Photoacid generator, curable composition and resist composition

Abstract

To provide: a novel photoacid generator comprising a sulfonyl imide salt compound that has high photosensitivity to i-line and also has excellent storage stability in a blend with a cationic polymerizable compound such as an epoxy compound; and an energy ray-curable composition, a chemically amplified positive photoresist composition and a chemically amplified negative photoresist composition, each containing the photoacid generator.SOLUTION: A photoacid generator comprises a sulfonyl imide salt compound represented by the following general formula (1). (In formula (1), X+ is a sulfonium cation represented by the following general formula (2), (20) or (21)).SELECTED DRAWING: None

Description

[Technical Field]

[0001] First, the present invention relates to a photoacid generator, more specifically, a photoacid generator containing a specific sulfonylimide salt compound that is suitable for curing a cationically polymerizable compound by the action of active energy rays such as light, electron beams, or X-rays. Second, the present invention relates to a curable composition containing the photoacid generator and a cured product obtained by curing the same. Third, 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. Fourth, the present invention relates to a chemically amplified negative photoresist composition containing the photoacid generator and a cured product obtained by curing the same. [Background technology]

[0002] Photoacid generators are a general term for compounds that decompose to generate an acid when irradiated with active energy rays such as light, electron beams, or X-rays. The acid generated by irradiation with active energy rays is used as an active species in various reactions such as polymerization, crosslinking, and deprotection reactions. Specific examples include the polymerization of cationically polymerizable compounds in fields such as paints, adhesives, and coatings, and photolithography in the manufacture of electronic components and the formation of semiconductor elements (crosslinking reaction of phenolic resins in the presence of crosslinking agents, and acid-catalyzed deprotection reaction of polymers in which protecting groups have been introduced into alkali-soluble resins).

[0003] In recent years, photolithography technology using chemically amplified photoresists has been widely used in the manufacture of electronic components and the formation of semiconductor elements, and i-lines with a wavelength of 365 nm are widely used as active energy rays, particularly in the manufacture of various precision components such as semiconductor packages. This is because medium- and high-pressure mercury lamps, which are inexpensive as irradiation light sources and have good luminous intensity, can be used.

[0004] Furthermore, with the downsizing of electronic devices, high-density packaging technology for semiconductor packages is advancing, with efforts being made to increase packaging density through the adoption of high-pin, thin-film packaging, miniaturization of package sizes, and two-dimensional packaging technology using the flip-chip method, as well as three-dimensional packaging technology. In order to achieve high-precision formation for such high-density packaging technology, chemically amplified photoresists are required to have excellent pattern shape and high photosensitivity, so that highly rectangular resist patterns can be obtained with less exposure.

[0005] Onium salts such as iodonium salts and sulfonium salts are known as existing photoacid generators (Patent Documents 1 to 6). Sulfonium salts have better storage stability and longer absorption wavelengths than iodonium salts, so sulfonium salts with various structures have been developed. The anion moiety of these sulfonium salts is SbF6 - , AsF6 - , BF4 - , B(C6F5)4 - , PF6 - However, since Sb is a deleterious substance and As is a poison, onium salts containing these metal elements have safety issues and their applications are limited. In addition, in the field of semiconductor photolithography, metals (SbF6 - , AsF6 - ), phosphorus (PF6 - ), boron (BF4 - , B(C6F5)4 - Photoacid generators containing elements such as HCl cannot be used for chemically amplified resists because these elements act as impurities and have a significant effect on transistor performance (Non-Patent Document 1).

[0006] Examples of photoacid generators that can solve the above problems include sulfonium salts in which the cation moiety is an arylsulfonium and the anion moiety is a fluorine-containing sulfonimidate. However, chemically amplified photoresists containing such photoacid generators still have low photosensitivity to i-line and also suffer from poor pattern shapes. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-89777 [Patent Document 2] Special Publication No. 2001-512714 [Patent Document 3] Japanese Patent Application Laid-Open No. 2005-275153 [Patent Document 4] Japanese Patent Application Laid-Open No. 2007-114719 [Patent Document 5] Japanese Patent Application Laid-Open No. 2008-222657 [Patent Document 6] Japanese Patent Application Laid-Open No. 2001-288193 [Patent Document 7] JP 2017-508723 A [Non-patent literature]

[0008] [Non-Patent Document 1] "Latest Trends in UV / EB Curing Technology," edited by RadTech Research Group and supervised by Mitsuru Ueda, Chapter 2: Trends in Material Development, 3. Photopolymerization Initiators, CMC Publishing (2006) Summary of the Invention [Problem to be solved by the invention]

[0009] A first object of the present invention is to provide a new photoacid generator containing a sulfonylimide salt compound, which has high photosensitivity to i-line and excellent storage stability when blended with a cationically polymerizable compound such as an epoxy compound. A second object of the present invention is to provide an energy ray-curable composition and a cured product that utilize the above photoacid generator. A third object of the present invention is to provide a chemically amplified positive photoresist composition utilizing the above photoacid generator, and a method for producing the same. A fourth object of the present invention is to provide a chemically amplified negative photoresist composition that utilizes the above photoacid generator, and a cured product thereof. [Means for solving the problem]

[0010] The present inventors have found that a photoacid generator containing a sulfonylimide salt compound represented by the following general formula (1) is suitable for each of the above purposes.

[0011] [ka]

[0012] (In formula (1), X + is a sulfonium cation represented by the following general formula (2), (20), or (21):

[0013] [ka]

[0014] [In formula (2), R 1 are each independently an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group or a halogen atom; 1 m1 represents an integer of 0 to 5, n represents an integer of 1 to 3, and when n=1, Y is represented by the following general formulas (3) to (11), when n=2, Y is represented by the following general formulas (12) to (16), and when n=3, Y is represented by the following general formulas (17) to (19).

[0015] [ka]

[0016] [In formulas (3) to (11), R 2 ~R 15 each independently represents an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom; m2 to m14 are each R 2 ~R 11 and R 13 ~R 15 m2 and m8 are integers from 0 to 5, m3, m6, m11, m12, and m14 are integers from 0 to 4, m4 and m10 are integers from 0 to 7, m5 is an integer from 0 to 9, and m7, m9, and m13 are integers from 0 to 3; Z 1 , Z 2 and Z 4 ~Z 6 -S-, -SO-, -O-, -CO-, -NR 16 -, -R 17 CR 18 - and Z 3 , Z 7 is -O- or -S-, and R 16 ~R 18 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or an optionally substituted aralkyl group having 7 to 20 carbon atoms.

[0017] [ka]

[0018] [In formulas (12) to (16), R 19 ~R 26each independently represents an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom; m15 to m22 are each R 19 ~R 25 m15 represents an integer of 0 to 5, m16, m19, and m21 represent integers of 0 to 4, m17 and m20 represent integers of 0 to 7, and m18 and m22 represent integers of 0 to 3; Z 8 ~Z 10 is -O- or -S-, and Z 11 ~Z 13 -S-, -SO-, -O-, -CO-, -NR 27 -, -R 28 CR 29 - and R 27 ~R 29 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or an optionally substituted aralkyl group having 7 to 20 carbon atoms.

[0019] [ka]

[0020] [In formulas (17) to (19), R 30 ~R 36each independently represents an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom; m23 to m28 are each R 30 ~R 34 and R 36 m23 represents an integer of 0 to 5, m24, m26, m27, and m28 represent integers of 0 to 4, and m25 represents an integer of 0 to 3; Z 14 ~Z 18 is -O- or -S-.

[0021] [ka]

[0022] [In formula (20), R 37 , R 38 each independently represents an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom; m29 and m30 are each R 37 , R 38 m29 represents an integer of 0 to 5, and m30 represents an integer of 0 to 4.

[0023] [ka]

[0024] [In formula (21), R 39 ~R 41 each independently represents an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom; 39 ~R 41 m31 and m32 are integers from 0 to 4, m33 is an integer from 0 to 5, Z 19 -S-, -O-, -CO-, -NR 42 -, -R 43 CR 44 - or a direct bond, and R 42 ~R 44 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or an optionally substituted aralkyl group having 7 to 20 carbon atoms.

[0025] The present invention also provides an energy ray-curable composition comprising the above photoacid generator and a cationically polymerizable compound.

[0026] The present invention further relates to a cured product obtained by curing the above energy ray-curable composition.

[0027] The present invention further provides a chemically amplified positive photoresist composition comprising component (A) containing the above-mentioned photoacid generator and component (B) which is a resin whose solubility in alkali increases under the action of acid.

[0028] The present invention further provides a method for producing a resist pattern, comprising: a lamination step of laminating a photoresist layer having a thickness of 5 to 150 μm and made of the above-mentioned chemically amplified positive photoresist composition on a support to obtain a photoresist laminate; an exposure step of selectively irradiating the photoresist laminate with light or radiation; and a development step of developing the photoresist laminate after the exposure step to obtain a resist pattern.

[0029] The present invention further relates to a chemically amplified negative photoresist composition comprising component (E) containing the above-mentioned photoacid generator, component (F) which is an alkali-soluble resin having a phenolic hydroxyl group, and crosslinker component (G).

[0030] The present invention further relates to a cured product obtained by curing the above-mentioned chemically amplified negative photoresist composition. [Effects of the Invention]

[0031] The photoacid generator containing the sulfonylimide salt compound of the present invention has excellent photosensitivity to active energy rays such as visible light, ultraviolet light, electron beams, and X-rays, has high compatibility with solvents and cationically polymerizable compounds such as epoxy compounds, and exhibits excellent storage stability when blended with cationically polymerizable compounds such as epoxy compounds. When used to cure a cationically polymerizable compound, the photoacid generator of the present invention has excellent curing properties due to the action of ultraviolet light, particularly i-rays, and can cure the cationically polymerizable compound. The energy ray-curable composition of the present invention contains the above-mentioned photoacid generator, and therefore can be cured by ultraviolet light. Furthermore, the energy ray-curable composition of the present invention has high storage stability and does not require the use of a sensitizer, and therefore is excellent in cost and workability. The chemically amplified positive photoresist composition and chemically amplified negative photoresist composition of the present invention contain the above-mentioned photoacid generator, and therefore it is possible to obtain a resist that is highly sensitive to i-line (enabling pattern formation with a lower exposure dose than conventional compositions). Furthermore, the chemically amplified positive photoresist composition and chemically amplified negative photoresist composition of the present invention have high storage stability and produce a good resist pattern shape. DETAILED DESCRIPTION OF THE INVENTION

[0032] Hereinafter, embodiments of the present invention will be described in detail.

[0033] The present invention is a photoacid generator containing a sulfonylimide salt compound represented by the following general formula (1).

[0034] [ka]

[0035] (In formula (1), X + is a sulfonium cation represented by the following general formula (2), (20), or (21):

[0036] [ka]

[0037] [In formula (2), R 1 are each independently an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group or a halogen atom; 1m1 represents an integer of 0 to 5, n represents an integer of 1 to 3, and when n=1, Y is represented by the following general formulas (3) to (11), when n=2, Y is represented by the following general formulas (12) to (16), and when n=3, Y is represented by the following general formulas (17) to (19).

[0038] [ka]

[0039] [In formulas (3) to (11), R 2 ~R 15 each independently represents an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom; m2 to m14 are each R 2 ~R 11 and R 13 ~R 15 m2 and m8 are integers from 0 to 5, m3, m6, m11, m12, and m14 are integers from 0 to 4, m4 and m10 are integers from 0 to 7, m5 is an integer from 0 to 9, and m7, m9, and m13 are integers from 0 to 3; Z 1 , Z 2 and Z 4 ~Z 6 -S-, -SO-, -O-, -CO-, -NR 16 -, -R 17 CR 18 - and Z 3 , Z 7 is -O- or -S-, and R 16 ~R 18 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or an optionally substituted aralkyl group having 7 to 20 carbon atoms.

[0040] [ka]

[0041] [In formulas (12) to (16), R 19 ~R 26 each independently represents an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom; m15 to m22 are each R 19 ~R 25 m15 represents an integer of 0 to 5, m16, m19, and m21 represent integers of 0 to 4, m17 and m20 represent integers of 0 to 7, and m18 and m22 represent integers of 0 to 3; Z 8 ~Z 10 is -O- or -S-, and Z 11 ~Z 13 -S-, -SO-, -O-, -CO-, -NR 27 -, -R 28 CR 29 - and R 27 ~R 29 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or an optionally substituted aralkyl group having 7 to 20 carbon atoms.

[0042] [ka]

[0043] [In formulas (17) to (19), R 30 ~R 36each independently represents an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom; m23 to m28 are each R 30 ~R 34 and R 36 m23 represents an integer of 0 to 5, m24, m26, m27, and m28 represent integers of 0 to 4, and m25 represents an integer of 0 to 3; Z 14 ~Z 18 is -O- or -S-.

[0044] [ka]

[0045] [In formula (20), R 37 , R 38 each independently represents an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom; m29 and m30 are each R 37 , R 38 m29 represents an integer of 0 to 5, and m30 represents an integer of 0 to 4.

[0046] [ka]

[0047] [In formula (21), R 39 ~R 41 each independently represents an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom; 39 ~R 41 m31 and m32 are integers from 0 to 4, m33 is an integer from 0 to 5, Z 19 -S-, -O-, -CO-, -NR 42 -, -R 43 CR 44 - or a direct bond, and R 42 ~R 44 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or an optionally substituted aralkyl group having 7 to 20 carbon atoms.

[0048] In equation (2), R 1 Among these, examples of the alkyl group include linear alkyl groups 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.), branched alkyl groups having 3 to 18 carbon atoms (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, and isooctadecyl), and cycloalkyl groups having 3 to 18 carbon atoms (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-decylcyclohexyl, etc.).

[0049] In equation (2), R 1Among these, examples of the alkoxy group include linear alkoxy groups having 1 to 18 carbon atoms, and branched alkoxy groups having 3 to 18 carbon atoms (such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy, and octadecyloxy).

[0050] In equation (2), R 1 Among these, examples of the alkylcarbonyl group include linear or branched alkylcarbonyl groups having 2 to 18 carbon atoms (acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, and octadecanoyl).

[0051] In equation (2), R 1 Among these, examples of the arylcarbonyl group include arylcarbonyl groups having 7 to 11 carbon atoms (such as benzoyl and naphthoyl).

[0052] In equation (2), R 1 Among these, examples of the alkoxycarbonyl group include linear alkoxycarbonyl groups having 2 to 19 carbon atoms and branched alkoxycarbonyl groups having 4 to 19 carbon atoms (such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, and octadecyloxycarbonyl).

[0053] In equation (2), R 1 Among these, examples of the aryloxycarbonyl group include aryloxycarbonyl groups having 7 to 11 carbon atoms (such as phenoxycarbonyl and naphthoxycarbonyl).

[0054] In equation (2), R 1Among these, examples of the arylthiocarbonyl group include arylthiocarbonyl groups having 7 to 11 carbon atoms (such as phenylthiocarbonyl and naphthoxythiocarbonyl).

[0055] In equation (2), R 1 Among these, examples of the acyloxy group include linear acyloxy groups having 2 to 19 carbon atoms and branched acyloxy groups having 4 to 19 carbon atoms (acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, and octadecylcarbonyloxy).

[0056] In equation (2), R 1 Among these, examples of the alkylthio group include linear alkylthio groups having 1 to 18 carbon atoms and branched alkylthio groups 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).

[0057] In equation (2), R 1 Among these, examples of the aryl group include aryl groups having 6 to 12 carbon atoms (such as phenyl, tolyl, dimethylphenyl, naphthyl, and biphenylyl).

[0058] In equation (2), R 1Among these, examples of the heterocyclic hydrocarbon group include heterocyclic hydrocarbon groups having 4 to 20 carbon atoms (such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, and dibenzofuranyl).

[0059] In equation (2), R 1 Among these, examples of the alkylsulfinyl group include linear alkylsulfinyl groups having 1 to 18 carbon atoms and branched sulfinyl groups having 3 to 18 carbon atoms (methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, isooctadecylsulfinyl, and the like).

[0060] In equation (2), R 1 Among these, examples of the arylsulfinyl group include arylsulfinyl groups having 6 to 10 carbon atoms (such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl).

[0061] In equation (2), R 1Among these, examples of the alkylsulfonyl group include linear alkylsulfonyl groups having 1 to 18 carbon atoms and branched alkylsulfonyl groups having 3 to 18 carbon atoms (methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl, octadecylsulfonyl, etc.).

[0062] In equation (2), R 1 Among these, examples of the arylsulfonyl group include arylsulfonyl groups having 6 to 10 carbon atoms (such as phenylsulfonyl, tolylsulfonyl (tosyl group), and naphthylsulfonyl).

[0063] In equation (2), R 1 Among these, examples of the hydroxy(poly)alkyleneoxy group include a hydroxy(poly)alkyleneoxy group represented by formula (22). HO(-AO)q- (22) [AO represents an ethyleneoxy group and / or a propyleneoxy group, and q represents an integer of 1 to 5.]

[0064] In equation (2), R 1 Among these, examples of the silyl group which may be substituted include silyl and substituted silyl groups having 1 to 18 carbon atoms (methylsilyl, dimethylsilyl, trimethylsilyl, phenylsilyl, methylphenylsilyl, dimethylphenylsilyl, diphenylsilyl, diphenylmethylsilyl, triphenylsilyl, etc.).

[0065] In equation (2), R 1Among these, examples of the amino group which may be substituted include an amino group (-NH2) and substituted amino groups 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, and isopropylphenylamino).

[0066] In equation (2), R 1 Among these, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0067] In equation (2), R 1 are mutually independent and therefore may be the same or different from each other.

[0068] In equation (2), R 1 Among these, preferred are alkyl groups, hydroxy groups, alkoxy groups, arylthio groups and halogen atoms, and more preferred are methyl groups, hydroxy groups, methoxy groups, butoxy groups, phenylthio groups and fluorine atoms.

[0069] In equation (2), m1 is R 1 m1 is an integer of 0 to 5, preferably 0 to 2, and more preferably 0 or 1.

[0070] In formulas (3) to (11), R 2 ~R 15Among these, 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]phenyl ... [phenyloxy]phenylthio, 4-[4-(phenylthio)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, and 4-(p-tert-butylbenzoyl)phenylthio).

[0071] In formulas (3) to (11), R 2 ~R 15 Among these, examples of the aryloxy group include aryloxy groups having 6 to 10 carbon atoms (such as phenoxy and naphthyloxy).

[0072] In formulas (3) to (11), R 2 ~R 15Among these, examples of alkyl groups, alkoxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, arylthiocarbonyl groups, acyloxy groups, alkylthio groups, aryl groups, heterocyclic hydrocarbon groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, hydroxy(poly)alkyleneoxy groups, optionally substituted silyl groups, optionally substituted amino groups, and halogen atoms include, for example, R 1 In the above, the alkyl group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, alkylthio group, aryl group, heterocyclic hydrocarbon group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy(poly)alkyleneoxy group, optionally substituted silyl group, optionally substituted amino group, and halogen atom are the same.

[0073] In formulas (3) to (11), R 2 ~R 15 are mutually independent and therefore may be the same or different from each other.

[0074] In equations (3) to (11), m2 to m14 are R 2 ~R 15 m2 and m8 are integers of 0 to 5, m3, m6, m11, m12, and m15 are integers of 0 to 4, m4 and m10 are integers of 0 to 7, m5 is an integer of 0 to 9, and m7, m9, and m14 are integers of 0 to 3, and m2 to m14 are preferably 0 to 2, and more preferably 0 or 1.

[0075] In formulas (3) to (11), Z 1 , Z 2 and Z 4 ~Z 6 -S-, -SO-, -O-, -CO-, -NR 16 -, -R 17 CR 18 - and Z 3 , Z 7 is -O- or -S-.

[0076] In formulas (3) to (11), Z 1 , Z 2 and Z 4 ~Z 6 Among them, -NR 16 -and-CR 17 R 18 -, R 16 ~R 18 Examples of the alkyl group include a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms (methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, isohexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and isooctadecyl), an optionally substituted aryl group having 6 to 20 carbon atoms (phenyl, tolyl, 4-fluorophenyl, 4-hydroxyphenyl, 4-methoxyphenyl), and an optionally substituted aralkyl group having 7 to 20 carbon atoms (benzyl, 2-methylbenzyl, 3-hydroxybenzyl, 3-methoxybenzyl).

[0077] In formulas (12) to (16), R 19 ~R 26 Among these, examples of alkyl groups, alkoxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, arylthiocarbonyl groups, acyloxy groups, arylthio groups, alkylthio groups, aryl groups, heterocyclic hydrocarbon groups, aryloxy groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, hydroxy(poly)alkyleneoxy groups, optionally substituted silyl groups, optionally substituted amino groups, and halogen atoms include R 1 or R in formulas (3) to (11) 2 ~R 15In the above, the alkyl group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, 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, optionally substituted silyl group, optionally substituted amino group, and halogen atom are the same.

[0078] In formulas (12) to (16), R 19 ~R 26 are mutually independent and therefore may be the same or different from each other.

[0079] In formulas (12) to (16), R 19 ~R 26 Among these, alkylcarbonyl and arylcarbonyl groups are preferred, alkylcarbonyl groups are more preferred, and acetyl groups are particularly preferred.

[0080] In equations (12) to (16), m15 to m22 are R 19 ~R 26 m15 is an integer of 0 to 5, m16, m19, and m21 are integers of 0 to 4, m17 and m20 are integers of 0 to 7, and m18 and m22 are integers of 0 to 3, and m15 to m22 are preferably 0 to 2, more preferably 0 or 1, and particularly preferably 1.

[0081] In formulas (12) to (16), Z 8 ~Z 10 is -O- or -S-, and Z 11 ~Z 13 -S-, -SO-, -O-, -CO-, -NR 27 -, -R 28 CR 29 -It is.

[0082] In formulas (12) to (16), Z 11 ~Z 13 Among them, -NR27 -and-CR 28 R 29 -, R 27 ~R 29 In equations (3) to (11), Z 1 , Z 2 and Z 4 ~Z 6 Among them, -NR 16 -and-CR 17 R 18 -, R 16 ~R 18 is the same as:

[0083] In formulas (17) to (19), R 30 ~R 36 Among these, examples of alkyl groups, alkoxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, arylthiocarbonyl groups, acyloxy groups, arylthio groups, alkylthio groups, aryl groups, heterocyclic hydrocarbon groups, aryloxy groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, hydroxy(poly)alkyleneoxy groups, optionally substituted silyl groups, optionally substituted amino groups, and halogen atoms include R 1 or R in formulas (3) to (11) 2 ~R 15 In the above, the alkyl group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, 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, optionally substituted silyl group, optionally substituted amino group, and halogen atom are the same.

[0084] In formulas (17) to (19), R 30 ~R 36 are mutually independent and therefore may be the same or different from each other.

[0085] In formulas (17) to (19), R 30 ~R 36 Among these, preferred are alkyl groups, alkoxy groups, alkylcarbonyl groups and arylcarbonyl groups, more preferred are alkyl groups and alkylcarbonyl groups, and particularly preferred are methyl groups and acetyl groups.

[0086] In equations (17) to (19), m23 to m28 are R 30 ~R 36 m15 is an integer of 0 to 5, m16, m19, and m21 are integers of 0 to 4, m17 and m20 are integers of 0 to 7, m18 and m22 are integers of 0 to 3, and m23 to m28 are preferably 0 to 2.

[0087] In formulas (17) to (19), Z 14 ~Z 18 is -O- or -S-.

[0088] In equation (20), R 37 , R 38 Among these, examples of alkyl groups, alkoxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, arylthiocarbonyl groups, acyloxy groups, arylthio groups, alkylthio groups, aryl groups, heterocyclic hydrocarbon groups, aryloxy groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, hydroxy(poly)alkyleneoxy groups, optionally substituted silyl groups, optionally substituted amino groups, and halogen atoms include, for example, R 2 ~R 15In the above, the alkyl group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, 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, optionally substituted silyl group, optionally substituted amino group, and halogen atom are the same.

[0089] In equation (20), R 37 , R 38 are mutually independent and therefore may be the same or different from each other.

[0090] In equation (20), R 37 , R 38 Among these, preferred are alkyl groups, alkoxy groups, alkylcarbonyl groups and arylcarbonyl groups, more preferred are alkoxy groups, and particularly preferred is 4-hydroxyethoxy group.

[0091] In equation (20), m29 and m30 are R 37 , R 38 m29 is an integer of 0 to 5, m30 is an integer of 0 to 4, and m29 and m30 are preferably 0 to 2, and more preferably 0 or 1.

[0092] In equation (21), R 39 ~R 41 Among these, examples of alkyl groups, alkoxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, arylthiocarbonyl groups, acyloxy groups, arylthio groups, alkylthio groups, aryl groups, heterocyclic hydrocarbon groups, aryloxy groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, hydroxy(poly)alkyleneoxy groups, optionally substituted silyl groups, optionally substituted amino groups, and halogen atoms include R 1 or R in formulas (3) to (11)2 ~R 15 In the above, the alkyl group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, 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, optionally substituted silyl group, optionally substituted amino group, and halogen atom are the same.

[0093] In equation (21), R 39 ~R 41 are mutually independent and therefore may be the same or different from each other.

[0094] In equation (21), R 39 ~R 41 Among these, preferred are an alkyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an aryl group, and a halogen atom, and more preferred are a methyl group, an isopropyl group, a 4-hydroxyethoxy group, an acetyl group, a 3-methylbenzoyl group, a phenyl group, and a fluorine atom.

[0095] In equation (21), m31 to m33 are R 39 ~R 41 m31 and m32 are integers of 0 to 4, m33 is an integer of 0 to 5, and m31 to m33 are preferably 0 to 2, more preferably 0 or 1, and particularly preferably 1.

[0096] In equation (21), Z 19 -S-, -O-, -CO-, -NR 42 -, -R 43 CR 44 - or a direct bond.

[0097] In equation (21), Z 9 Among them, -NR 42 -, -R 43 CR 44 -, R42 ~R 44 In formulas (3) to (11), Z 1 , Z 2 and Z 4 ~Z 6 Among them, -NR 16 -and-CR 17 R 18 -, R 16 ~R 18 is the same as:

[0098] The photoacid generator of the present invention is characterized by containing a sulfonylimide salt compound represented by general formula (1), but may also contain other conventionally known photoacid generators.

[0099] When another photoacid generator is contained, the content (mol %) of the other photoacid generator is preferably 0.1 to 100, more preferably 0.5 to 50, relative to the total number of moles of the sulfonylimide salt compound represented by general formula (1) of the present invention.

[0100] Other photoacid generators include conventionally known salts such as onium salts (sulfonium, iodonium, selenium, ammonium, and phosphonium), and salts of transition metal complex ions and anions.

[0101] When using the photoacid generator of the present invention, in order to facilitate dissolution into a cationically polymerizable compound or a chemically amplified resist composition, the photoacid generator may be dissolved in advance in a solvent that does not inhibit polymerization, crosslinking, deprotection reactions, etc.

[0102] Examples of the solvent include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, and diethyl carbonate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; polyhydric alcohols and derivatives thereof such as ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of dipropylene glycol monoacetate; and dioxane. cyclic ethers such as 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, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone; and aromatic hydrocarbons such as toluene and xylene.

[0103] When a solvent is used, the proportion of the solvent used is preferably 15 to 1000 parts by weight, more preferably 30 to 500 parts by weight, relative to 100 parts by weight of the photoacid generator containing the sulfonylimide salt compound of the present invention. The solvents used may be used alone or in combination of two or more kinds.

[0104] The energy ray-curable composition of the present invention comprises the above-mentioned photoacid generator and a cationically polymerizable compound.

[0105] Examples of the cationically polymerizable compound that is a component of the energy ray-curable composition include cyclic ethers (epoxides, oxetanes, and the like), ethylenically unsaturated compounds (vinyl ethers, styrenes, and the like), bicycloorthoesters, spiroorthocarbonates, and spiroorthoesters (see, for example, JP-A Nos. 11-060996, 09-302269, and 2003-026993).

[0106] As the epoxide, known epoxides can be used, including aromatic epoxides, alicyclic epoxides and aliphatic epoxides.

[0107] Examples of aromatic epoxides include glycidyl ethers of mono- or polyhydric phenols having at least one aromatic ring (phenol, bisphenol A, phenol novolak, and alkylene oxide adducts thereof).

[0108] Examples of alicyclic epoxides include compounds obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (e.g., 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate).

[0109] Examples of aliphatic epoxides include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.), polyglycidyl esters of aliphatic polybasic acids (diglycidyl tetrahydrophthalate, etc.), and epoxidized products of long-chain unsaturated compounds (epoxidized soybean oil, epoxidized polybutadiene, etc.).

[0110] As the oxetane, known oxetanes can be used, and examples thereof include 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl(3-ethyl-3-oxetanylmethyl)ether, 2-hydroxyethyl(3-ethyl-3-oxetanylmethyl)ether, 2-hydroxypropyl(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, oxetanylsilsesquioxetane, and phenol novolac oxetane.

[0111] As the ethylenically unsaturated compound, known cationically polymerizable monomers can be used, including aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrenes, and cationically polymerizable nitrogen-containing monomers.

[0112] Examples of the aliphatic monovinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.

[0113] Examples of aromatic monovinyl ethers include 2-phenoxyethyl vinyl ether, phenyl vinyl ether, and p-methoxyphenyl vinyl ether.

[0114] Examples of polyfunctional vinyl ethers include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.

[0115] Examples of styrenes include styrene, α-methylstyrene, p-methoxystyrene, and p-tert-butoxystyrene.

[0116] Examples of the cationically polymerizable nitrogen-containing monomer include N-vinylcarbazole and N-vinylpyrrolidone.

[0117] Examples of bicyclo orthoesters 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.

[0118] Examples of spiro orthocarbonates include 1,5,7,11-tetraoxaspiro[5.5]undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5.5]undecane.

[0119] Examples of spiro orthoesters include 1,4,6-trioxaspiro[4.4]nonane, 2-methyl-1,4,6-trioxaspiro[4.4]nonane, and 1,4,6-trioxaspiro[4.5]decane.

[0120] Furthermore, polyorganosiloxanes having at least one cationically polymerizable group per molecule can be used (described in JP-A No. 2001-348482, Journal of Polym. Sci., Part A, Polym. Chem., Vol. 28, 497 (1990), etc.). These polyorganosiloxanes may be linear, branched, or cyclic, or may be mixtures of these.

[0121] Among these cationically polymerizable compounds, epoxides, oxetanes, and vinyl ethers are preferred, epoxides and oxetanes are more preferred, and alicyclic epoxides and oxetanes are particularly preferred. These cationically polymerizable compounds may be used alone or in combination of two or more.

[0122] The content of the photoacid generator containing the sulfonylimide salt compound of the present invention in the energy ray-curable composition is preferably 0.5 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the cationically polymerizable compound. This range ensures more sufficient polymerization of the cationically polymerizable compound, resulting in better physical properties of the cured product. The content is determined by taking into consideration various factors, such as the properties of the cationically polymerizable compound, the type and dose of energy rays, temperature, curing time, humidity, and coating thickness, and is not limited to the above range.

[0123] The energy ray-curable composition of the present invention may contain, as needed, known additives (sensitizers, pigments, fillers, antistatic agents, flame retardants, antifoaming agents, flow control agents, light stabilizers, antioxidants, adhesion imparting agents, ion scavengers, coloration inhibitors, solvents, non-reactive resins, radically polymerizable compounds, and the like).

[0124] As the sensitizer, known sensitizers (such as those disclosed in JP-A-11-279212 and JP-A-09-183960) can be used, and examples thereof include anthracene (anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dipropoxyanthracene, etc.); pyrene; 1,2-benzanthracene; perylene; tetrahydrofuran; Thracene; 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-methylthioxanthone, 2 ... ketones {dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 4-benzoyl-4'-methyldiphenyl sulfide, etc.}; carbazoles {N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole, N-glycidylcarbazole, etc.}; chrysene {1,4-dimethoxychrysene, 1,4-di-α-methylbenzyloxychrysene, etc.}; phenanthrene {9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, 9-hydroxy-10-ethoxyphenanthrene, etc.}.

[0125] When a sensitizer is contained, the content of the sensitizer is preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight, relative to 100 parts by weight of the photoacid generator of the present invention.

[0126] As the pigment, known pigments can be used, including inorganic pigments (titanium oxide, iron oxide, carbon black, etc.) and organic pigments (azo pigments, cyanine pigments, phthalocyanine pigments, quinacridone pigments, etc.).

[0127] When a pigment is contained, the content of the pigment is preferably 0.5 to 400,000 parts by weight, and more preferably 10 to 150,000 parts by weight, relative to 100 parts of the photoacid generator of the present invention.

[0128] As the filler, known fillers can be used, and examples thereof include fused silica, crystalline silica, calcium carbonate, aluminum oxide, aluminum hydroxide, zirconium oxide, magnesium carbonate, mica, talc, calcium silicate, and lithium aluminum silicate.

[0129] When a filler is contained, the content of the filler is preferably 50 to 600,000 parts by weight, more preferably 300 to 200,000 parts by weight, relative to 100 parts of the photoacid generator of the present invention.

[0130] As the antistatic agent, known antistatic agents can be used, and examples thereof include nonionic antistatic agents, anionic antistatic agents, cationic antistatic agents, amphoteric antistatic agents, and polymeric antistatic agents.

[0131] When an antistatic agent is contained, the content of the antistatic agent is preferably 0.1 to 20,000 parts by weight, more preferably 0.6 to 5,000 parts by weight, relative to 100 parts of the photoacid generator of the present invention.

[0132] As the flame retardant, known flame retardants can be used, and examples thereof include inorganic flame retardants {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 retardants {tetrabromophthalic anhydride, hexabromobenzene, decabromobiphenyl ether, etc.}; and phosphate ester flame retardants {tris(tribromophenyl)phosphate, etc.}.

[0133] When a flame retardant is contained, the content of the flame retardant is preferably 0.5 to 40,000 parts by weight, more preferably 5 to 10,000 parts by weight, relative to 100 parts of the photoacid generator of the present invention.

[0134] As the defoaming agent, known defoaming agents can be used, and examples thereof include alcohol defoaming agents, metal soap defoaming agents, phosphate ester defoaming agents, fatty acid ester defoaming agents, polyether defoaming agents, silicone defoaming agents, and mineral oil defoaming agents.

[0135] As the flow modifier, known flow modifiers can be used, and examples thereof include hydrogenated castor oil, oxidized polyethylene, organic bentonite, colloidal silica, amide wax, metal soap, and acrylic ester polymer. As the light stabilizer, known light stabilizers can be used, and examples thereof include ultraviolet absorbing stabilizers (benzotriazole, benzophenone, salicylate, cyanoacrylate, and derivatives thereof, etc.); radical scavenging stabilizers (hindered amines, etc.); and quenching stabilizers (nickel complexes, etc.). As the antioxidant, known antioxidants can be used, and examples thereof include phenol-based antioxidants (monophenol-based, bisphenol-based, polymeric phenol-based, etc.), sulfur-based antioxidants, and phosphorus-based antioxidants. As the adhesion promoter, known adhesion promoters can be used, and examples thereof include coupling agents, silane coupling agents, and titanium coupling agents. As the ion scavenger, known ion scavenger can be used, and examples thereof include organic aluminum (alkoxy aluminum, phenoxy aluminum, etc.). As the coloring inhibitor, known coloring inhibitors can be used, and generally, antioxidants are effective, and examples thereof include phenol-based antioxidants (monophenol-based, bisphenol-based, polymeric phenol-based, etc.), sulfur-based antioxidants, and phosphorus-based antioxidants, but they are almost ineffective in preventing coloring during heat resistance tests at high temperatures.

[0136] When an antifoaming agent, a flow control agent, a light stabilizer, an antioxidant, an adhesion imparting agent, an ion scavenger, or a coloring inhibitor is contained, the content of each is preferably 0.1 to 20,000 parts by weight, and more preferably 0.5 to 5,000 parts by weight, relative to 100 parts of the photoacid generator of the present invention.

[0137] There are no limitations on the solvent as long as it can be used to dissolve the cationically polymerizable compound and adjust the viscosity of the energy ray-curable composition, and the solvents listed above as solvents for the photoacid generator can be used.

[0138] When a solvent is contained, the content of the solvent is preferably 50 to 2,000,000 parts by weight, and more preferably 200 to 500,000 parts by weight, relative to 100 parts of the photoacid generator of the present invention.

[0139] Examples of non-reactive resins include polyester, polyvinyl acetate, polyvinyl chloride, polybutadiene, polycarbonate, polystyrene, polyvinyl ether, polyvinyl butyral, polybutene, hydrogenated styrene-butadiene block copolymer, (meth)acrylic acid ester copolymer, polyurethane, etc. The number average molecular weight of these resins is preferably 1,000 to 500,000, more preferably 5,000 to 100,000 (the number average molecular weight is a value measured by a general method such as GPC).

[0140] When a non-reactive resin is contained, the content of the non-reactive resin is preferably 5 to 400,000 parts by weight, more preferably 50 to 150,000 parts by weight, relative to 100 parts of the photoacid generator of the present invention.

[0141] 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 in the cationically polymerizable compound or the like.

[0142] As the radical polymerizable compound, known radical polymerizable compounds (such as those described in "Photopolymer Handbook" edited by the Photopolymer Forum (1989, Industrial Research Institute), "UV / EB Curing Technology" edited by the General Technology Center (1982, General Technology Center), and "UV / EB Curing Materials" edited by the RadTech Research Group (1992, CMC)) can be used, including monofunctional monomers, bifunctional monomers, polyfunctional monomers, epoxy (meth)acrylates, polyester (meth)acrylates, and urethane (meth)acrylates.

[0143] When a radical polymerizable compound is contained, the content of the radical polymerizable compound is preferably 5 to 400,000 parts by weight, more preferably 50 to 150,000 parts by weight, relative to 100 parts of the photoacid generator of the present invention.

[0144] When a radically polymerizable compound is contained, it is preferable to use a radical polymerization initiator that initiates polymerization by heat or light in order to increase the molecular weight of the compound by radical polymerization.

[0145] As the radical polymerization initiator, known radical polymerization initiators can be used, including thermal radical polymerization initiators (organic peroxides, azo compounds, etc.) and photoradical polymerization initiators (acetophenone-based initiators, benzophenone-based initiators, Michler's ketone-based initiators, benzoin-based initiators, thioxanthone-based initiators, acylphosphine-based initiators, etc.).

[0146] When a 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, based on 100 parts of the radical polymerizable compound.

[0147] The energy ray-curable composition of the present invention can be prepared by uniformly mixing and dissolving the cationically polymerizable compound, the photoacid generator, and, if necessary, the additives at room temperature (about 20 to 30°C) or, if necessary, under heating (about 40 to 90°C), or further by kneading them with a three-roll mill or the like.

[0148] The energy ray-curable composition of the present invention can be cured by irradiating it with energy rays to give a cured product. The energy rays may be any rays as long as they have energy sufficient to induce decomposition of the photoacid generator of the present invention, but are preferably energy rays in the ultraviolet to visible light region (wavelength: about 100 to about 800 nm) obtained from low-pressure, medium-pressure, high-pressure, or ultra-high-pressure mercury lamps, metal halide lamps, LED lamps, xenon lamps, carbon arc lamps, fluorescent lamps, semiconductor solid-state lasers, argon lasers, He—Cd lasers, KrF excimer lasers, ArF excimer lasers, F2 lasers, etc. High-energy radiation such as electron beams or X-rays can also be used as the energy rays.

[0149] The irradiation time of the energy ray is affected by the intensity of the energy ray and the transmittance of the energy ray through the energy ray-curable composition, but about 0.1 to 10 seconds at room temperature (about 20 to 30°C) is sufficient. However, if the transmittance of the energy ray is low or if the film thickness of the energy ray-curable composition is thick, it may be preferable to apply a longer time. Furthermore, if necessary, after the irradiation of the energy ray, the film may be post-cured by heating at room temperature (about 20 to 30°C) to 200°C for several seconds to several hours.

[0150] Specific applications of the energy ray-curable composition of the present invention include paints, coating agents, various coating materials (hard coats, stain-resistant coatings, anti-fogging coatings, contact-resistant coatings, optical fibers, etc.), backside treatment agents for adhesive tapes, release coating materials for release sheets for adhesive labels (release paper, release plastic films, release metal foils, etc.), printing plates, dental materials (dental compounds, dental composites), inkjet inks, positive resists (for forming connection terminals and wiring patterns in the manufacture of electronic parts such as circuit boards, CSPs, and MEMS elements), resist films, liquid resists, negative resists (for forming surface protective films for semiconductor elements, etc., interlayer insulating films, planarizing films, and other permanent film materials). etc.), MEMS resists, positive photosensitive materials, negative photosensitive materials, various adhesives (temporary fixing agents for various electronic components, adhesives for HDDs, adhesives for pickup lenses, adhesives for functional films for FPDs (deflectors, anti-reflection films, etc.)), holographic resins, FPD materials (color filters, black matrices, partition materials, photospacers, ribs, alignment films for liquid crystals, sealants for FPDs, etc.), optical members, molding materials (for construction materials, optical components, lenses), casting materials, putty, glass fiber impregnation agents, sealing materials, sealants, encapsulants, optical semiconductor (LED) encapsulants, optical waveguide materials, nanoimprint materials, materials for stereolithography, and materials for micro stereolithography.

[0151] Since the photoacid generator of the present invention generates a strong acid upon irradiation with light, it can also be used as a photoacid generator for known chemically amplified resist materials (e.g., JP-A Nos. 2003-267968, 2003-261529, and 2002-193925).

[0152] Chemically amplified resist materials include (1) two-component chemically amplified positive resists whose essential components are a resin that becomes soluble in alkaline developer by the action of acid and a photoacid generator; (2) three-component chemically amplified positive resists whose essential components are a resin that is soluble in alkaline developer, a dissolution inhibitor that becomes soluble in alkaline developer by the action of acid, and a photoacid generator; and (3) chemically amplified negative resists whose essential components are a resin that is soluble in alkaline developer, a crosslinker that crosslinks the resin by heat treatment in the presence of acid to make it insoluble in alkaline developer, and a photoacid generator.

[0153] The chemically amplified positive photoresist composition of the present invention is characterized by containing a component (A) containing the photoacid generator of the present invention, which is a compound that generates an acid upon exposure to light or radiation, and a resin component (B) whose solubility in alkali increases under the action of an acid.

[0154] In the chemically amplified positive photoresist composition of the present invention, component (A) may be used in combination with other conventionally known photoacid generators, such as onium salt compounds, sulfone compounds, sulfonate ester compounds, sulfonimide compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, triazine compounds, and nitrobenzyl compounds, as well as organic halides and disulfones.

[0155] As other conventionally known photoacid generators, preferably, at least one member selected from the group consisting of onium compounds, sulfonimide compounds, diazomethane compounds and oxime sulfonate compounds is preferred.

[0156] When such other conventionally known photoacid generators are used in combination, the proportion of the other photoacid generators may be any proportion, but typically the proportion of the other photoacid generators is 10 to 900 parts by weight, preferably 25 to 400 parts by weight, per 100 parts by weight of the total weight of the sulfonylimide salt compound represented by the general formula (1) above.

[0157] The content of the component (A) is preferably 0.05 to 5% by weight based on the solid content of the chemically amplified positive photoresist composition.

[0158] <Resin component (B) whose solubility in alkali increases under the action of an acid> The "resin (B) whose alkali solubility increases under the action of an acid" (referred to herein as "component (B)") used in the chemically amplified positive photoresist composition of the present invention is at least one resin selected from the group consisting of novolak resins (B1), polyhydroxystyrene resins (B2), and acrylic resins (B3), or a mixed resin or copolymer thereof.

[0159] [Novolac resin (B1)] As the novolak resin (B1), a resin represented by the following general formula (b1) can be used.

[0160] [ka]

[0161] In formula (b1), R 1b represents an acid-dissociable dissolution-inhibiting group, and R 2b , R 3b each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents the number of repeating units of the structure in the parentheses.

[0162] Furthermore, the above R 1b The acid dissociable, dissolution inhibiting group represented by the formula (I) is preferably a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a cyclic alkyl group having 3 to 6 carbon atoms, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

[0163] Here, the above R 1b Specific examples of acid-dissociable, dissolution-inhibiting groups represented by the formula (I) include a methoxyethyl group, an ethoxyethyl group, an n-propoxyethyl group, an isopropoxyethyl group, an n-butoxyethyl group, an isobutoxyethyl group, a tert-butoxyethyl group, a cyclohexyloxyethyl group, a methoxypropyl group, an ethoxypropyl group, a 1-methoxy-1-methylethyl group, a 1-ethoxy-1-methylethyl group, a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl group, and a tri-tert-butyldimethylsilyl group.

[0164] [Polyhydroxystyrene resin (B2)] As the polyhydroxystyrene resin (B2), a resin represented by the following general formula (b2) can be used.

[0165] [ka]

[0166] In formula (b2), R 4b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 5b represents an acid dissociable, dissolution inhibiting group, and n represents the number of repeating units of the structure in parentheses.

[0167] The alkyl group having 1 to 6 carbon atoms is a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, such as 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, or a neopentyl group, and examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

[0168] Above R 5b The acid dissociable dissolution inhibiting group represented by the formula (I) is the same as the above R 1b Acid-dissociable, dissolution-inhibiting groups similar to those exemplified in can be used.

[0169] Furthermore, the polyhydroxystyrene resin (B2) may contain other polymerizable compounds as structural units in order to appropriately control the physical and chemical properties. Examples of such polymerizable compounds include known radically polymerizable compounds and anionically polymerizable compounds. Examples include monocarboxylic acids such as acrylic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond, such as 2-methacryloyloxyethyl succinic acid; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate; (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate; vinyl group-containing aromatic compounds such as styrene and vinyltoluene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride; and amide bond-containing polymerizable compounds such as acrylamide.

[0170] [Acrylic resin (B3)] As the acrylic resin (B3), resins represented by the following general formulas (b3) to (b8) can be used.

[0171] [ka]

[0172] [ka]

[0173] In formulas (b3) to (b5), R 6b ~R 13b each independently represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a fluorine atom, a linear fluorinated alkyl group having 1 to 6 carbon atoms, or a branched fluorinated alkyl group having 3 to 6 carbon atoms; X bforms a hydrocarbon ring having 5 to 20 carbon atoms together with the carbon atom to which it is attached, and Y b represents an aliphatic cyclic group or alkyl group which may have a substituent; n represents the number of repeating units of the structure in the parentheses; p is an integer of 0 to 4; and q is 0 or 1.

[0174] In formulas (b6) to (b8), R 14b ~R 17b each independently represents a hydrogen atom or a methyl group, and in formula (b6), each R 15b are each independently a hydrogen atom, a hydroxyl group, a cyano group or a COOR 19b group (where R 19b represents a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 to 4 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms. 18b each independently represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms 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 R 18b At least one of R is the alicyclic hydrocarbon group or a derivative thereof, or any two of R 18b are bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the common carbon atom to which each is bonded, and the remaining R 18b represents a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 to 4 carbon atoms, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof.

[0175] Among the above components (B), it is preferable to use the acrylic resin (B3).

[0176] Furthermore, the polystyrene-equivalent weight average molecular weight of component (B) is preferably 10,000 to 600,000, more preferably 50,000 to 600,000, and even more preferably 230,000 to 550,000. By adjusting the weight average molecular weight within this range, the physical properties of the resist resin will be excellent.

[0177] Furthermore, component (B) is preferably a resin with a polydispersity of 1.05 or more. Here, "polydispersity" refers to the value obtained by dividing the weight-average molecular weight by the number-average molecular weight. By achieving such a polydispersity, the resist has excellent plating resistance and resin physical properties.

[0178] The content of the component (B) is preferably 5 to 60% by weight based on the total solid content of the chemically amplified positive photoresist composition.

[0179] <Alkali-soluble resin (C)> In order to improve the resin properties of the resist, the chemically amplified positive photoresist composition of the present invention preferably further contains an alkali-soluble resin (herein referred to as "component (C)"). Component (C) is preferably at least one resin selected from the group consisting of novolak resins, polyhydroxystyrene resins, acrylic resins, and polyvinyl resins.

[0180] The content of the component (C) is preferably 5 to 95 parts by weight, more preferably 10 to 90 parts by weight, per 100 parts by weight of the component (B). By using an amount of 5 parts by weight or more, the resin properties of the resist can be improved, and by using an amount of 95 parts by weight or less, film loss during development tends to be prevented.

[0181] <Acid diffusion controller (D)> The chemically amplified positive photoresist composition of the present invention preferably further contains an acid diffusion controller (D) (herein referred to as "component (D)") in order to improve the resist pattern shape, deposition stability, etc. Component (D) is preferably a nitrogen-containing compound, and may further contain an organic carboxylic acid or a phosphorus oxo acid or a derivative thereof, as necessary.

[0182] The chemically amplified positive photoresist composition of the present invention may further contain an adhesion promoter to improve adhesion to a substrate. The adhesion promoter used is preferably a functional silane coupling agent.

[0183] The chemically amplified positive photoresist composition of the present invention may further contain a surfactant in order to improve coating properties, defoaming properties, leveling properties, and the like.

[0184] The chemically amplified positive photoresist composition of the present invention may further contain an acid, an acid anhydride, or a high-boiling solvent in order to finely adjust the solubility in an alkaline developer.

[0185] Furthermore, the chemically amplified positive photoresist composition of the present invention does not basically require a sensitizer, but may contain a sensitizer to enhance sensitivity, if necessary. As such a sensitizer, any of the conventionally known sensitizers can be used, and specific examples thereof include those listed above.

[0186] The amount of these sensitizers used is 5 to 500 parts by weight, preferably 10 to 300 parts by weight, per 100 parts by weight of the total weight of the sulfonylimide salt compounds represented by the general formula (1).

[0187] The chemically amplified positive photoresist composition of the present invention may contain an organic solvent to adjust the viscosity. Specific examples of the organic solvent include those listed above.

[0188] The amount of these organic solvents used is preferably in the range of 30% by weight or more solids concentration so that the thickness of the photoresist layer obtained using the chemically amplified positive photoresist composition of the present invention (e.g., by spin coating) is 5 μm or more.

[0189] The chemically amplified positive photoresist composition of the present invention can be prepared, for example, by simply mixing and stirring the above-mentioned components by a conventional method, or, if necessary, by using a dispersing machine such as a dissolver, homogenizer, or triple-roll mill to disperse and mix them. After mixing, the components may be further filtered using a mesh, membrane filter, or the like.

[0190] The chemically amplified positive photoresist composition of the present invention is suitable for forming a photoresist layer having a thickness of typically 5 to 150 μm, more preferably 10 to 120 μm, and even more preferably 10 to 100 μm, on a support. This photoresist laminate comprises a photoresist layer comprising the chemically amplified positive photoresist composition of the present invention laminated on a support.

[0191] The substrate is not particularly limited and can be a conventionally known substrate, such as a substrate for electronic components or a substrate having a predetermined wiring pattern formed thereon. Examples of the substrate include substrates made of metals such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, and aluminum, and glass substrates. In particular, the chemically amplified positive photoresist composition of the present invention can form a good resist pattern even on a copper substrate. Examples of materials for the wiring pattern include copper, solder, chromium, aluminum, nickel, and gold.

[0192] The photoresist laminate can be produced, for example, as follows. That is, a solution of the chemically amplified positive photoresist composition prepared as described above is applied to a substrate, and the solvent is removed by heating to form a desired coating film. Methods that can be used to apply the composition to a substrate include spin coating, slit coating, roll coating, screen printing, and applicator methods. The pre-baking conditions for the coating film of the composition of the present invention vary depending on the type and blending ratio of each component in the composition, the coating film thickness, etc., but are typically 70 to 150°C, preferably 80 to 140°C, for about 2 to 60 minutes.

[0193] The thickness of the photoresist layer is usually in the range of 5 to 150 μm, preferably 10 to 120 μm, and more preferably 10 to 100 μm.

[0194] To form a resist pattern using the photoresist laminate obtained in this manner, the obtained photoresist layer may be selectively irradiated (exposed) to light or radiation, for example, ultraviolet light or visible light having a wavelength of 300 to 500 nm, through a mask having a predetermined pattern.

[0195] Here, "light" refers to any light that activates a photoacid generator to generate an acid, and includes ultraviolet light, visible light, and far ultraviolet light. "Radiation" refers to X-rays, electron beams, ion beams, etc. Examples of light or radiation sources that can be used include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, and LED lamps. The radiation dose varies depending on the type and amount of each component in the composition, the thickness of the coating film, etc., but for example, when an ultra-high-pressure mercury lamp is used, it is 50 to 10,000 mJ / cm. 2 is.

[0196] After exposure, the photoresist layer is heated by a known method to promote diffusion of the acid and change the alkali solubility of the exposed portions of the photoresist layer. The unwanted portions are then dissolved and removed using, for example, a specific alkaline aqueous solution as a developer, to obtain the desired resist pattern.

[0197] The development time varies depending on the type and blending ratio of each component of the composition and the dry film thickness of the composition, but is usually 1 to 30 minutes, and the development method may be any of the puddle method, dipping method, puddle method, spray development method, etc. After development, the film is washed with running water for 30 to 90 seconds and dried using an air gun, oven, etc.

[0198] By embedding a conductor such as a metal by plating or the like in the non-resist portions (portions removed with the alkaline developer) of the resist pattern thus obtained, it is possible to form connection terminals such as metal posts or bumps. The plating method is not particularly limited, and various conventionally known methods can be used. Suitable plating solutions include solder plating, copper plating, gold plating, and nickel plating. Finally, the remaining resist pattern is removed using a stripper or the like according to a standard method.

[0199] 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 of the chemically amplified positive photoresist composition of the present invention. The thickness of the layer of the chemically amplified positive photoresist composition is typically 10 to 150 μm, preferably 20 to 120 μm, and more preferably 20 to 80 μm. The protective film is not particularly limited, and any resin film conventionally used in dry films can be used. For example, one film can be a polyethylene terephthalate film, and the other film can be one selected from the group consisting of polyethylene terephthalate film, polypropylene film, and polyethylene film.

[0200] The above-described chemically amplified positive dry film can be produced, for example, as follows. A solution of the chemically amplified positive photoresist composition prepared as described above is applied to one of the protective films, and the solvent is removed by heating to form the desired coating film. Drying conditions vary depending on the type and proportion of each component in the composition, the coating film thickness, etc., but typically require drying at 60 to 100°C for about 5 to 20 minutes.

[0201] To form a resist pattern using the chemically amplified dry film obtained in this manner, one protective film of the chemically amplified positive dry film is peeled off, and the exposed surface is laminated onto a support with the support facing the above-mentioned support to obtain a photoresist layer, and then the resist is pre-baked to dry, and the other protective film is peeled off.

[0202] A resist pattern can be formed on the photoresist layer thus obtained on the support in the same manner as described above for the photoresist layer formed by directly coating on the support.

[0203] The chemically amplified negative photoresist composition of the present invention is characterized by containing a component (E) containing the photoacid generator of the present invention, which is a compound that generates an acid upon exposure to light or radiation, an alkali-soluble resin (F) having a phenolic hydroxyl group, and a crosslinking agent (G).

[0204] Alkali-soluble resin containing phenolic hydroxyl groups (F) Examples of the "alkali-soluble resin having a phenolic hydroxyl group" (hereinafter referred to as "phenolic resin (F)") used in the present invention include novolak resins, polyhydroxystyrenes, copolymers of polyhydroxystyrenes, copolymers of hydroxystyrene and styrene, copolymers of hydroxystyrene, styrene and a (meth)acrylic acid derivative, phenol-xylylene glycol condensation resins, cresol-xylylene glycol condensation resins, and phenol-dicyclopentadiene condensation resins. Among these, novolak resins, polyhydroxystyrenes, copolymers of polyhydroxystyrenes, copolymers of hydroxystyrene and styrene, copolymers of hydroxystyrene, styrene and a (meth)acrylic acid derivative, and phenol-xylylene glycol condensation resins are preferred. These phenolic resins (F) may be used alone or in combination of two or more.

[0205] The phenolic resin (F) may contain a low molecular weight phenolic compound as part of its components. Examples of the phenolic low molecular weight compound include 4,4'-dihydroxydiphenylmethane and 4,4'-dihydroxydiphenyl ether.

[0206] Crosslinker (G) The "crosslinking agent" (hereinafter also referred to as "crosslinking agent (G)") in the present invention is not particularly limited as long as it acts as a crosslinking component (curing component) that reacts with the phenolic resin (F). Examples of the crosslinking agent (G) include compounds having at least two or more alkyl-etherified amino groups in the molecule, compounds having at least two or more alkyl-etherified benzene groups in the molecule as a skeleton, oxirane ring-containing compounds, thiirane ring-containing compounds, oxetanyl group-containing compounds, and isocyanate group-containing compounds (including blocked compounds).

[0207] Among these crosslinking agents (G), compounds having at least two alkyl-etherified amino groups in the molecule and oxirane ring-containing compounds are preferred, and it is more preferred to use a compound having at least two alkyl-etherified amino groups in the molecule and an oxirane ring-containing compound in combination.

[0208] The amount of the crosslinking agent (G) in the present invention is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, relative to 100 parts by weight of the phenolic resin (F). When the amount of the crosslinking agent (G) is 1 to 100 parts by weight, the curing reaction proceeds sufficiently, and the resulting cured product has a high resolution and a good pattern shape, and is excellent in heat resistance and electrical insulation, which is preferable. Furthermore, when a compound having an alkyl-etherified amino group and an oxirane ring-containing compound are used in combination, the content of the oxirane ring-containing compound is preferably 50% by weight or less, more preferably 5 to 40% by weight, and particularly preferably 5 to 30% by weight, when the total of the compound having an alkyl-etherified amino group and the oxirane ring-containing compound is taken as 100% by weight. In this case, the resulting cured film is preferable because it has excellent chemical resistance without impairing high resolution.

[0209] Crosslinked fine particles (H) The chemically amplified negative photoresist composition of the present invention may further contain crosslinked fine particles (hereinafter also referred to as "crosslinked fine particles (H)") in order to improve the durability and thermal shock resistance of the resulting cured product.

[0210] The average particle size of the crosslinked fine particles (H) is usually 30 to 500 nm, preferably 40 to 200 nm, and more preferably 50 to 120 nm. The method for controlling the particle size of the crosslinked microparticles (H) is not particularly limited. For example, when synthesizing crosslinked microparticles by emulsion polymerization, the particle size can be controlled by controlling the number of micelles during emulsion polymerization through the amount of emulsifier used. The average particle size of the crosslinked fine particles (H) is a value measured by diluting a dispersion of the crosslinked fine particles in a conventional manner using a light scattering flow distribution measuring device or the like.

[0211] The amount of crosslinked fine particles (H) blended is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight, per 100 parts by weight of the phenolic resin (F). When the amount of crosslinked fine particles (H) blended is 0.5 to 50 parts by weight, excellent compatibility or dispersibility with other components can be achieved, and the thermal shock resistance and heat resistance of the resulting cured film can be improved.

[0212] Adhesion aid The chemically amplified negative photoresist composition of the present invention may also contain an adhesion aid in order to improve adhesion to a substrate. Examples of the adhesion aid include functional silane coupling agents having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group.

[0213] The amount of the adhesion aid is preferably 0.2 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, relative to 100 parts by weight of the phenolic resin (F). When the amount of the adhesion aid is 0.2 to 10 parts by weight, excellent storage stability and good adhesion can be obtained, which is preferable.

[0214] solvent The chemically amplified negative photoresist composition of the present invention may contain a solvent in order to improve the handleability of the resin composition and to adjust the viscosity and storage stability. The solvent is not particularly limited, but specific examples include those mentioned above.

[0215] The chemically amplified negative photoresist composition of the present invention may contain a sensitizer, if necessary. As such a sensitizer, any of the conventionally known sensitizers may be used, and specific examples thereof include those listed above.

[0216] The amount of these sensitizers used is 5 to 500 parts by weight, preferably 10 to 300 parts by weight, per 100 parts by weight of the total weight of the sulfonylimide salt compounds represented by the general formula (1).

[0217] The chemically amplified negative photoresist composition of the present invention may contain other additives, if necessary, to the extent that the properties of the present invention are not impaired. Examples of such additives include inorganic fillers, quenchers, leveling agents, surfactants, etc.

[0218] The method for preparing the chemically amplified negative photoresist composition of the present invention is not particularly limited, and it can be prepared by any known method. It can also be prepared by stirring a sample bottle containing each component and a completely stoppered sample bottle on a wave rotor.

[0219] The cured product of the present invention is characterized by being obtained by curing the chemically amplified negative photoresist composition. The chemically amplified negative photoresist composition according to the present invention has a high film retention rate and excellent resolution, and the cured product thereof has excellent electrical insulation properties, thermal shock resistance, etc., and therefore the cured product thereof can be suitably used as a surface protection film, a planarizing film, an interlayer insulating film material, etc. for electronic components such as semiconductor elements and semiconductor packages.

[0220] To form the cured product of the present invention, the aforementioned chemically amplified negative photoresist composition of the present invention is first applied to a support (such as a resin-coated copper foil, a copper-clad laminate, or a silicon wafer or alumina substrate with a metal sputtered film), and then dried to volatilize the solvent, forming a coating film. The resulting coating is then exposed to light through a desired mask pattern and heat-treated (hereinafter, this heat treatment is referred to as "PEB") to promote the reaction between the phenolic resin (F) and the crosslinking agent (G). The resulting coating is then developed with an alkaline developer to dissolve and remove the unexposed areas, yielding the desired pattern. A heat treatment is then performed to develop insulating film properties, yielding a cured film.

[0221] The resin composition can be applied to a support by a coating method such as dipping, spraying, bar coating, roll coating, spin coating, etc. The thickness of the coating film can be appropriately controlled by adjusting the coating means and the solids concentration and viscosity of the composition solution. Examples of radiation used for exposure include ultraviolet rays from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-line steppers, h-line steppers, i-line steppers, gh-line steppers, ghi-line steppers, etc., electron beams, laser beams, etc. The exposure dose is appropriately selected depending on the light source used, the resin film thickness, etc. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the exposure dose is 100 to 50,000 J / m for a resin film thickness of 1 to 50 μm. 2 That's about it.

[0222] After exposure, the PEB treatment is carried out to promote the curing reaction between the phenolic resin (F) and the crosslinking agent (G) due to the generated acid. The PEB conditions vary depending on the amount of resin composition used, the film thickness used, and other factors, but are typically performed at 70 to 150°C, preferably 80 to 120°C, for approximately 1 to 60 minutes. The film is then developed with an alkaline developer to dissolve and remove the unexposed areas, forming the desired pattern. Examples of development methods include shower development, spray development, immersion development, and puddle development. Development conditions typically involve a temperature of 20 to 40°C for approximately 1 to 10 minutes.

[0223] Furthermore, after development, the composition can be sufficiently cured by a heat treatment to fully develop its insulating film properties. The curing conditions are not particularly limited, but depending on the intended use of the cured product, the composition can be cured by heating at a temperature of 50 to 250°C for approximately 30 minutes to 10 hours. Alternatively, to fully promote curing or prevent deformation of the resulting pattern, the composition can be heated in two stages. For example, in the first stage, the composition can be heated at a temperature of 50 to 120°C for approximately 5 minutes to 2 hours, and then further heated at a temperature of 80 to 250°C for approximately 10 minutes to 10 hours to achieve curing. Under these curing conditions, a typical oven, infrared furnace, or the like can be used as heating equipment. [Example]

[0224] The present invention will be further described below with reference to examples, but is not intended to be limited thereto. Unless otherwise specified, parts mean parts by weight and % means % by weight.

[0225] (Synthesis Example 1) Synthesis of Photoacid Generator (a1) 16.0 parts of methanesulfonic acid and 2.5 parts of diphosphorus pentoxide were charged and purged with nitrogen, then heated to 100°C and dissolved. After cooling the mixed solution to room temperature, 3.4 parts of diphenyl sulfoxide and 4.3 parts of phenyl ether were added and stirred for 3 hours under water cooling. Next, the reaction solution was poured into 100 parts of ice water, stirred for 1 hour, and then allowed to stand. The upper layer was removed, and 100 parts of dichloromethane was added to the lower layer. The dichloromethane layer was washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 3.3 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer under stirring, and stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with ion-exchanged water by a liquid separation operation, transferred to a rotary evaporator, and the solvent was distilled off to obtain a1. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0226] [ka]

[0227] (Synthesis Example 2) Synthesis of Photoacid Generator (a2) (a2) was obtained in the same manner as in Synthesis Example 1, except that 3.4 parts of diphenyl sulfoxide was changed to 4.4 parts of bis(4-methoxyphenyl) sulfoxide. 1 H-NMR, 19 Identification was performed using F-NMR.

[0228] [ka]

[0229] (Synthesis Example 3) Synthesis of Photoacid Generator (a3) 4.0 parts of diphenyl sulfoxide and 40 parts of dichloromethane were charged, and 6.5 parts of trimethylsilyl chloride was added dropwise while maintaining the internal temperature at 20°C or below. Next, a Grignard reagent prepared from 1.5 parts of metallic magnesium, 12.4 parts of 2-bromonaphthalene, and 20 parts of tetrahydrofuran was added dropwise, and the mixture was stirred at 20°C or below for 1 hour. The reaction solution was poured into 100 parts of ion-exchanged water containing 1.0 part of 12N hydrochloric acid, extracted with 100 parts of dichloromethane, and washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 3.9 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer with stirring, and the mixture was stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with ion-exchanged water by a separation operation, transferred to a rotary evaporator, and the solvent was distilled off to obtain a3. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0230] [ka]

[0231] (Synthesis Example 4) Synthesis of Photoacid Generator (a4) A4 was obtained in the same manner as in Synthesis Example 3, except that 12.4 parts of 2-bromonaphthalene was replaced with 15.4 parts of 9-bromoanthracene. 1 H-NMR, 19 Identification was performed using F-NMR.

[0232] [ka]

[0233] (Synthesis Example 5) Synthesis of Photoacid Generator (a5) 5.0 parts of phenothiazine, 6.0 parts of bis(4-fluorophenyl) sulfoxide, 12.5 parts of acetic anhydride, and 50 parts of methanesulfonic acid were charged and stirred at 80°C for approximately 8 hours. After cooling to room temperature, the mixture was poured into 100 parts of ion-exchanged water, extracted with 100 parts of dichloromethane, and washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 5.0 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer while stirring, and the mixture was stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with ion-exchanged water by a separation operation, transferred to a rotary evaporator, and the solvent was distilled off to obtain a5. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0234] [ka]

[0235] (Synthesis Example 6) Synthesis of Photoacid Generator (a6) A5 was obtained in the same manner as in Synthesis Example 5, except that 6.0 parts of bis(4-fluorophenyl) sulfoxide was replaced with 5.8 parts of bis(4-methylphenyl) sulfoxide. 1 H-NMR, 19 Identification was performed using F-NMR.

[0236] [ka]

[0237] (Synthesis Example 7) Synthesis of Photoacid Generator (a7) 65.4 parts of methanesulfonic acid and 6.4 parts of diphosphorus pentoxide were charged and purged with nitrogen, then heated to 100°C and dissolved. After cooling to room temperature, 9.5 parts of N-methylacridone and 10.6 parts of bis(4-hydroxyphenyl) sulfoxide were added, and the mixture was stirred at 50°C for 4 hours. Next, 180 parts of ice water, 190 parts of methanol, and 110 parts of isopropyl ether were mixed, and the reaction solution was poured into this mixture. After stirring for 1 hour, the mixture was allowed to stand. The upper layer was removed, and 370 parts of dichloromethane was added to the lower layer. The dichloromethane layer was washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 8.9 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer while stirring, and the mixture was stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with ion-exchanged water by a liquid-separating operation, transferred to a rotary evaporator, and the solvent was distilled off to obtain a7. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0238] [ka]

[0239] (Synthesis Example 8) Synthesis of Photoacid Generator (a8) A8 was obtained in the same manner as in Synthesis Example 7, except that 10.6 parts of bis(4-hydroxyphenyl) sulfoxide was replaced with 10.8 parts of bis(4-fluorophenyl) sulfoxide. 1 H-NMR, 19 Identification was performed using F-NMR.

[0240] [ka]

[0241] (Synthesis Example 9) Synthesis of Photoacid Generator (a9) A9 was obtained in the same manner as in Synthesis Example 7, except that 9.5 parts of N-methylacridone was changed to 9.5 parts of anthraquinone. 1 H-NMR, 19 Identification was performed using F-NMR.

[0242] [ka]

[0243] (Synthesis Example 10) Synthesis of Photoacid Generator (a10) A10 was obtained in the same manner as in Synthesis Example 7, except that 9.5 parts of N-methylacridone was replaced with 9.5 parts of anthraquinone and 10.6 parts of bis(4-hydroxyphenyl) sulfoxide was replaced with 10.8 parts of bis(4-fluorophenyl) sulfoxide. 1 H-NMR, 19 Identification was performed using F-NMR.

[0244] [ka]

[0245] (Synthesis Example 11) Synthesis of Photoacid Generator (a11) While stirring 2.0 parts of dithiosalicylic acid and 60 parts of sulfuric acid, 16.9 parts of (4-phenylthio)phenyldiphenylsulfonium trifluoromethanesulfonate was gradually added, and the mixture was stirred at room temperature for 1 hour. The reaction solution was poured into 600 parts of ion-exchanged water to precipitate the product. This was filtered, and the residue was washed with ion-exchanged water until the pH of the filtrate became neutral, yielding a solid. This solid was dissolved in 70 parts of dichloromethane, and 6.1 parts of lithium bis(fluorosulfonyl)imide was added, followed by stirring at room temperature for 1 hour. The dichloromethane layer was washed three times with ion-exchanged water by a separation operation, transferred to a rotary evaporator, and the solvent was distilled off to obtain a11. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0246] [ka]

[0247] (Synthesis Example 12) Synthesis of Photoacid Generator (a12) 8.81 parts of 7-methoxycoumarin, 10.8 parts of diphenyl sulfoxide, and 30 parts of polyphosphoric acid were charged and stirred at 120°C for 6 hours. After cooling to room temperature, the mixture was poured into 200 parts of ion-exchanged water, extracted with 200 parts of dichloromethane, and washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 8.7 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer while stirring, and the mixture was stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with ion-exchanged water by a liquid-separating operation, transferred to a rotary evaporator, and the solvent was distilled off to obtain a12. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0248] [ka]

[0249] (Synthesis Example 13) Synthesis of Photoacid Generator (a13) A13 was obtained in the same manner as in Synthesis Example 12, except that 10.8 parts of diphenyl sulfoxide was changed to 11.9 parts of bis(4-fluorophenyl) sulfoxide. 1 H-NMR, 19 Identification was performed using F-NMR.

[0250] [ka]

[0251] (Synthesis Example 14) Synthesis of Photoacid Generator (a14) 4.3 parts of diphenyl sulfoxide, 3.2 parts of 2-phenylthiophene, and 10.2 parts of acetic anhydride were charged, and while maintaining the internal temperature at 10°C or below, 7.7 parts of methanesulfonic acid was added, followed by stirring for 3 hours and then stirring at room temperature for 4 hours. The reaction solution was poured into 100 parts of ion-exchanged water, extracted with 100 parts of dichloromethane, and washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 4.0 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer while stirring, and the mixture was stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with ion-exchanged water by a separation operation, transferred to a rotary evaporator, and the solvent was distilled off to obtain a14. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0252] [ka]

[0253] (Synthesis Example 15) Synthesis of Photoacid Generator (a15) A15 was obtained in the same manner as in Synthesis Example 14, except that 4.3 parts of diphenyl sulfoxide was changed to 4.6 parts of bis(4-methylphenyl) sulfoxide. 1 H-NMR, 19 Identification was performed using F-NMR.

[0254] [ka]

[0255] (Synthesis Example 16) Synthesis of Photoacid Generator (a16) 14.4 parts of methanesulfonic acid and 14.2 parts of diphosphorus pentoxide were charged, purged with nitrogen, and heated to 100°C to dissolve. After cooling to room temperature, 23.4 parts of bis(4-hydroxyphenyl) sulfoxide and 35.0 parts of 9,9-bis(4-hydroxyphenyl)-9H-fluorene were added, and the mixture was stirred at 15°C for 2 hours. Next, the reaction solution was poured into a solution containing 500 parts of ice water and 250 parts of methanol. The precipitated solid was collected by filtration, and 400 parts of methyl isobutyl ketone and 300 parts of ion-exchanged water were added. The aqueous layer was washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 9.4 parts of lithium bis(fluorosulfonyl)imide was added to the methyl isobutyl ketone layer under stirring, and the mixture was stirred at room temperature for 1 hour. The methyl isobutyl ketone layer was washed three times with ion-exchanged water by a liquid-separating operation, transferred to a rotary evaporator, and the solvent was distilled off to obtain a16. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0256] [ka]

[0257] (Synthesis Example 17) Synthesis of Photoacid Generator (a17) 7.2 parts of a16 obtained in Example 16, 22 parts of dimethylformamide, and 11.1 parts of potassium carbonate were charged and stirred, and the atmosphere was replaced with nitrogen. 6.4 parts of methyl iodide were added dropwise to the mixture, and the mixture was stirred at room temperature for 8 hours. 75 parts of dichloromethane and 100 parts of ion-exchanged water were added, and the mixture was washed with ion-exchanged water until the pH of the aqueous layer became neutral. The mixture was then transferred to a rotary evaporator and the solvent was distilled off to obtain a17. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0258] [ka]

[0259] (Synthesis Example 18) Synthesis of Photoacid Generator (a18) 36.0 parts of methanesulfonic acid and 3.6 parts of diphosphorus pentoxide were charged and purged with nitrogen, followed by heating to dissolve. After cooling, 4.9 parts of N-ethylcarbazole was added, and 4.8 parts of diphenyl sulfoxide dissolved in 9.6 parts of chlorobenzene was added dropwise at room temperature, followed by stirring at 53°C for 3 hours. Next, a mixture of 100 parts of ion-exchanged water, 275 parts of diisopropyl ether, and 255 parts of acetone was ice-cooled, and the reaction solution was added to the mixture while stirring. After stirring, the mixture was allowed to stand for a while. The upper layer was removed, and the dichloromethane layer was washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 4.4 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer while stirring, followed by stirring at room temperature for 1 hour. The dichloromethane layer was washed three times with ion-exchanged water by a liquid-separating operation, transferred to a rotary evaporator, and the solvent was distilled off to obtain a18. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0260] [ka]

[0261] (Synthesis Example 19) Synthesis of Photoacid Generator (a19) A19 was obtained in the same manner as in Synthesis Example 18, except that 4.8 parts of diphenyl sulfoxide was changed to 5.3 parts of bis(4-fluorophenyl) sulfoxide. 1 H-NMR, 19 Identification was performed using F-NMR.

[0262] [ka]

[0263] (Synthesis Example 20) Synthesis of Photoacid Generator (a20) 33.8 parts of a22 obtained in Example 22, 50 parts of N,N-dimethylformamide, 6.2 parts of sodium hydroxide, and 4.5 g of tetrabutylammonium hydrosulfate (TBAHS) were charged and stirred, and the atmosphere was replaced with nitrogen. Under water cooling, 15.6 parts of benzenethiol was added dropwise, and the reaction was carried out at room temperature for 5 hours. The reaction solution was washed with a mixed solvent of methyl isobutyl ketone and ion-exchanged water, then with aqueous sodium hydroxide, and further with ion-exchanged water until the pH of the aqueous layer became neutral. The solution was then transferred to a rotary evaporator and the solvent was distilled off. The resulting solid was dissolved in 70 parts of methyl isobutyl ketone, and 250 parts of 2-propanol was gradually added while stirring. The precipitated viscous material was removed and dried to obtain a20. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0264] [ka]

[0265] (Synthesis Example 21) Synthesis of Photoacid Generator (a21) 60 parts of dichloromethane, 9.3 parts of aluminum chloride, 10.8 parts of dibenzothiophene, and 8.2 parts of benzoyl chloride were charged and stirred at room temperature for 2 hours. The reaction solution was then poured into 100 parts of ice water. The dichloromethane layer was washed with ion-exchanged water until the pH of the aqueous layer became neutral. The mixture was then transferred to a rotary evaporator and the solvent was removed to obtain a product. Next, 4.8 parts of di-p-fluorophenyl sulfoxide and 5.8 parts of the product obtained above were added to 29.5 parts of 95% sulfuric acid with stirring, and the mixture was stirred at room temperature for 10 hours. The reaction solution was then poured into a solution containing 50 parts of ice water, 60 parts of methanol, and 30 parts of toluene. The upper layer was removed, and 50 parts of dichloromethane was added to the lower layer. The dichloromethane layer was washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 11.0 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer with stirring, and the mixture was stirred at room temperature for 1 hour. The dichloromethane layer was separated and washed three times with ion-exchanged water, then transferred to a rotary evaporator to remove the solvent, yielding a21. 1 Identification was performed by H-NMR.

[0266] [ka]

[0267] (Synthesis Example 22) Synthesis of Photoacid Generator (a22) 5.2 parts of bis(4-butoxyphenyl) sulfoxide, 2.0 parts of benzo[b]thiophene, and 7.7 parts of acetic anhydride were charged, and while maintaining the internal temperature at 0 to 10°C, 4.3 parts of methanesulfonic acid was added, followed by stirring at 10°C for 3 hours. The reaction solution was poured into 100 parts of ion-exchanged water, extracted with 100 parts of dichloromethane, and washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 17.1 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer while stirring, and the mixture was stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with ion-exchanged water by a separation operation, transferred to a rotary evaporator, and the solvent was distilled off to obtain a21. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0268] [ka]

[0269] (Synthesis Example 23) Synthesis of Photoacid Generator (a23) 38.5 parts of ortho-dichlorobenzene and 4.7 parts of aluminum chloride were charged and stirred. Next, 4.2 parts of thionyl chloride and 2.8 parts of benzene were added in an ice bath and stirred at 0°C. This mixture was added dropwise to a mixture of 23.7 parts of aluminum chloride, 77.0 parts of ortho-dichlorobenzene, and 20.0 parts of 4-phenylthioacetophenone in an ice bath and stirred at room temperature for 3 hours. Next, the reaction solution was poured into 200 parts of ice water, the lower layer was removed, and the ortho-dichloromethane layer was washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 6.6 parts of lithium bis(fluorosulfonyl)imide was added to the ortho-dichloromethane layer with stirring and stirred at room temperature for 1 hour. The ortho-dichloromethane layer was washed three times with ion-exchanged water by a liquid separation operation and transferred to a rotary evaporator to distill off the solvent, yielding a23. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0270] [ka]

[0271] (Synthesis Example 24) Synthesis of Photoacid Generator (a24) A24 was obtained in the same manner as in Synthesis Example 23, except that 20.0 parts of 4-phenylthioacetophenone was replaced with 18.6 parts of 4-phenyloxyacetophenone. 1 H-NMR, 19 Identification was performed using F-NMR.

[0272] [ka]

[0273] (Synthesis Example 25) Synthesis of Photoacid Generator (a25) A25 was obtained in the same manner as in Synthesis Example 23, except that 20.0 parts of 4-phenylthioacetophenone was replaced with 20.5 parts of 2-acetyl-5-(phenylthio)thiophene. 1 H-NMR, 19 Identification was performed using F-NMR.

[0274] [ka]

[0275] (Synthesis Example 26) Synthesis of Photoacid Generator (a26) A26 was obtained in the same manner as in Synthesis Example 23, except that 20.0 parts of 4-phenylthioacetophenone was replaced with 19.1 parts of 2-acetyl-5-(phenylthio)furan. 1 H-NMR, 19 Identification was performed using F-NMR.

[0276] [ka]

[0277] (Synthesis Example 27) Synthesis of Photoacid Generator (a27) 1.5 parts of thionyl chloride, 10.4 parts of aluminum chloride, and 9.6 parts of 4-phenoxyacetophenone were slowly added to 40 parts of orthodichlorobenzene at room temperature, and the reaction mixture was stirred at room temperature for 3 hours, then at 50°C for 3 hours. The reaction solution was then poured into 100 parts of ice water, the lower layer was removed, and the orthodichloromethane layer was washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 2.9 parts of lithium bis(fluorosulfonyl)imide was added to the orthodichloromethane layer while stirring, and the mixture was stirred at room temperature for 1 hour. The orthodichloromethane layer was washed three times with ion-exchanged water by a separation operation, transferred to a rotary evaporator, and the solvent was distilled off to obtain a27. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0278] [ka]

[0279] (Synthesis Example 28) Synthesis of Photoacid Generator (a28) A28 was obtained in the same manner as in Synthesis Example 27, except that 9.6 parts of 4-phenoxyacetophenone was replaced with 10.4 parts of 4-phenylthioacetophenone. 1 H-NMR, 19 Identification was performed using F-NMR.

[0280] [ka]

[0281] (Synthesis Example 29) Synthesis of Photoacid Generator (a29) 38 parts of dimethylformamide, 25.0 parts of 2-acetyl-5-bromothiophene, and 15.4 parts of sodium carbonate were charged, and 15.9 parts of thiophenol was added dropwise. The mixture was stirred at 35°C for 6 hours. The reaction mixture was poured into 100 parts of ice water, extracted with 100 parts of ethyl acetate, washed with ion-exchanged water until the pH of the aqueous layer became neutral, and then transferred to a rotary evaporator to remove the solvent, yielding a product. 13.2 parts of aluminum chloride and 23 parts of dichloromethane were charged and stirred. A reaction solution prepared by dissolving 12.0 parts of the product obtained above in 8 parts of dichloromethane was added dropwise at 0°C. 1.9 parts of thionyl chloride was then added dropwise at -5°C, and the mixture was stirred at 25°C for 5 hours. The reaction mixture was poured into 10 parts of ice water, stirred for 1 hour, and then allowed to stand. The upper layer was removed, and the dichloromethane layer was washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 3.2 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer under stirring, and the mixture was stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with ion-exchanged water by a separation operation, and transferred to a rotary evaporator to remove the solvent, thereby obtaining a29. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0282] [ka]

[0283] (Synthesis Example 30) Synthesis of Photoacid Generator (a30) A30 was obtained in the same manner as in Synthesis Example 29, except that 25.0 parts of 2-acetyl-5-bromothiophene was replaced with 23.0 parts of 1-(5-bromo-2-furyl)ethanone. 1 H-NMR, 19 Identification was performed using F-NMR.

[0284] [ka]

[0285] (Synthesis Example 31) Synthesis of Photoacid Generator (a31) A31 was obtained in the same manner as in Synthesis Example 29, except that 15.9 parts of thiophenol was changed to 13.6 parts of phenol. 1 H-NMR, 19 Identification was performed using F-NMR.

[0286] [ka]

[0287] (Synthesis Example 32) Synthesis of Photoacid Generator (a32) A32 was obtained in the same manner as in Example 29, except that 25.0 parts of 2-acetyl-5-bromothiophene was replaced with 24.0 parts of 2-bromobenzofuran and 15.9 parts of thiophenol was replaced with 20.0 parts of 2,6-dimethylthiophenol. 1 H-NMR, 19 Identification was performed using F-NMR.

[0288] [ka]

[0289] (Synthesis Example 33) Synthesis of Photoacid Generator (a33) A33 was obtained in the same manner as in Synthesis Example 29, except that 25.0 parts of 2-acetyl-5-bromothiophene was replaced with 26.0 parts of 2-bromobenzothiophene and 15.9 parts of thiophenol was replaced with 17.6 parts of 2,6-dimethylphenol. 1 H-NMR, 19 Identification was performed using F-NMR.

[0290] [ka]

[0291] (Synthesis Example 34) Synthesis of Photoacid Generator (a34) The same procedure as in Synthesis Example 29 was repeated except that 25.0 parts of 2-acetyl-5-bromothiophene was replaced with 24.0 parts of 2-bromobenzofuran and 15.9 parts of thiophenol was replaced with 17.6 parts of 2,6-dimethylphenol to obtain a34. 1 H-NMR, 19 Identification was performed using F-NMR.

[0292] [ka]

[0293] (Synthesis Example 35) Synthesis of Photoacid Generator (A-35) 31.7 parts of methanesulfonic acid and 3.4 parts of phosphorus pentoxide were charged, purged with nitrogen, and then heated to 100°C to dissolve. After cooling to room temperature, 26.3 parts of bis(4-hydroxyethoxyphenyl) sulfide and 3.1 parts of diphenyl sulfide were added, and the mixture was stirred at room temperature for 5 hours. Next, the mixture was poured into 400 parts of ion-exchanged water, extracted with 200 parts of dichloromethane, and washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 3.6 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer while stirring, and the mixture was stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with ion-exchanged water by a separation operation, transferred to a rotary evaporator, and the solvent was distilled off to obtain a35. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0294] [ka]

[0295] (Synthesis Example 36) Synthesis of Photoacid Generator (a36) A36 was obtained in the same manner as in Synthesis Example 35, except that 26.3 parts of bis(4-hydroxyethoxyphenyl) sulfide was changed to 8.7 parts of diphenyl sulfide. 1 H-NMR, 19 Identification was performed using F-NMR.

[0296] [ka]

[0297] (Synthesis Example 37) Synthesis of Photoacid Generator (a37) 1.0 parts of 2-isopropylthioxanthone, 0.8 parts of biphenyl, 7.4 parts of acetic acid, 2.3 parts of dichloromethane, and 7.6 parts of acetic anhydride were charged, and 4.8 parts of concentrated sulfuric acid was added dropwise while maintaining the internal temperature at 15°C or below, followed by stirring for 2 hours. The reaction solution was then warmed to room temperature, poured into 100 parts of ion-exchanged water, extracted with 100 parts of dichloromethane, and washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 0.8 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer while stirring, and the mixture was stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with ion-exchanged water by a separation operation, transferred to a rotary evaporator, and the solvent was distilled off to obtain a37. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0298] [ka]

[0299] (Synthesis Example 38) Synthesis of Photoacid Generator (a38) 2.2 parts of thianthrene and 40 parts of glacial acetic acid were charged, and 1.1 parts of 35% hydrogen peroxide was added dropwise. The mixture was stirred at 90°C for 2 hours. Next, 0.05 parts of 35% hydrogen peroxide was added, and the mixture was stirred at 90°C for 30 minutes. The reaction solution was poured into 100 parts of ion-exchanged water, suction filtered, and then vacuum dried to obtain a solid. Next, 0.5 parts of this solid, 10.0 parts of fluorobenzene, and 1.6 parts of aluminum chloride were charged, and the mixture was stirred under reflux for 90 minutes. After cooling to room temperature, the mixture was poured into 100 parts of ion-exchanged water, extracted with 100 parts of dichloromethane, and washed with ion-exchanged water until the pH of the aqueous layer became neutral. The mixture was transferred to a rotary evaporator and the solvent was distilled off to obtain a solid. Next, 0.2 parts of this solid and 5 parts of ethylene glycol were charged, and the mixture was heated to 120°C to dissolve. 0.05 parts of potassium hydroxide was added to the mixed solution, and the mixture was stirred for 1 hour. The reaction solution was poured into the ion-exchanged water portion, extracted with 100 parts of dichloromethane, and washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 0.1 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer under stirring, and the mixture was stirred at room temperature for 1 hour. The dichloromethane layer was separated and washed three times with ion-exchanged water, and then transferred to a rotary evaporator to remove the solvent, yielding a38. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0300] [ka]

[0301] (Synthesis Example 39) Synthesis of Photoacid Generator (a39) 200 parts of concentrated sulfuric acid was ice-cooled, and 43.2 parts of 2-(3-methylbenzoyl)dibenzothiophene-5-oxide and 15.0 parts of toluene were added, followed by stirring at 15°C for 2 hours. The reaction solution was then poured into a mixture of 200 parts of ice water, 200 parts of methanol, and 200 parts of toluene. The upper layer was removed, and 200 parts of dichloromethane was added to the lower layer. The dichloromethane layer was washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 25.2 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer while stirring, followed by stirring at room temperature for 1 hour. The dichloromethane layer was washed three times with ion-exchanged water by a separation operation, transferred to a rotary evaporator, and the solvent was distilled off to obtain a39. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0302] [ka]

[0303] (Synthesis Example 40) Synthesis of Photoacid Generator (a40) A40 was obtained in the same manner as in Synthesis Example 39, except that 43.2 parts of 2-(3-methylbenzoyl)dibenzothiophene-5-oxide was replaced with 32.9 parts of 2-acetyldibenzothiophene-5-oxide and 15.0 parts of toluene was replaced with 15.3 parts of fluorobenzene. 1 H-NMR, 19 Identification was performed using F-NMR.

[0304] [ka]

[0305] (Synthesis Example 41) Synthesis of Photoacid Generator (a41) 25 parts of phenoxatiline were mixed in 200 parts of tetrahydrofuran, and 25 parts of trimethylsilyl chloride were added dropwise thereto. After cooling to 0°C, 39 parts of a THF solution (16%) of phenylmagnesium bromide were added dropwise, and the mixture was aged for 2 hours. 200 parts of dichloromethane and 200 parts of ion-exchanged water were then added, and the dichloromethane layer was washed with ion-exchanged water until the pH of the aqueous layer became neutral. 3.3 parts of lithium bis(fluorosulfonyl)imide was then added to the dichloromethane layer under stirring, and the mixture was stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with ion-exchanged water by a separation operation, and transferred to a rotary evaporator to distill off the solvent, yielding a40. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0306] [ka]

[0307] (Synthesis Example 42) Synthesis of Photoacid Generator (a42) 1.8 parts of diphenyl sulfoxide, 1.7 parts of diphenyl sulfide, and 23.3 parts of methanesulfonic acid were charged, and 2.8 parts of acetic anhydride were added dropwise at room temperature. The mixture was then stirred at 60°C for 6 hours, and the reaction solution was cooled to room temperature. It was then poured into 200 parts of ion-exchanged water, extracted with 100 parts of dichloromethane, and washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 1.8 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer under stirring, and the mixture was stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with ion-exchanged water by a separation operation, transferred to a rotary evaporator, and the solvent was distilled off to obtain a42. The product was 1 H-NMR, 19 Identification was performed using F-NMR.

[0308] [ka]

[0309] (Synthesis Example 43) Synthesis of Photoacid Generator (a43) A43 was obtained in the same manner as in Synthesis Example 41, except that 1.8 parts of lithium bis(fluorosulfonyl)imide was replaced with 1.8 parts of potassium trifluoromethanesulfonate. 1 H-NMR, 19 Identification was performed using F-NMR.

[0310] [ka]

[0311] Examples 1 to 41, Comparative Examples 1 to 6 [Preparation and Evaluation of Energy Ray-Curable Composition] <Preparation of Curable Composition> The components shown in Tables 1, 2, and 3 below were blended according to the formulation (unit: parts by weight), and the blended components were stirred and mixed at room temperature using a planetary centrifugal mixer to obtain uniform, transparent energy ray-curable compositions (Examples 1 to 41, Comparative Examples 1 to 6). The obtained energy ray-curable compositions were evaluated according to the following evaluation methods.

[0312] [Curability] A 0.04 mm spacer was placed on each end of a glass slide, and the energy ray-curable composition was dropped in the center. The adhesive was spread using a squeegee to a thickness of 0.04 mm, and then irradiated with light from a high-pressure mercury lamp under the following conditions. After irradiation, the sample was heated at 100°C for 5 minutes to obtain a cured product. The tackiness of the surface of the obtained cured product was judged by touch, and the curability was evaluated according to the following criteria. Evaluation criteria ○: The surface was not tacky, and the surface shape of the cured product did not change when palpated. △: There is no tackiness on the surface, but the surface shape of the cured product changes when palpated. ×: The surface had tackiness <High-pressure mercury lamp> Irradiation device: Belt conveyor type UV irradiation device (manufactured by Eye Graphics Co., Ltd.) Lamp: 1.5kW high-pressure mercury lamp Filter: L-34 (Kenko Optical Co., Ltd.) Irradiation intensity (measured with a 365nm illuminometer): 100mW / cm 2 Accumulative irradiation dose: 1000mJ / cm 2

[0313] [Adhesiveness] A 0.04 mm spacer was placed on each end of the glass slide, and the adhesive was dropped in the center. A squeegee was used to spread the adhesive to a thickness of 0.03 mm, and an epoxy resin cube (outer diameter: 4 mm x 4 mm x 1 mm, inner diameter: 3.7 mm x 3.7 mm x 0.8 mm, adhesive area: 2.3 mm) was placed on top of it. 2 ) was set and light irradiation was carried out in the same manner as above. After light irradiation, the sample was heated at 100°C for 5 minutes, and the resulting sample was evaluated for adhesion based on the load (kgf) at which the epoxy resin cube peeled off using a die shear tester (product name "4000PXY", manufactured by DAGE) under the following conditions. Five samples were prepared, and the average value was used for evaluation. The higher the load, the better the adhesion. Adhesion measurement conditions Shear height: 0.65mm Shear speed: 500 μm / s

[0314] [Table 1]

[0315] [Table 2]

[0316] [Table 3]

[0317] <Cationic polymerizable compound> Celloxide 2021P: 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, manufactured by Daicel Corporation THI-DE: Diepoxidized tetrahydroindene, manufactured by JXTG Nippon Oil & Energy Corporation jER 828: Bisphenol A diglycidyl ether, manufactured by Mitsubishi Chemical Corporation jER YX8000: Hydrogenated bisphenol A diglycidyl ether, manufactured by Mitsubishi Chemical Corporation TECHMORE VG3101L: 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-[2,3-epoxypropoxy]phenyl]ethyl]phenyl]propane, manufactured by Printec Co., Ltd. SR-NPG: Neopentyl glycol diglycidyl ether, manufactured by Sakamoto Pharmaceutical Co., Ltd. OXT-121: Xylylene bisoxetane, manufactured by Toagosei Co., Ltd. OXT-221: 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane, manufactured by Toagosei Co., Ltd. X-22-169: alicyclic epoxy-modified silicone oligomer, manufactured by Shin-Etsu Chemical Co., Ltd. Denacol EX-146: p-tert-butylphenyl glycidyl ether, manufactured by Nagase ChemteX Corporation <Photoacid generator> a1 to a43: Compounds obtained in Synthesis Examples 1 to 43 <Coupling agent> KBM-403: 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. <Antifoaming agent> BYK-1790: BYK Japan <Leveling agent> LS-460: Polyether-modified silicone, manufactured by Kusumoto Chemicals Co., Ltd.

[0318] The evaluation results are shown in Tables 1, 2 and 3. As can be seen from Tables 1, 2 and 3, the energy ray-curable composition of the present invention is excellent in curability and thermal stability.

[0319] Examples 42 to 82, Comparative Examples 7 to 9 [Evaluation of Chemically Amplified Positive Photoresist Compositions] <Preparation of evaluation samples> As shown in Table 4 below, 1 part by weight of component (A) as a photoacid generator, 40 parts by weight of a resin represented by the following chemical formula (Resin-1) as resin component (B), and 60 parts by weight of a novolak resin obtained by addition-condensation of m-cresol and p-cresol in the presence of formaldehyde and an acid catalyst as resin component (C) were uniformly dissolved in solvent-1 (propylene glycol monomethyl ether acetate) and filtered through a membrane filter with a pore size of 1 μm to prepare chemically amplified positive photoresist compositions (Examples 41 to 80, Comparative Examples 7 to 9) with a solids concentration of 40% by weight. The prepared chemically amplified positive photoresist compositions were evaluated according to the following evaluation methods.

[0320] <Sensitivity evaluation> The chemically amplified positive resist compositions prepared in Examples 41 to 80 and Comparative Examples 7 to 9 were spin-coated onto silicon wafer substrates and then dried to obtain photoresist layers with a thickness of approximately 20 μm. The resist layers were prebaked on a hot plate at 130°C for 6 minutes. After prebaking, they were subjected to patternwise exposure (i-line) using a TME-150RSC (manufactured by Topcon Corporation) and post-exposure baking (PEB) on a hot plate at 75°C for 5 minutes. The resist layers were then developed for 5 minutes using an immersion method using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, rinsed with running water, and blown with nitrogen to obtain a 10 μm line-and-space (L&S) pattern. Furthermore, the minimum exposure dose below which no residue was observed in the pattern, i.e., the minimum required exposure dose (corresponding to sensitivity) required to form the resist pattern, was measured. A smaller required exposure dose indicates better photoreactivity of the positive resist composition, i.e., superior photosensitivity of the sulfonium salt.

[0321] <Storage stability evaluation> In addition, the photosensitivity (sensitivity) of the chemically amplified positive resist composition prepared above was evaluated as described above immediately after preparation and after storage at 40°C for one month, and the storage stability was judged according to the following criteria. ○: The change in sensitivity after storage at 40℃ for 1 month is less than 5% of the sensitivity immediately after preparation. ×: The change in sensitivity after storage at 40°C for 1 month is 5% or more of the sensitivity immediately after preparation.

[0322] <Pattern shape evaluation> The bottom dimension La and top dimension Lb of the cross section of the 10 μm L&S pattern formed on the silicon wafer substrate by the above procedure were measured using a scanning electron microscope, and the pattern shape was evaluated according to the following criteria. The results are shown in Table 4. ◎: 0.90≦Lb / La≦1 ○: 0.85≦Lb / La<0.90 ×: Lb / La<0.85

[0323] [Table 4]

[0324] [ka]

[0325] [ka]

[0326] The evaluation results are shown in Table 4. As can be seen from Table 4, the chemically amplified positive photoresist compositions of Examples 42 to 82 have higher sensitivity than those of Comparative Examples 7 to 9 which use conventional photoacid generators, and are excellent in storage stability and pattern shape.

[0327] Examples 83 to 123, Comparative Examples 10 to 12 [Evaluation of Chemically Amplified Negative Photoresist Compositions] <Preparation of evaluation samples> As shown in Table 5 below, the composition contained 1 part by weight of component (E) as a photoacid generator, 100 parts by weight of a copolymer (Mw=10,000) consisting of p-hydroxystyrene / styrene = 80 / 20 (molar ratio) as component (F) as a phenolic resin, 20 parts by weight of hexamethoxymethylmelamine (manufactured by Sanwa Chemical Co., Ltd., trade name "Nikarak MW-390") as component (G) as a crosslinking agent, and 10 parts by weight of butadiene / acrylonitrile / hydroxybutylmethacrylate as component (H) as crosslinked fine particles. Chemically amplified negative photoresist compositions (Examples 83-123, Comparative Examples 10-12) of the present invention were prepared by uniformly dissolving 10 parts by weight of a copolymer (average particle size 65 nm, Tg = -38°C) consisting of acrylate / methacrylic acid / divinylbenzene = 64 / 20 / 8 / 6 / 2 (wt%) and 5 parts by weight of γ-glycidoxypropyltrimethoxysilane (Chisso Corporation, trade name "S510") as an adhesion aid component (I) in 145 parts by weight of solvent-2 (ethyl lactate). The prepared chemically amplified negative photoresist compositions were evaluated according to the following evaluation methods.

[0328] <Sensitivity evaluation> Each composition was spin-coated onto a silicon wafer substrate and then heated and dried at 110°C for 3 minutes using a hot plate to obtain a resin coating film with a thickness of approximately 20 μm. Subsequently, pattern exposure (i-line) was performed using a TME-150RSC (manufactured by Topcon Corporation), followed by post-exposure baking (PEB) at 110°C for 3 minutes using a hot plate. Subsequently, development was performed for 2 minutes using an immersion method using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, followed by rinsing with running water and blowing with nitrogen to obtain a 10 μm line-and-space pattern. Furthermore, the minimum required exposure dose (corresponding to sensitivity) required to form a pattern with a residual film ratio of 95% or more, which indicates the ratio of the residual film before and after development, was measured.

[0329] <Storage stability evaluation> In addition, the photosensitivity (sensitivity) of the chemically amplified negative resist composition prepared above was evaluated as described above immediately after preparation and after storage at 40°C for one month, and the storage stability was judged according to the following criteria. ○: The change in sensitivity after storage at 40℃ for 1 month is less than 5% of the sensitivity immediately after preparation. ×: The change in sensitivity after storage at 40°C for 1 month is 5% or more of the sensitivity immediately after preparation.

[0330] <Pattern shape evaluation> The bottom dimension La and top dimension Lb of the cross section of the 20 μm L&S pattern formed on the silicon wafer substrate by the above procedure were measured using a scanning electron microscope, and the pattern shape was evaluated according to the following criteria. The results are shown in Table 5. ◎: 0.90≦La / Lb≦1 ○: 0.85≦La / Lb<0.90 ×: La / Lb<0.85

[0331] [Table 5]

[0332] The evaluation results are shown in Table 5. As can be seen from Table 5, the chemically amplified negative photoresist compositions of Examples 83 to 123 required a lower minimum exposure dose than the compositions of Comparative Examples 10 to 12 in which conventional photoacid generators were used. In other words, the photoacid generators of the present invention have higher sensitivity than the comparative photoacid generators, and are also superior in storage stability and pattern shape. [Industrial Applicability]

[0333] The photoacid generator containing the sulfonylimide salt compound of the present invention can be used in paints, coating agents, various coating materials (hard coats, stain-resistant coatings, anti-fogging coatings, contact-resistant coatings, optical fibers, etc.), backside treatment agents for adhesive tapes, release coating materials for release sheets for adhesive labels (release paper, release plastic films, release metal foils, etc.), printing plates, dental materials (dental compounds, dental composites), inkjet inks, positive resists (for forming connection terminals and wiring patterns in the manufacture of electronic parts such as circuit boards, CSPs, and MEMS elements), resist films, liquid resists, negative resists (for surface protection films for semiconductor elements, etc., permanent film materials such as interlayer insulating films and planarizing films), MEMS resists, and the like. It is suitably used as a photoacid generator in resists, positive-tone photosensitive materials, negative-tone photosensitive materials, various adhesives (temporary fixing agents for various electronic components, adhesives for HDDs, adhesives for pickup lenses, adhesives for functional films for FPDs (deflectors, anti-reflection films, etc.)), holographic resins, FPD materials (color filters, black matrices, partition materials, photospacers, ribs, alignment films for liquid crystal displays, sealants for FPDs, etc.), optical members, molding materials (for construction materials, optical components, lenses), casting materials, putty, glass fiber impregnation agents, fillers, sealants, encapsulants, optical semiconductor (LED) encapsulants, optical waveguide materials, nanoimprint materials, materials for stereolithography, and materials for microstereolithography.

Claims

1. A photoacid generator containing a sulfonylimide salt compound represented by the following general formula (1): 【Chemistry 1】 (In formula (1), X ＋ is a sulfonium cation represented by the following general formula (2) or (21): 【Chemistry 2】 [In formula (2), R １ are each independently an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom; １ m1 represents an integer of 0 to 5, n represents an integer of 1 to 3, and when n=1, Y is represented by the following general formulas (3), (5) to (11), when n=2, Y is represented by the following general formulas (12) to (16), and when n=3, Y is represented by the following general formulas (17) to (19). 【Transformation 3】 [In formulas (3), (5) to (11), R 2 to R 3 and R 5 to R 15 each independently represent an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom; m2 to m3 and m5 to m14 each independently represent R 2 to R 3 , R 5 to R 11, and R １３ ~R １５ m2 and m8 each represent an integer of 0 to 5, m3, m6, m11, m12, and m14 each represent an integer of 0 to 4, m10 represents an integer of 0 to 7, m5 represents an integer of 0 to 9, and m7, m9, and m13 each represent an integer of 0 to 3; Z １ , Z ２ and Z ４ ~Z ６ is -S-, -SO-, -O-, -CO-, -NR １６ -, -R １７ CR １８ - and Z ３ , Z ７ is —O— or —S—, and R １６ ~R １８ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or an optionally substituted aralkyl group having 7 to 20 carbon atoms. 【Chemistry 4】 [In formulas (12) to (16), R １９ ~R ２６ each independently represents an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom; m15 to m22 each independently represent an alkyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom; １９ ~R ２５ m15 represents an integer of 0 to 5, m16, m19, and m21 represent integers of 0 to 4, m17 and m20 represent integers of 0 to 7, and m18 and m22 represent integers of 0 to 3; Z ８ ~Z １０ is —O— or —S—, and Z １１ ~Z １３ is -S-, -SO-, -O-, -CO-, -NR ２７ -, -R ２８ CR ２９ - and R ２７ ~R ２９ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or an optionally substituted aralkyl group having 7 to 20 carbon atoms. 【Transformation 5】 [In formulas (17) to (19), R ３０ ~R ３６ each independently represents an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom; m23 to m28 each independently represent an alkyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom; ３０ ~R ３４ and R ３６ m23 represents an integer of 0 to 5, m24, m26, m27, and m28 represent integers of 0 to 4, and m25 represents an integer of 0 to 3; Z １４ ~Z １８ is —O— or —S—.] 【Transformation 6】 [In formula (21), R ３９ ~R ４１ each independently represents an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom; m31 to m33 each independently represent an alkyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted silyl group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom; ３９ ~R ４１ m31 and m32 each represent an integer of 0 to 4, m33 represents an integer of 0 to 5, Z １９ is -S-, -O-, -CO-, -NR ４２ -, -R ４３ CR ４４ - or a direct bond, R ４２ ~R ４４ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or an optionally substituted aralkyl group having 7 to 20 carbon atoms.

2. An energy ray-curable composition comprising the photoacid generator according to claim 1 and a cationically polymerizable compound.

3. A cured product obtained by curing the energy ray-curable composition according to claim 2.

4. 2. A chemically amplified positive photoresist composition comprising: a component (A) containing the photoacid generator according to claim 1; and a component (B) which is a resin whose solubility in alkali increases under the action of an acid.

5. 5. The chemically amplified positive photoresist composition according to claim 4, wherein component (B), which is a resin whose solubility in alkali increases under the action of an acid, comprises at least one resin selected from the group consisting of novolak resins (B1), polyhydroxystyrene resins (B2), and acrylic resins (B3).

6. 6. The chemically amplified positive photoresist composition according to claim 4, further comprising an alkali-soluble resin (C) and an acid diffusion controller (D).

7. 7. A method for producing a resist pattern, comprising: a laminating step of laminating a photoresist layer having a thickness of 5 to 150 μm, which is made of the chemically amplified positive photoresist composition according to claim 4, on a support, to obtain a photoresist laminate; an exposing step of selectively irradiating light or radiation onto the photoresist laminate; and a developing step of developing the photoresist laminate after the exposing step to obtain a resist pattern.

8. A chemically amplified negative photoresist composition comprising: a component (E) containing the photoacid generator according to claim 1; a component (F) which is an alkali-soluble resin having a phenolic hydroxyl group; and a crosslinker component (G).

9. 9. The chemically amplified negative photoresist composition according to claim 8, further comprising a crosslinked fine particle component (H).

10. A cured product obtained by curing the chemically amplified negative photoresist composition according to claim 8 or 9.

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