JP7779782B2 - Photoacid generator, curable composition and resist composition - Google Patents

Description

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.

A photoacid generator is 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 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).

In recent years, photolithography technology using chemically amplified photoresists has been widely used to manufacture electronic components and form 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 can be used as irradiation light sources, which are inexpensive and have good luminous intensity.

Furthermore, with the downsizing of electronic devices, advances have been made in high-density packaging technology for semiconductor packages, with efforts being made to increase packaging density through the use 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. 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.

Known photoacid generators include onium salts such as iodonium salts and sulfonium salts (see Patent Documents 1 to 6). Compared to iodonium salts, sulfonium salts have better storage stability and longer absorption wavelengths, leading to the development of sulfonium salts with a variety of structures. SbF ₆ ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ , B(C ₆ F ₅ ) ₄ ⁻ , PF ₆ ^{− ,} and the like are used as the anion moiety of these sulfonium salts. However, since Sb is a deleterious substance and As is a toxic substance, onium salts containing these metal elements pose safety issues and their applications are limited. Furthermore, in the field of semiconductor photolithography, photoacid generators containing elements such as metals (SbF ₆ ⁻ , AsF ₆ ⁻ ), phosphorus (PF ₆ ⁻ ), and boron (BF ₄ ⁻ , B(C ₆ F ₅ ) ₄ ⁻ ) cannot be used in chemically amplified resist applications. This is because these elements act as impurities and have a significant effect on transistor performance (Non-Patent Document 1).

Photoacid generators that solve the above problems include, for example, sulfonium salts in which the cation moiety consists of an arylsulfonium and the anion moiety consists of a fluorine-containing sulfonimidate. However, chemically amplified photoresists containing these photoacid generators still have low photosensitivity to i-line light and also suffer from poor pattern shape.

Japanese Patent Application Laid-Open No. 2008-89777 Special Publication No. 2001-512714 Japanese Patent Application Laid-Open No. 2005-275153 Japanese Patent Application Laid-Open No. 2007-114719 Japanese Patent Application Laid-Open No. 2008-222657 Japanese Patent Application Laid-Open No. 2001-288193 JP 2017-508723 A

"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)

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 thereof that utilize the above-mentioned 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 utilizing the above photoacid generator, and a cured product thereof.

The inventors have discovered that a photoacid generator containing a sulfonylimide salt compound represented by the following general formula (1) is suitable for achieving the above purposes.

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

[In formula (2), each R ¹ 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 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; m1 represents the number of R ^1s ; m1 represents an integer of 0 to 5; n represents an integer of 1 to 3; 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)]

[In formulas (3) to (11), R ² 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; and m2 to m14 each independently represent R ² to R ¹¹ and R ¹³ to R ^m2 and m8 represent integers of 0 to 5, m3, m6, m11, m12 and m14 represent integers of 0 to 4, m4 and m10 represent integers of 0 to 7, m5 represents an integer of 0 to 9 and m7, m9 and m13 represent integers of 0 to 3, Z ¹ , Z ² and Z ⁴ to Z ⁶ are -S-, -SO-, -O-, -CO-, -NR ¹⁶ - or -R ¹⁷ CR ¹⁸ -, Z ³ and Z ⁷ are -O- or -S-, and R ¹⁶ to R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may be substituted, an aryl group having 6 to 20 carbon atoms which may be substituted or an aralkyl group having 7 to 20 carbon atoms which may be substituted.

[In formulas (12) to (16), R ¹⁹ to R ²⁶ 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; m15 to m22 each represent the number of R ¹⁹ to R ²⁵ ; 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; Z ⁸ to Z ¹⁰ is —O— or —S—, Z ¹¹ to Z ¹³ are —S—, —SO—, —O—, —CO—, —NR ²⁷ —, or —R ²⁸ CR ²⁹ —, and R ²⁷ to R ²⁹ each independently represent 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.

[In formulas (17) to (19), R ³⁰ to R ³⁶ 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; m23 to m28 represent the number of R ³⁰ to R ³⁴ and R ³⁶ , respectively; 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 to Z ¹⁸ is —O— or —S—.]

[In formula (20), R ³⁷ and R ³⁸ 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; m29 and m30 represent the number of R ³⁷ and R ³⁸ , respectively; m29 represents an integer of 0 to 5, and m30 represents an integer of 0 to 4.]

[In formula (21), R ³⁹ to R ⁴¹ 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; m31 to m33 each represent the number of R ³⁹ to R ⁴¹ ; m31 and m32 each represent an integer of 0 to 4, and m33 represents an integer of 0 to 5; Z ¹⁹ represents -S-, -O-, -CO-, -NR ⁴² -, -R ⁴³ CR ⁴⁴ -, or a direct bond; R ^{R 42} to R ⁴⁴ each independently represent 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.

The present invention also relates to an energy ray-curable composition containing the above-mentioned photoacid generator and a cationically polymerizable compound.

The present invention also relates to a cured product obtained by curing the above-mentioned energy ray-curable composition.

The present invention also relates to 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.

The present invention also provides a method for producing a resist pattern, comprising: a lamination step in which a photoresist layer having a thickness of 5 to 150 μm and made of the above-mentioned chemically amplified positive photoresist composition is laminated on a support to obtain a photoresist laminate; an exposure step in which the photoresist laminate is selectively irradiated with light or radiation; and a development step in which the photoresist laminate is developed after the exposure step to obtain a resist pattern.

The present invention also 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 component (G) which is a crosslinker.

The present invention also relates to a cured product obtained by curing the above-mentioned chemically amplified negative photoresist composition.

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.

Embodiments of the present invention are described in detail below.

The present invention relates to a photoacid generator containing a sulfonylimide 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).)

[In formula (2), each R ¹ 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 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; m1 represents the number of R ^1s ; m1 represents an integer of 0 to 5; n represents an integer of 1 to 3; 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)]

[In formulas (3) to (11), R ² 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; and m2 to m14 each independently represent R ² to R ¹¹ and R ¹³ to R ^m2 and m8 represent integers of 0 to 5, m3, m6, m11, m12 and m14 represent integers of 0 to 4, m4 and m10 represent integers of 0 to 7, m5 represents an integer of 0 to 9 and m7, m9 and m13 represent integers of 0 to 3, Z ¹ , Z ² and Z ⁴ to Z ⁶ are -S-, -SO-, -O-, -CO-, -NR ¹⁶ - or -R ¹⁷ CR ¹⁸ -, Z ³ and Z ⁷ are -O- or -S-, and R ¹⁶ to R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may be substituted, an aryl group having 6 to 20 carbon atoms which may be substituted or an aralkyl group having 7 to 20 carbon atoms which may be substituted.

[In formulas (12) to (16), R ¹⁹ to R ²⁶ 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; m15 to m22 each represent the number of R ¹⁹ to R ²⁵ ; 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; Z ⁸ to Z ¹⁰ is —O— or —S—, Z ¹¹ to Z ¹³ are —S—, —SO—, —O—, —CO—, —NR ²⁷ —, or —R ²⁸ CR ²⁹ —, and R ²⁷ to R ²⁹ each independently represent 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.

[In formulas (17) to (19), R ³⁰ to R ³⁶ 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; m23 to m28 represent the number of R ³⁰ to R ³⁴ and R ³⁶ , respectively; 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 to Z ¹⁸ is —O— or —S—.]

[In formula (20), R ³⁷ and R ³⁸ 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; m29 and m30 represent the number of R ³⁷ and R ³⁸ , respectively; m29 represents an integer of 0 to 5, and m30 represents an integer of 0 to 4.]

[In formula (21), R ³⁹ to R ⁴¹ 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; m31 to m33 each represent the number of R ³⁹ to R ⁴¹ ; m31 and m32 each represent an integer of 0 to 4, and m33 represents an integer of 0 to 5; Z ¹⁹ represents -S-, -O-, -CO-, -NR ⁴² -, -R ⁴³ CR ⁴⁴ -, or a direct bond; R ^{R 42} to R ⁴⁴ each independently represent 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.

In formula (2), examples of the alkyl group for ^R1 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, and 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, and 4-decylcyclohexyl, etc.).

In formula (2), the alkoxy group for R ¹ includes a linear alkoxy group having 1 to 18 carbon atoms, or a branched alkoxy group having 3 to 18 carbon atoms (such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy, and octadecyloxy).

In formula (2), the alkylcarbonyl group represented by R ¹ includes linear or branched alkylcarbonyl groups having 2 to 18 carbon atoms (acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, octadecanoyl, etc.).

In formula (2), the arylcarbonyl group represented by R ¹ includes arylcarbonyl groups having 7 to 11 carbon atoms (such as benzoyl and naphthoyl).

In formula (2), the alkoxycarbonyl group for R ¹ includes a linear alkoxycarbonyl group having 2 to 19 carbon atoms and a branched alkoxycarbonyl group having 4 to 19 carbon atoms (such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, and octadecyloxycarbonyl).

In formula (2), the aryloxycarbonyl group represented by R ¹ includes aryloxycarbonyl groups having 7 to 11 carbon atoms (such as phenoxycarbonyl and naphthoxycarbonyl).

In formula (2), the arylthiocarbonyl group represented by R ¹ includes arylthiocarbonyl groups having 7 to 11 carbon atoms (such as phenylthiocarbonyl and naphthoxythiocarbonyl).

In formula (2), the acyloxy group represented by ^R1 includes a linear acyloxy group having 2 to 19 carbon atoms and a branched acyloxy group having 4 to 19 carbon atoms (e.g., acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, and octadecylcarbonyloxy).

In formula (2), the alkylthio group for ^R1 includes a linear alkylthio group having 1 to 18 carbon atoms and a branched alkylthio group having 3 to 18 carbon atoms (methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, isooctadecylthio, etc.).

In formula (2), the aryl group represented by R ¹ includes aryl groups having 6 to 12 carbon atoms (such as phenyl, tolyl, dimethylphenyl, naphthyl, and biphenylyl).

In formula (2), examples of the heterocyclic hydrocarbon group for ^R1 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).

In formula (2), the alkylsulfinyl group for R ¹ includes a linear alkylsulfinyl group having 1 to 18 carbon atoms and a branched sulfinyl group having 3 to 18 carbon atoms (methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, isooctadecylsulfinyl, etc.).

In formula (2), the arylsulfinyl group represented by R ¹ includes arylsulfinyl groups having 6 to 10 carbon atoms (such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl).

In formula (2), the alkylsulfonyl group for R ¹ includes 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.).

In formula (2), the arylsulfonyl group represented by R ¹ includes arylsulfonyl groups having 6 to 10 carbon atoms (such as phenylsulfonyl, tolylsulfonyl (tosyl), and naphthylsulfonyl).

In formula (2), examples of the hydroxy(poly)alkyleneoxy group represented by R ¹ 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.]

In formula (2), examples of the silyl group that may be substituted for R ¹ include silyl and substituted silyl groups having 1 to 18 carbon atoms (methylsilyl, dimethylsilyl, trimethylsilyl, phenylsilyl, methylphenylsilyl, dimethylphenylsilyl, diphenylsilyl, diphenylmethylsilyl, triphenylsilyl, etc.).

In formula (2), the optionally substituted amino group for R ¹ includes an amino group (—NH ₂ ) 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).

In formula (2), examples of the halogen atom in R ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In formula (2), R ¹ 's are independent of each other and may be the same or different.

In formula (2), ^R1 is preferably an alkyl group, a hydroxy group, an alkoxy group, an arylthio group, or a halogen atom, and more preferably a methyl group, a hydroxy group, a methoxy group, a butoxy group, a phenylthio group, or a fluorine atom.

In formula (2), m1 represents the number of ^R1 , and m1 is an integer of 0 to 5, preferably 0 to 2, and more preferably 0 or 1.

In formulas (3) to (11), the arylthio group among R ² to R ¹⁵ 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 ... [phenoxy]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).

In the formulas (3) to (11), the aryloxy group among R ² to R ¹⁵ includes aryloxy groups having 6 to 10 carbon atoms (such as phenoxy and naphthyloxy).

In formulas (3) to (11), among R ² to R ¹⁵ , 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 as 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 in R 1 in formula (2).

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

In formulas (3) to (11), m2 to m14 represent the numbers of R ² to R ¹⁵ , respectively, 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.

In the formulas (3) to (11), Z ¹ , Z ² and Z ⁴ to Z ⁶ are —S—, —SO—, —O—, —CO—, —NR ¹⁶ — or —R ¹⁷ CR ¹⁸ —, and Z ³ and Z ⁷ are —O— or —S—.

In formulas (3) to (11), among Z ¹ , Z ² and Z ⁴ to Z ⁶ , R ¹⁶ to R 18 of the groups represented by —NR ¹⁶ — and —CR ¹⁷ R ¹⁸ — Examples of ¹⁸ 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).

In formulas (12) to (16), among R ¹⁹ to R ²⁶ , 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 those in R ¹ in formula (2) or R ² to R in formulas (3) to (11). ^{The same} applies to 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 in 15.

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

In the formulas (12) to (16), among R ¹⁹ to R ²⁶ , an alkylcarbonyl group and an arylcarbonyl group are preferred, an alkylcarbonyl group is more preferred, and an acetyl group is particularly preferred.

In formulas (12) to (16), m15 to m22 represent the numbers of R ¹⁹ to R ²⁶ , respectively, 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. m15 to m22 are preferably 0 to 2, more preferably 0 or 1, and particularly preferably 1.

In the formulas (12) to (16), Z ⁸ to Z ¹⁰ are —O— or —S—, and Z ¹¹ to Z ¹³ are —S—, —SO—, —O—, —CO—, —NR ²⁷ —, or —R ²⁸ CR ²⁹ —.

In formulas (12) to (16), R 27 to R ²⁹ of the groups represented by —NR ²⁷ — and —CR ²⁸ R 29 — among Z ¹¹ to Z ¹³ are the same as R ¹⁶ to R ¹⁸ of the groups represented by —NR ¹⁶ — and —CR ¹⁷ R ¹⁸ — among Z ¹ , Z ² , and Z ⁴ to Z ⁶ in formulas ( ³⁾ to ( ¹¹⁾ .

In formulas (17) to (19), among R ³⁰ to R ³⁶ , 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 those in R ¹ in formula (2) or R ² to R in formulas (3) to (11). ^{The same} applies to 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 in 15.

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

In formulas (17) to (19), among R ³⁰ to R ³⁶ , an alkyl group, an alkoxy group, an alkylcarbonyl group, and an arylcarbonyl group are preferred, an alkyl group and an alkylcarbonyl group are more preferred, and a methyl group and an acetyl group are particularly preferred.

In formulas (17) to (19), m23 to m28 represent the numbers of R ³⁰ to R ³⁶ , respectively; 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.

In the formulae (17) to (19), Z ¹⁴ to Z ¹⁸ are —O— or —S—.

In formula (20), among R ³⁷ and R ³⁸ , examples of an alkyl 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, and a halogen atom include R ² to R ^{The same} applies to 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 in 15.

In formula (20), R ³⁷ and R ³⁸ are independent of each other and therefore may be the same or different.

In formula (20), R ³⁷ and R ³⁸ are preferably an alkyl group, an alkoxy group, an alkylcarbonyl group, or an arylcarbonyl group, more preferably an alkoxy group, and particularly preferably a 4-hydroxyethoxy group.

In formula (20), m29 and m30 represent the number of R ³⁷ and R ³⁸ , respectively. 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, more preferably 0 or 1.

In formula (21), among R ³⁹ to R ⁴¹ , 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 those in R ¹ in formula (2) or R ² to R in formulas (3) to (11). ^{The same} applies to 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 in 15.

In formula (21), R ³⁹ to R ⁴¹ are independent of each other and therefore may be the same or different.

In formula (21), of R ³⁹ to R ⁴¹ , an alkyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an aryl group, and a halogen atom are preferred, and a methyl group, an isopropyl group, a 4-hydroxyethoxy group, an acetyl group, a 3-methylbenzoyl group, a phenyl group, and a fluorine atom are more preferred.

In formula (21), m31 to m33 represent the number of R ³⁹ to R ⁴¹ , respectively, 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.

In formula (21), Z ¹⁹ is —S—, —O—, —CO—, —NR ⁴² —, —R ⁴³ CR ⁴⁴ — or a direct bond.

In formula (21), R to R in the groups represented ^{by —NR — and —R 43 CR —} in Z ⁹ are the same as ^R to ^R in the groups represented by —NR — and ^{—CR 17 R —} in Z ¹ , Z ² and Z ⁴ to Z ⁶ in formulas ( ³ ) to ( ¹¹ ).

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

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

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

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, it may be dissolved in advance in a solvent that does not inhibit polymerization, crosslinking, deprotection reactions, etc.

Solvents 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 their derivatives such as ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and the monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or 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.

When a solvent is used, the proportion of the solvent used is preferably 15 to 1,000 parts by weight, and more preferably 30 to 500 parts by weight, per 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 types.

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

Examples of cationically polymerizable compounds that are components of energy ray-curable compositions include cyclic ethers (epoxides, oxetanes, etc.), ethylenically unsaturated compounds (vinyl ethers, styrenes, etc.), bicycloorthoesters, spiroorthocarbonates, and spiroorthoesters (see, for example, JP-A Nos. 11-060996, 09-302269, and 2003-026993).

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

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).

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).

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 long-chain unsaturated compounds (epoxidized soybean oil, epoxidized polybutadiene, etc.).

Known oxetanes can be used, such as 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.

The ethylenically unsaturated compound may be any known cationically polymerizable monomer, including aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrenes, and cationically polymerizable nitrogen-containing monomers.

Aliphatic monovinyl ethers include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.

Aromatic monovinyl ethers include 2-phenoxyethyl vinyl ether, phenyl vinyl ether, and p-methoxyphenyl vinyl ether.

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

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

Cationically polymerizable nitrogen-containing monomers include N-vinylcarbazole and N-vinylpyrrolidone.

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.

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.

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.

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.

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. Furthermore, these cationically polymerizable compounds may be used alone or in combination of two or more types.

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, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the cationically polymerizable compound. Within this range, polymerization of the cationically polymerizable compound is more sufficient, resulting in better physical properties of the cured product. Note that this 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.

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 promoters, ion scavengers, color inhibitors, solvents, non-reactive resins, radically polymerizable compounds, etc.).

As a sensitizer, known sensitizers (such as those described in JP-A Nos. 11-279212 and 09-183960) can be used, such as 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; 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.};

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

Pigments that can be used include known pigments, such as inorganic pigments (titanium oxide, iron oxide, and carbon black) and organic pigments (azo pigments, cyanine pigments, phthalocyanine pigments, and quinacridone pigments).

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, per 100 parts of the photoacid generator of the present invention.

The filler may be any known filler, such as fused silica, crystalline silica, calcium carbonate, aluminum oxide, aluminum hydroxide, zirconium oxide, magnesium carbonate, mica, talc, calcium silicate, and lithium aluminum silicate.

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

As the antistatic agent, known antistatic agents can be used, including nonionic antistatic agents, anionic antistatic agents, cationic antistatic agents, amphoteric antistatic agents, and polymeric antistatic agents.

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

Known flame retardants can be used, including 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.).

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

As the defoaming agent, known defoaming agents can be used, including 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.

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, 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 agents 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.

When an antifoaming agent, flow control agent, light stabilizer, antioxidant, adhesion promoter, ion scavenger, or 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, per 100 parts of the photoacid generator of the present invention.

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 those listed above as solvents for the photoacid generator can be used.

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, per 100 parts of the photoacid generator of the present invention.

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, and polyurethane. The number average molecular weight of these resins is preferably 1,000 to 500,000, and more preferably 5,000 to 100,000 (the number average molecular weight is a value measured by a common method such as GPC).

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

When a non-reactive resin is included, it is desirable to dissolve the non-reactive resin in a solvent beforehand to make it easier to dissolve in the cationic polymerizable compound, etc.

The radical polymerizable compound may be any known radical polymerizable compound (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), or "UV/EB Curing Materials" edited by the RadTech Research Group (1992, CMC)), including monofunctional monomers, difunctional monomers, polyfunctional monomers, epoxy (meth)acrylates, polyester (meth)acrylates, and urethane (meth)acrylates.

When a radically polymerizable compound is contained, the content of the radically polymerizable compound is preferably 5 to 400,000 parts by weight, and more preferably 50 to 150,000 parts by weight, per 100 parts of the photoacid generator of the present invention.

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

The radical polymerization initiator may be any known radical polymerization initiator, 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.).

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

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

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.

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

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 film, release metal foil, etc.), printing plates, dental materials (dental compounds, dental composites), inks, inkjet inks, positive resists (for forming connection terminals and wiring patterns in the manufacture of electronic components 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 crystal displays, sealants for FPDs, etc.), optical components, molding materials (for construction materials, optical components, lenses), casting materials, putty, glass fiber impregnation agents, sealing materials, sealants, encapsulants for optical semiconductors (LEDs), optical waveguide materials, nanoimprint materials, materials for stereolithography, and materials for micro stereolithography.

The photoacid generator of the present invention generates a strong acid upon irradiation with light, and therefore can also be used as a photoacid generator for chemically amplified resist materials as disclosed in the prior art (JP-A Nos. 2003-267968, 2003-261529, and 2002-193925, etc.).

Chemically amplified resist materials include: (1) two-component chemically amplified positive resists, the essential components of which are a resin that becomes soluble in alkaline developer under the action of acid and a photoacid generator; (2) three-component chemically amplified positive resists, the essential components of which are a resin that is soluble in alkaline developer, a dissolution inhibitor that becomes soluble in alkaline developer under the action of acid, and a photoacid generator; and (3) chemically amplified negative resists, the essential components of which are a resin that is soluble in alkaline developer, a crosslinker that crosslinks the resin when heated in the presence of acid, making it insoluble in alkaline developer, and a photoacid generator.

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

In the chemically amplified positive photoresist composition of the present invention, component (A) may be used in combination with other conventionally known photoacid generators. Examples of other photoacid generators include 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.

Other conventionally known photoacid generators are preferably one or more of the group consisting of onium compounds, sulfonimide compounds, diazomethane compounds, and oxime sulfonate compounds.

When such other conventionally known photoacid generators are used in combination, the proportions may be arbitrary, but typically the proportion of the other photoacid generator 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 general formula (1) above.

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

<Resin Component (B) Having Increased Solubility in Alkali by the Action of Acid>
The "resin (B) whose solubility in alkali 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.

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

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

Furthermore, the acid dissociable, dissolution inhibiting group represented by R ^1b above 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.

Specific examples of the acid dissociable, dissolution inhibiting group represented by R ^1b above 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.

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

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

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

As the acid dissociable, dissolution inhibiting group represented by R ^5b , the same acid dissociable, dissolution inhibiting groups as those exemplified for R ^1b can be used.

Furthermore, 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.

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

In formulas (b3) to (b5), R ^6b to R ^13b each independently represent 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, or a linear fluorinated alkyl group having 1 to 6 carbon atoms or a branched fluorinated alkyl group having 3 to 6 carbon atoms; X ^b forms a hydrocarbon ring having 5 to 20 carbon atoms together with the carbon atom to which it is bonded; 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 parentheses; p is an integer of 0 to 4; and q is 0 or 1.

In formulae (b6) to (b8), R ^14b to R ^17b each independently represent a hydrogen atom or a methyl group; in formula (b6), each R ^15b each independently represent a hydrogen atom, a hydroxyl group, a cyano group, or a COOR ^19b group (wherein 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); in formula (b8), each R ^18b each independently represent a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms; and at least one R ^18b is the alicyclic hydrocarbon group or a derivative thereof, or any two R ^18b are bonded to each other to form, together with the common carbon atom to which they are bonded, a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, and the remaining R ^18b represents a linear alkyl group having 1 to 4 carbon atoms or 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.

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

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 achieving such a weight-average molecular weight, the resist resin's physical properties will be excellent.

Furthermore, component (B) is preferably a resin with a dispersity of 1.05 or greater. Here, "dispersity" refers to the weight-average molecular weight divided by the number-average molecular weight. Achieving such a dispersity results in excellent plating resistance and resin physical properties for the resist.

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

<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.

The content of component (C) is preferably 5 to 95 parts by weight, and more preferably 10 to 90 parts by weight, per 100 parts by weight of component (B). A content of 5 parts by weight or more can improve the resin properties of the resist, while a content of 95 parts by weight or less tends to prevent film loss during development.

<Acid Diffusion Controller (D)>
The chemically amplified positive photoresist composition of the present invention preferably further contains an acid diffusion controller (D) (referred to herein 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.

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

The chemically amplified positive photoresist composition of the present invention may further contain a surfactant to improve coating properties, defoaming properties, leveling properties, etc.

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

Furthermore, although the chemically amplified positive photoresist composition of the present invention does not generally require a sensitizer, it can contain a sensitizer to enhance sensitivity, if necessary. As such a sensitizer, conventionally known sensitizers can be used, and specific examples include those listed above.

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 compound represented by general formula (1) above.

The chemically amplified positive photoresist composition of the present invention can also contain an organic solvent to adjust viscosity. Specific examples of organic solvents include those listed above.

The amount of these organic solvents used is preferably in a range that results in a solids concentration of 30% by weight or more, 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.

The chemically amplified positive photoresist composition of the present invention can be prepared, for example, by simply mixing and stirring the above-mentioned components using a conventional method. If necessary, dispersion and mixing can be carried out using a dispersing machine such as a dissolver, homogenizer, or triple-roll mill. After mixing, the components can also be filtered using a mesh or membrane filter.

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 made of the chemically amplified positive photoresist composition of the present invention laminated on a support.

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

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 the desired coating film. Methods that can be used to apply the composition to the 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 proportion of each component in the composition, the coating film thickness, etc., but are typically 70 to 150°C, preferably 80 to 140°C, for approximately 2 to 60 minutes.

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

To form a resist pattern using the photoresist laminate obtained in this way, the resulting photoresist layer is selectively irradiated (exposed) to light or radiation, such as ultraviolet or visible light with a wavelength of 300 to 500 nm, through a mask with a predetermined pattern.

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 coating film thickness, and other factors, but is, for example, 50 to 10,000 mJ/ ^cm2 when an ultra-high-pressure mercury lamp is used.

After exposure, the photoresist layer is heated using a known method to promote the diffusion of the acid and change the alkaline solubility of the exposed areas. Next, the unwanted areas are dissolved and removed using, for example, a specific alkaline aqueous solution as a developer, to obtain the desired resist pattern.

Developing time varies depending on the type and ratio of each component of the composition and the dry film thickness of the composition, but is usually 1 to 30 minutes. The developing method can be any of the following: puddle, dipping, puddle, or spray development. After development, the film is washed with running water for 30 to 90 seconds and then dried using an air gun or oven.

Connecting terminals such as metal posts or bumps can be formed by embedding a conductor such as metal, for example by plating, into the non-resist portions of the resist pattern thus obtained (portions removed with alkaline developer). There are no particular restrictions on the plating method, 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 similar solution according to standard procedures.

The chemically amplified positive photoresist composition of the present invention can also be used as a dry film. This dry film has a protective film formed on both sides of a layer made of the chemically amplified positive photoresist composition of the present invention. The film thickness of the layer made of the chemically amplified positive photoresist composition is typically in the range of 10 to 150 μm, preferably 20 to 120 μm, and more preferably 20 to 80 μm. There are no particular restrictions on the protective film, 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 can be a film selected from the group consisting of polyethylene terephthalate film, polypropylene film, and polyethylene film.

The above-mentioned chemically amplified positive dry film 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 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 60 to 100°C for about 5 to 20 minutes is sufficient.

To form a resist pattern using the chemically amplified dry film obtained in this manner, one protective film from 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. The resist is then pre-baked to dry, and the other protective film is then peeled off.

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 direct coating on the support.

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

Alkali-soluble resin having a phenolic hydroxyl group (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.

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.

Crosslinking agent (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 alkyl-etherified amino groups in the molecule, compounds having at least two 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).

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

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, per 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, relative to 100% by weight of the total of the compound having an alkyl-etherified amino group and the oxirane ring-containing compound.
In this case, the resulting cured film is preferable because it has excellent chemical resistance without impairing high resolution.

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.

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 the crosslinked microparticles are synthesized 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.

The amount of crosslinked fine particles (H) blended is preferably 0.5 to 50 parts by weight, and 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 is achieved, and the thermal shock resistance and heat resistance of the resulting cured film can be improved.

Adhesion Aid The chemically amplified negative photoresist composition of the present invention may 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.

The amount of adhesion aid blended is preferably 0.2 to 10 parts by weight, and more preferably 0.5 to 8 parts by weight, per 100 parts by weight of the phenolic resin (F). A blending amount of this adhesion aid of 0.2 to 10 parts by weight is preferred because it provides excellent storage stability and good adhesion.

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.

The chemically amplified negative photoresist composition of the present invention can also contain a sensitizer, if necessary. As such a sensitizer, conventionally known sensitizers can be used, and specific examples include those listed above.

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 compound represented by general formula (1) above.

Furthermore, the chemically amplified negative photoresist composition of the present invention can contain other additives as needed, to the extent that the properties of the present invention are not impaired. Such other additives include inorganic fillers, quenchers, leveling agents, surfactants, etc.

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

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.

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, a silicon wafer or an alumina substrate with a metal sputtered film), and then dried to volatilize the solvent, forming a coating. 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 the insulating film properties, yielding a cured film.

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., but for example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the exposure dose is about 100 to 50,000 J/ ^m2 for a resin film thickness of 1 to 50 μm.

After exposure, the above-mentioned 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 and the film thickness used, but are typically 70 to 150°C, preferably 80 to 120°C, for approximately 1 to 60 minutes. The film is then developed using 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 paddle development. Development conditions typically involve 20 to 40°C for approximately 1 to 10 minutes.

Furthermore, after development, the composition can be sufficiently cured by heat treatment to fully develop its insulating film properties. While there are no particular limitations on the curing conditions, the composition can be cured by heating at a temperature of 50 to 250°C for approximately 30 minutes to 10 hours, depending on the intended use of the cured product. Furthermore, to fully promote curing and prevent deformation of the resulting pattern, heating can be performed 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 other heating equipment can be used.

The present invention will be further explained below with reference to examples, but is not intended to be limited to these. Unless otherwise specified, all parts and percentages are by weight.

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. The reaction solution was then 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 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 a1. The product was identified by ^1H -NMR and ^19F -NMR.

(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. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

(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 below 20°C. 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 removed, yielding a3. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

(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 changed to 15.4 parts of 9-bromoanthracene. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

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 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 a5. The product was identified by ^1H -NMR and ^19F -NMR.

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 changed to 5.8 parts of bis(4-methylphenyl) sulfoxide. The product was identified by ^H -NMR and ^F -NMR.

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. The mixture was stirred for 1 hour and then 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 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 removed to obtain a7. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

(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 changed to 10.8 parts of bis(4-fluorophenyl) sulfoxide. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

(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. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

(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. The product was identified by ^H -NMR and ^F -NMR.

Synthesis Example 11: Synthesis of Photoacid Generator (a11) 2.0 parts of dithiosalicylic acid and 60 parts of sulfuric acid were stirred, while 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, to which 6.1 parts of lithium bis(fluorosulfonyl)imide was added, 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 a11. The product was identified by ^1H -NMR and ^19F -NMR.

(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 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 distill off the solvent, yielding a12. The product was identified by ^1H -NMR and ^19F -NMR.

(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. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

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 below 10°C, 7.7 parts of methanesulfonic acid was added. The mixture was stirred for 3 hours, followed by 4 hours at room temperature. 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 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 a14. The product was identified by ^1H -NMR and ^19F -NMR.

(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. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

Synthesis Example 16: Synthesis of Photoacid Generator (a16) 14.4 parts of methanesulfonic acid and 14.2 parts of diphosphorus pentoxide were charged and purged with nitrogen. The mixture was heated to 100°C and dissolved. 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. The reaction solution was then poured into a mixture of 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 mixture 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 with stirring, and the mixture was stirred at room temperature for 1 hour. The methyl isobutyl ketone layer was separated and washed three times with ion-exchanged water, and then transferred to a rotary evaporator to remove the solvent, yielding a16. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

(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 was 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 identified by ^1H -NMR and ^19F -NMR.

(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 then 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 with stirring, followed by stirring and then 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 was neutral. Next, 4.4 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer with 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 removed to obtain a18. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

(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. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

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 purged with nitrogen. Under water cooling, 15.6 parts of benzenethiol was added dropwise, and the reaction was allowed to proceed 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 removed. 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 identified by ^1H -NMR and ^19F -NMR.

(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, and the dichloromethane layer was washed with ion-exchanged water until the pH of the aqueous layer became neutral. The solution was then transferred to a rotary evaporator to remove the solvent, yielding 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 then 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 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 then transferred to a rotary evaporator to remove the solvent, thereby obtaining a21. The product was identified by ^1H -NMR.

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 0-10°C, 4.3 parts of methanesulfonic acid was added and stirred 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 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. The product was identified by ^1H -NMR and ^19F -NMR.

(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 the mixture was 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 the mixture was 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 the mixture was stirred at room temperature for 1 hour. The ortho-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 a23. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

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 changed to 18.6 parts of 4-phenyloxyacetophenone. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

(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 changed to 20.5 parts of 2-acetyl-5-(phenylthio)thiophene. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

(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 changed to 19.1 parts of 2-acetyl-5-(phenylthio)furan. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

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. The reaction mixture was stirred at room temperature for 3 hours and 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 with stirring, and the mixture was stirred at room temperature for 1 hour. The orthodichloromethane layer was separated and washed three times with ion-exchanged water, then transferred to a rotary evaporator to remove the solvent, yielding a27. The product was identified by ^1H -NMR and ^19F -NMR.

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 changed to 10.4 parts of 4-phenylthioacetophenone. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

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. Next, 1.9 parts of thionyl chloride was 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 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, and then transferred to a rotary evaporator to remove the solvent, yielding a29. The product was identified by ^1H -NMR and ^19F -NMR.

(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 changed to 23.0 parts of 1-(5-bromo-2-furyl)ethanone. The product was identified by ^H -NMR and ^F -NMR.

(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. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

(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. The product was identified by ^H -NMR and F-NMR.

(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. The product was identified by ^H -NMR and F-NMR.

(Synthesis Example 34) Synthesis of Photoacid Generator (a34) a34 was obtained in the same manner as in Synthesis Example 29, except that 25.0 parts of 2-acetyl-5-bromothiophene was changed to 24.0 parts of 2-bromobenzofuran and 15.9 parts of thiophenol was changed to 17.6 parts of ^2,6 -dimethylphenol. The product was identified by ^H -NMR and F-NMR.

Synthesis Example 35: Synthesis of Photoacid Generator (A-35): 31.7 parts of methanesulfonic acid and 3.4 parts of phosphorus pentoxide were charged and purged with nitrogen. The mixture was then heated to 100°C and dissolved. After cooling to room temperature, 26.3 parts of bis(4-hydroxyethoxyphenyl) sulfide and 3.1 parts of diphenyl sulfide were added and stirred at room temperature for 5 hours. The mixture was then 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 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 a-35. The product was identified by ^1H -NMR and ^19F -NMR.

(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. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

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 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 removed to obtain a37. The product was identified by ^1H -NMR and ^19F -NMR.

(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 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 removed 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. To the mixed solution, 0.05 parts of potassium hydroxide was added and 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 while 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 and the solvent was removed to obtain a38. The product was identified by ^1H -NMR and ^19F -NMR.

Synthesis Example 39: Synthesis of Photoacid Generator (a39) 200 parts of concentrated sulfuric acid were ice-cooled, and 43.2 parts of 2-(3-methylbenzoyl)dibenzothiophene-5-oxide and 15.0 parts of toluene were added. The mixture was stirred 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 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 removed to obtain a39. The product was identified by ^1H -NMR and ^19F -NMR.

(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. The product was identified by ^H -NMR ^and F-NMR.

(Synthesis Example 41) Synthesis of Photoacid Generator (a41): 25 parts of phenoxatiline were mixed with 200 parts of tetrahydrofuran, and 25 parts of trimethylsilyl chloride were added dropwise. After cooling to 0°C, 39 parts of a THF solution (16%) of phenylmagnesium bromide was 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. Next, 3.3 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 removed to obtain a40. The product was identified by ^1H -NMR and ^19F -NMR.

(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 was added dropwise at room temperature. The mixture was then stirred at 60°C for 6 hours. After cooling to room temperature, the reaction solution was 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 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 a42. The product was identified by ^1H -NMR and ^19F -NMR.

(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. The product was identified by ¹ H-NMR and ¹⁹ F-NMR.

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.

[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 light irradiation was performed using a high-pressure mercury lamp under the following conditions. After light irradiation, the glass slide 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. △: The surface was not tacky, but the surface shape of the cured product changed when palpated. ×: The surface was tacky. <High-pressure mercury lamp>
Irradiation device: Belt conveyor type UV irradiation device (manufactured by iGraphics Co., Ltd.)
Lamp: 1.5kW high-pressure mercury lamp Filter: L-34 (Kenko Optical Co., Ltd.)
Irradiation intensity (measured with a 365 nm illuminometer): 100 mW/cm ²
Accumulated irradiation amount: 1000 mJ/cm ²

[Adhesiveness]
A 0.04 mm spacer was placed on each end of a glass slide, and the adhesive was dropped in the center. The adhesive was spread using a squeegee to a thickness of 0.03 mm, and an epoxy resin cube (outer diameter: 4 mm × 4 mm × 1 mm, inner diameter: 3.7 mm × 3.7 mm × 0.8 mm, adhesive area: 2.3 ^mm2 ) was placed on top of the adhesive, and light irradiation was performed in the same manner as above.
After light irradiation, the sample was heated at 100°C for 5 minutes, and the adhesiveness of the obtained sample was evaluated 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. A larger load indicates better adhesiveness.
Adhesion measurement conditions: Shear height: 0.65 mm
Shear speed: 500 μm/s

<Cationically 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, manufactured by Mitsubishi Chemical Corporation. 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: both-end 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. (defoaming agent)
BYK-1790: BYK Japan <Leveling agent>
LS-460: Polyether-modified silicone, manufactured by Kusumoto Chemicals Co., Ltd.

The above 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 has excellent curability and thermal stability.

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.

<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 film thickness of approximately 20 μm. This resist layer was pre-baked on a hot plate at 130°C for 6 minutes. After pre-baking, a pattern of i-line exposure was performed using a TME-150RSC (manufactured by Topcon Corporation), followed by post-exposure baking (PEB) on a hot plate at 75°C for 5 minutes. The resist layer was then developed for 5 minutes by immersion 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 this pattern, i.e., the minimum required exposure dose (corresponding to sensitivity) required to form a 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.

<Storage stability evaluation>
Furthermore, using the chemically amplified positive resist compositions prepared above, the photosensitivity (sensitivity) 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°C 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.

<Pattern shape evaluation>
The dimensions of the lower side La and the upper side 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

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 using conventional photoacid generators, as in Comparative Examples 7 to 9, and are superior in storage stability and pattern shape.

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 to 123, Comparative Examples 10 to 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 in a ratio of 64/20/8/6/2 (by weight) and 5 parts by weight of γ-glycidoxypropyltrimethoxysilane (manufactured by 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.

<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 having a film 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) for 3 minutes at 110°C using a hot plate. Subsequently, development was performed for 2 minutes by immersion 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.

<Storage stability evaluation>
Furthermore, 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 evaluated according to the following criteria.
○: The change in sensitivity after storage at 40°C 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.

<Pattern shape evaluation>
The dimensions of the lower side La and the upper side 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

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 those using conventional photoacid generators, as in Comparative Examples 10 to 12. In other words, the photoacid generators of the present invention are more sensitive than the comparative photoacid generators, and also have superior storage stability and pattern shape.

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 film, release metal foil, etc.), printing plates, dental materials (dental compounds, dental composites), inks, inkjet inks, positive resists (for forming connection terminals and wiring patterns in the manufacture of electronic components 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 ideally 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 (polarizers, 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 components, molding materials (for construction materials, optical components, lenses), casting materials, putty, glass fiber impregnation agents, sealing materials, encapsulants, optical semiconductor (LED) encapsulants, optical waveguide materials, nanoimprint materials, materials for stereolithography, and materials for microstereolithography.

Claims (10)

A photoacid generator containing a sulfonylimide salt compound represented by the following general formula (1):
(In formula (1), X ⁺ is a sulfonium cation represented by the following general formula (2) or (21) .)
[In formula (2), each R ¹ 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 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; m1 represents the number of R ^1s ; m1 represents an integer of 0 to 5; n represents an integer of 1 to 3; 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)]
[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 to R ^m2 and m8 are integers of 0 to 5, m3, m6, m11, m12 and m14 are integers of 0 to 4, m10 is an integer of 0 to 7, m5 is an integer of 0 to 9, m7, m9 and m13 are integers of 0 to 3, Z ¹ , Z ² and Z ⁴ to Z ⁶ are -S-, -SO-, -O-, -CO-, -NR ¹⁶ - or -R ¹⁷ CR ¹⁸ -, Z ³ and Z ⁷ are -O- or -S-, and R ¹⁶ to R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may be substituted, an aryl group having 6 to 20 carbon atoms which may be substituted, or an aralkyl group having 7 to 20 carbon atoms which may be substituted.
[In formulas (12) to (16), R ¹⁹ to R ²⁶ 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; m15 to m22 each represent the number of R ¹⁹ to R ²⁵ ; 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; Z ⁸ to Z ¹⁰ is —O— or —S—, Z ¹¹ to Z ¹³ are —S—, —SO—, —O—, —CO—, —NR ²⁷ —, or —R ²⁸ CR ²⁹ —, and R ²⁷ to R ²⁹ each independently represent 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.
[In formulas (17) to (19), R ³⁰ to R ³⁶ 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; m23 to m28 represent the number of R ³⁰ to R ³⁴ and R ³⁶ , respectively; 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 to Z ¹⁸ is —O— or —S—.]
[In formula (21), R ³⁹ to R ⁴¹ 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; m31 to m33 each represent the number of R ³⁹ to R ⁴¹ ; m31 and m32 each represent an integer of 0 to 4, and m33 represents an integer of 0 to 5; Z ¹⁹ represents -S-, -O-, -CO-, -NR ⁴² -, -R ⁴³ CR ⁴⁴ -, or a direct bond; and R ^{R 42} to R ⁴⁴ each independently represent 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.
An energy ray-curable composition comprising the photoacid generator of claim 1 and a cationically polymerizable compound. A cured product obtained by curing the energy ray-curable composition described in claim 2. A chemically amplified positive photoresist composition comprising component (A) containing the photoacid generator described in claim 1 and component (B) which is a resin whose solubility in alkali increases under the action of acid. The chemically amplified positive photoresist composition according to claim 4, wherein component (B), 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 resin (B1), polyhydroxystyrene resin (B2), and acrylic resin (B3). The chemically amplified positive photoresist composition according to claim 4 or 5, further comprising an alkali-soluble resin (C) and an acid diffusion controller (D). A method for producing a resist pattern, comprising: a lamination step of laminating a photoresist layer having a thickness of 5 to 150 μm, made of the chemically amplified positive photoresist composition according to any one of claims 4 to 6, onto 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. A chemically amplified negative photoresist composition comprising component (E) containing the photoacid generator described in claim 1, component (F) which is an alkali-soluble resin having a phenolic hydroxyl group, and component (G) which is a crosslinker. The chemically amplified negative photoresist composition according to claim 8, further comprising a crosslinked fine particle component (H). A cured product obtained by curing the chemically amplified negative photoresist composition described in claim 8 or 9.