9H, m), 7.2 to 7.6 (8H, m), 0.2 to 0.3 (18H , S). IR (KBr tablet method: CF bond characteristic absorption; around 1200 cm ^−1. LC-MS: molecular ion peak; 516.

Example 6
Preparation of [4- (4-trimethylsilyl) phenylthio] -3-methylphenyl (4-trimethylsilyl) phenyl 2-methylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate

4.8 parts of a mixture of [4- (trimethylsilyl) phenyl] 2-methylphenyl sulfide and [4- (trimethylsilyl) phenyl] 2-methylphenyl sulfoxide was prepared in Preparation Example 2 [4- (trimethylsilyl) phenyl] 2- [4- (4-Trimethylsilyl) phenylthio] -3-methyl was prepared in the same manner as in Example 1 except that the mixture was changed to 5.1 parts of a mixture of methylphenyl sulfide and [4- (trimethylsilyl) phenyl] 2-methylphenyl sulfoxide. 7.6 parts of phenyl (4-trimethylsilyl) phenyl 2-methylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate were obtained.
The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. { ¹ H-NMR: d6-dimethylsulfoxide; δ (ppm) 7.6 to 8.0 (8H, m), 7.2 to 7.6 (7H, m), 2.4 to 2.5 (6H , D), 0.2-0.3 (18H, s). IR (KBr tablet method: CF bond characteristic absorption; around 1200 cm ^−1. LC-MS: molecular ion peak; 572.

Example 7
Preparation of [4- (4-triphenylsilyl) phenylthio] phenyl (4-triphenylsilyl) phenylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate

4.8 parts of a mixture of [4- (trimethylsilyl) phenyl] phenyl sulfide and [4- (trimethylsilyl) phenyl] phenyl sulfoxide was prepared in Preparation Example 3 with [4- (triphenylsilyl) phenyl] phenyl sulfide and [4- [4- (4-Triphenyl) was prepared in the same manner as in Example 1 except that 8.2 parts of (triphenylsilyl) phenyl] phenyl sulfoxide was changed to 28.8 parts of methanesulfonic acid. 10.3 parts of (silyl) phenylthio] phenyl (4-triphenylsilyl) phenylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate were obtained.
The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. ^{1 H-NMR: d6- dimethylsulfoxide; δ (ppm) 7.6~8.0 (9H , m), 7.2~7.6 (38H, m). IR (KBr tablet method: CF bond characteristic absorption; around 1200 cm ^−1. LC-MS: molecular ion peak; 888.

Example 8
Preparation of [4- (4-triphenylsilyl) phenylthio] -3-methylphenyl (4-triphenylsilyl) phenyl 2-methylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate

4.8 parts of a mixture of [4- (trimethylsilyl) phenyl] phenyl sulfide and [4- (trimethylsilyl) phenyl] phenyl sulfoxide, and [4- (triphenylsilyl) phenyl] 2-methylphenyl sulfide prepared in Preparation Example 4 [4] [4 (triphenylsilyl) phenyl] 2-methylphenyl sulfoxide in the same manner as in Example 1, except that 23.3 parts of methanesulfonic acid was changed to 38.8 parts. 10.5 parts of-(4-triphenylsilyl) phenylthio] -3-methylphenyl (4-triphenylsilyl) phenyl 2-methylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate were obtained.
The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. { ¹ H-NMR: d6-dimethylsulfoxide; δ (ppm) 7.6 to 8.0 (8H, m), 7.2 to 7.6 (37H, m), 2.4 to 2.5 (6H , D). IR (KBr tablet method: CF bond characteristic absorption; around 1200 cm ^−1. LC-MS: molecular ion peak; 916.

[Comparative Example 1]
CPI-110P [4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, manufactured by San Apro Co., Ltd.] was used as a comparative sulfonium salt.

[Comparative Example 2]
CPI-110A [4- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, manufactured by San Apro Co., Ltd.] was used as a comparative sulfonium salt.

[Comparative Example 3]
Synthesis of 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate

While stirring 12.1 parts of diphenyl sulfoxide, 9.3 parts of diphenyl sulfide and 43.0 parts of methanesulfonic acid, 7.9 parts of acetic anhydride was added dropwise thereto and reacted at 40 to 50 ° C. for 5 hours. After cooling to room temperature (about 25 ° C.), the reaction solution was put into 121 parts of 20% aqueous potassium tris (pentafluoroethyl) trifluorophosphate and stirred at room temperature (about 25 ° C.) for 1 hour. A viscous oil precipitated. This oily substance was extracted with ethyl acetate, the organic layer was washed several times with water, the solvent was distilled off from the organic layer, and toluene was added to the resulting residue to dissolve it. The mixture was stirred well for 1 hour and allowed to stand. After 1 hour, since the solution was separated into two layers, the upper layer was removed by liquid separation. When hexane was added to the remaining lower layer and mixed well at room temperature (about 25 ° C.), pale yellow crystals were precipitated. This was filtered off and dried under reduced pressure to obtain 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate in a yield of 60%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 7.72-7.87 (12H, m), 7.54-7.63 (5H, m), 7.42. (2H, d)}. Further, absorption of C—F bond was confirmed in the vicinity of 1200 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

[Comparative Example 4]
Synthesis of 4- (phenylthio) phenyldiphenylsulfonium tetrakis (pentafluorophenyl) borate

4 except that “20% tris (pentafluoroethyl) potassium trifluorophosphate aqueous solution 121 parts” was changed to “10% lithium tetrakis (pentafluorophenyl) lithium borate 342.9 parts”. -(Phenylthio) phenyldiphenylsulfonium tetrakis (pentafluorophenyl) borate was obtained in a yield of 60%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 7.72-7.87 (12H, m), 7.54-7.63 (5H, m), 7.42. (2H, d)}. Further, absorption of BC bond was confirmed in the vicinity of 980 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

[Comparative Example 5]
Synthesis of diphenyl-2-thioxanthonylsulfonium tris (pentafluoroethyl) trifluorophosphate

15.0 parts of 2- (phenylthio) thioxanthone synthesized in Production Example 7, 4.4.9 parts of diphenyliodonium hexafluorophosphate, 0.4 part of copper (II) benzoate and 300 parts of chlorobenzene were mixed uniformly. After reacting at 125 ° C. for 3 hours, the reaction solution was cooled to room temperature (about 25 ° C.) and poured into 300 parts of distilled water to precipitate the product. This was filtered, the residue was washed with water until the pH of the filtrate became neutral, the residue was dried under reduced pressure, 100 parts of diethyl ether was added, and the mixture was dispersed in diethyl ether with an ultrasonic cleaner and allowed to stand for about 15 minutes. Then, the operation of removing the supernatant was repeated 3 times to wash the produced solid. The solid was then transferred to a rotary evaporator and the solvent was distilled off to obtain a yellow solid. This yellow solid was dissolved in 770 parts of dichloromethane and charged into 342 parts of 10% aqueous potassium tris (pentafluoroethyl) trifluorophosphate, followed by stirring at room temperature (about 25 ° C.) for 2 hours, and the organic layer was washed several times with water. By washing and drying under reduced pressure, diphenyl-2-thioxanthonylsulfonium tris (pentafluoroethyl) trifluorophosphate was obtained in a yield of 98% and a purity of 85%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.72 (1H, s), 8.47 (1H, d), 8.30 (1H, d), 8. 13 (2H, d), 7.78-7.98 (11 H, m), 7.70 (1 H, t)}. Purity was quantified by HPLC. Further, absorption of C—F bond was confirmed in the vicinity of 1200 cm ⁻¹ by infrared absorption analysis (KBr tablet method).

<Evaluation of energy beam curable composition>
1. Preparation of curable composition Evaluation sample {sulfonium salt of Examples 1-4 and 6-8, Comparative Examples 1-5} and epoxide (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, Dow Chemical Co., Ltd., UVR-6110) was heated at 60 ° C. in the blending amount (parts by weight) shown in Table 1 and uniformly mixed to prepare a composition for a photocuring test.

  The sulfonium salt obtained in Example 4 and Comparative Example 1 is hexafluorophosphate, and tris (pentafluoroethyl) trifluorophosphorin obtained in Examples 1-3, 6-8 and Comparative Examples 2-5. Compared to acid salts, hexafluoroantimonate and tetrakis (pentafluorophenyl) borate, the acid generated is weaker and less active against cationic polymerization, so the amount of sulfonium salt was increased.

2. Photocurability evaluation The curable composition obtained above was applied to a polyethylene terephthalate (PET) film with an applicator (40 μm). The PET film was irradiated with ultraviolet light having a wavelength limited by a filter using an ultraviolet irradiation device. The filter used was a 365 filter (manufactured by Eye Graphics Co., Ltd., a filter that cuts light of less than 365 nm) and L-34 (manufactured by Kenko Optical Co., Ltd., a filter that cuts light of less than 340 nm). After irradiation, the coating hardness after 40 minutes was measured with pencil hardness (JIS K5600-5-4.4999) and evaluated according to the following criteria (coating thickness after curing was about 40 μm). It was shown in 2. The higher the pencil hardness, the better the photocurability of the energy ray-curable composition, that is, the better the polymerization initiation ability of the sulfonium salt with respect to the cationically polymerizable compound (the photosensitivity of the sulfonium salt).

(Evaluation criteria)
◎: Pencil hardness is 2H or more ○: Pencil hardness is H to B
(Triangle | delta): Pencil hardness is 2B-4B
×: Liquid to tack and pencil hardness cannot be measured

(Ultraviolet light irradiation conditions)
・ Ultraviolet irradiation device: Belt conveyor type UV irradiation device (manufactured by Eye Graphics Co., Ltd.)
・ Lamp: 1.5kW high pressure mercury lamp ・ Filter: 365 filter (manufactured by Eye Graphics Co., Ltd.)
L-34 (manufactured by Kenko Optical Co., Ltd.)
Illuminance (measured with a 365 nm head illuminometer): 145 mW / cm ²

-Integrated light quantity (measured with 365nm head illuminometer):
Condition-1: 200 mJ / cm ²
Condition-2: 400 mJ / cm ²
Condition-3: 600 mJ / cm ²

3. Storage stability evaluation (sample preparation)
3 parts of evaluation samples {sulfonium salts of Examples 1 to 4, 6 to 8 and Comparative Examples 1 to 5} and epoxide (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, manufactured by Dow Chemical Co., Ltd.) , UVR-6110) 100 parts, respectively, mixed at 60 ° C., and then uniformly mixed to prepare a sample for storage stability test.
This blended sample was heated at 80 ° C. under light shielding and stored for 1 month, and then the viscosity of the blended sample before and after heating was measured and evaluated according to the following criteria. The storage stability is better as the viscosity does not increase. These results are shown in Table 2.
(Evaluation criteria)
X: Viscosity change after heating is 1.5 times or more.
○: Viscosity change after heating is less than 1.5 times.

  As can be seen from the results in Table 2, the sulfonium salt of the present invention is superior in curing performance (photosensitivity) of the cationically polymerizable compound under ultraviolet light of 365 nm or more as compared with the comparative sulfonium salt. Moreover, although the performance is excellent, the storage stability is equivalent to that of the comparative example.

[Evaluation of Positive Photoresist Composition]
<Preparation of sample for evaluation>
As a component (A) which is a photoacid generator, Examples 1 to 8 of the photoacid generator of the present invention are each 1 part by mass, and a component (B) is a resin represented by the following chemical formula (Resin-1) 40 masses And, as component (C), 60 parts by mass of novolak resin obtained by addition condensation of m-cresol and p-cresol in the presence of formaldehyde and an acid catalyst are uniformly dissolved in propylene glycol monomethyl ether acetate, The mixture was filtered through a membrane filter having a pore size of 1 μm to prepare a chemically amplified positive photoresist composition (Examples P1 to P8) having a solid concentration of 40% by mass. Further, as a comparative example, a conventional photoacid generator PAG-14 to PAG-16 shown below is used as a component (A) which is a photoacid generator, and a positive photoresist composition (Comparative Example P1) similar to the above is used. ~ P3) were prepared.

<Evaluation>
Using the chemically amplified positive resist compositions prepared in Examples P1 to P8 and Comparative Examples P1 to P3, photosensitivity (sensitivity) was evaluated as follows immediately after preparation and after storage at 40 ° C. for 1 month. The storage stability was judged according to the following criteria.
○: Sensitivity change after storage at 40 ° C. × 1 month is less than 5% of sensitivity immediately after preparation ×: Sensitivity change after storage at 40 ° C. × 1 month is 5% or more of sensitivity immediately after preparation

  Each composition was spin-coated on a silicon wafer substrate and then dried to obtain a photoresist layer having a thickness of about 20 μm. This resist layer was pre-baked at 130 ° C. for 6 minutes using a hot plate. After pre-baking, pattern exposure (i-line) was performed using TME-150RSC (manufactured by Topcon Corporation), and post-exposure heating (PEB) was performed at 75 ° C. for 5 minutes using a hot plate. Thereafter, the film was developed for 5 minutes by an immersion method using a 2.38 wt% tetramethylammonium hydroxide aqueous solution, washed with running water, and blown with nitrogen to obtain a 10 μm line and space pattern. Further, below that, the minimum exposure amount at which no residue of this pattern is recognized, that is, the minimum essential exposure amount (corresponding to the sensitivity) necessary for forming the resist pattern was measured. The results are shown in Table 3.

  As shown in Table 3, the chemically amplified positive photoresist compositions of Examples P1 to P8 were more sensitive than those using conventional photoacid generators as in Comparative Examples P1 to P3. Moreover, in the composition of an Example, the thing with bad storage stability like the comparative example P3 was not seen.

The sulfonium salt of the present invention includes paint, coating agent, ink, inkjet ink, positive resist, resist film, liquid resist, negative resist, MEMS resist, positive photosensitive material, negative photosensitive material, and various adhesives. , Molding material, casting material, putty, glass fiber impregnating agent, sealing material, sealing material, sealing material, optical semiconductor (LED) sealing material, optical waveguide material, nanoimprint material, for photofabrication, and for micro stereolithography It is suitably used as a photoacid generator used for materials and the like. In particular, the chemically amplified positive photoresist composition of the present invention has good storage stability and is highly sensitive to actinic rays or radiation, particularly i-line, as a circuit board, CSP, MEMS device. In addition, it is useful for forming connection terminals such as bumps and metal posts, wiring patterns, etc. in the manufacture of electronic components.

Claims (15)

A sulfonium salt represented by the following formula (1).

[In the formula (1), R ^{1 to} R ⁴ each independently represent an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, Acyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, substituted Represents an amino group, a cyano group, a nitro group or a halogen atom, and Ra, Rb and Rc each independently represent a phenyl group which may be substituted or an alkyl group which may be substituted; m ¹ ˜m ⁴ represents the number of R ^{1 to} R ⁴ , respectively. M ¹ , m ² and m ⁴ are integers from 0 to 4, and m ³ is an integer from 0 to 5. X ⁻ represents a monovalent polyatomic anion. ] The sulfonium salt shown by this. For R ^{1 to} R ⁴ , the alkyl group is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, or a cycloalkyl group having 3 to 18 carbon atoms, and the alkoxy group The group is a straight-chain alkoxy group having 1 to 18 carbon atoms or a branched-chain alkoxy group having 3 to 18 carbon atoms, and the alkylcarbonyl group is a straight-chain alkylcarbonyl group having 2 to 18 carbon atoms, or the number of carbon atoms The sulfonium salt according to claim 1, which is a 4-18 branched alkylcarbonyl group, and the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The sulfonium salt according to claim 1 or 2, wherein R ^{1 to} R ⁴ are one selected from the group consisting of a methyl group, a methoxy group, and an acetyl group. The sulfonium salt according to any one of claims 1 to 3, wherein R ² and R ³ are a methyl group or a methoxy group, m ² and m ³ are 1, and m ¹ and m ⁴ are 0. The sulfonium salt according to claim 1, wherein m ^{1 to} m ⁴ are all 0.   The sulfonium salt according to any one of claims 1 to 5, wherein Ra, Rb and Rc are all methyl groups or phenyl groups. Wherein X _{^{-, MY a -, (Rf)}} b PF 6-b -, R 5 c BY 4-c -, R 5 c GaY 4-c -, R 6 SO 3 -, (R 6 SO 2) 3 C An anion represented by ^— or (R ⁶ SO ₂ ) ₂ N ^— , wherein M is a phosphorus atom, boron atom or antimony atom; P is a phosphorus atom, F is a fluorine atom; Rf is 80 mol% or more of a hydrogen atom R ⁵ is a phenyl group in which at least one hydrogen atom is substituted with a halogen atom, trifluoromethyl group, nitro group or cyano group; B is a boron atom, Y is a halogen atom , Ga is a gallium atom; R ⁶ is an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; b is an integer of 1 to 5; Represents an integer of 4. The sulfonium salt according to any one of claims 1 to 6, wherein   A photoacid generator comprising the sulfonium salt according to any one of claims 1 to 7.   An energy ray-curable composition comprising the photoacid generator according to claim 8 and a cationically polymerizable compound.   A cured product obtained by curing the energy beam curable composition according to claim 9.   A chemical amplification type positive type comprising: a component (A) comprising the photoacid generator according to claim 8; and a resin component (B) whose solubility in alkali is increased by the action of an acid. Photoresist composition. X ^{− in the} formula (1) is (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ⁻ , (C ₆ F _{5 ^{) 4 Ga -, ((CF}} 3) 2 C 6 H 3) 4 Ga -, (CF 3 SO 2) 3 C -, (CF 3 SO 2) 2 N -, trifluoromethanesulfonic acid anion, nonafluorobutanesulfonic The chemically amplified positive photoresist composition according to claim 11, which is an anion represented by an acid anion, a benzenesulfonic acid anion, or a p-toluenesulfonic acid anion.   The chemistry according to claim 11 or 12, wherein the component (B) contains at least one resin selected from the group consisting of a novolak resin (B1), a polyhydroxystyrene resin (B2), and an acrylic resin (B3). Amplified positive photoresist composition.   The chemically amplified positive photoresist composition according to any one of claims 11 to 13, further comprising an alkali-soluble resin (C) and an acid diffusion controller (D). A laminating step of obtaining a photoresist laminate by laminating a photoresist layer having a thickness of 5 to 150 μm made of the chemically amplified positive photoresist composition according to claim 11 on a support, A method for producing a resist pattern, comprising: an exposure step of selectively irradiating light or radiation to the photoresist laminate, and a development step of developing the photoresist laminate after the exposure step to obtain a resist pattern .