Photoacid generator, curable composition and resist composition

Abstract

To provide: a new photoacid generator containing a sulfonylimide salt compound that exhibits high photosensitivity to i-line and excellent storage stability in a formulation with a cationically polymerizable compound such as an epoxy compound; and an energy-ray-curable composition, a chemically amplified positive photoresist composition, and a chemically amplified negative photoresist composition that contain the photoacid generator.SOLUTION: The invention provides a photoacid generator containing a sulfonylimide salt compound represented by the general formula (1) in the figure. (In the formula (1), X+ represents a sulfonium cation represented by the following general formula (4).)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates, firstly, to a photoacid generator containing a specific sulfonylimide salt compound suitable for curing cationic polymerizable compounds by reacting them with active energy rays such as light, electron beams, or X-rays. The present invention relates, secondly, to a curable composition containing the photoacid generator and a cured body obtained by curing the same. The present invention relates, thirdly, to a chemically amplified positive-type photoresist composition containing the photoacid generator and a method for producing a resist pattern using the same. The present invention relates, fourthly, to a chemically amplified negative-type photoresist composition containing the photoacid generator and a cured body obtained by curing the same. [Background technology]

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

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

[0004] In addition, with the downsizing of electronic devices, the high-density mounting technology of semiconductor packages has advanced, and efforts have been made to increase the mounting density based on multi-pin thin-film mounting of packages, miniaturization of package sizes, two-dimensional mounting technology using the flip-chip method, and three-dimensional mounting technology. In order to form such high-density mounting technology with high precision, a chemically amplified photoresist is required to have excellent pattern shape and high photosensitivity so that a resist pattern with high rectangularity can be obtained with a smaller exposure amount.

[0005] As existing photoacid generators, onium salts such as iodonium salts and sulfonium salts are known (Patent Documents 1 to 6). Sulfonium salts have better storage stability and longer absorption wavelengths compared to iodonium salts, and thus sulfonium salts with various structures have been developed. As the anion site of these sulfonium salts, SbF6 - 、AsF6 - 、BF4 - 、B(C6F5)4 - 、PF6 - etc. are used. However, since Sb is a poisonous drug and As is a poison, onium salts containing these metal elements have safety problems and their uses are limited. Also, in the field of semiconductor photolithography, photoacid generators having elements such as metals (SbF6 - 、AsF6 - ), phosphorus (PF6 - ), boron (BF4 - 、B(C6F5)4 - ) etc. cannot be used for chemically amplified resist applications. This is because these elements become impurities and have a great impact on transistor performance (Non-Patent Document 1).

[0006] As a photoacid generator for solving the above problems, for example, a sulfonium salt in which the cation site consists of arylsulfonium and the anion site consists of a fluorine-containing sulfonimidate can be mentioned. However, there is a problem that the photosensitivity of the chemically amplified photoresist containing this photoacid generator to i-line is still low and the pattern shape is also poor.

Prior Art Documents

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

[0008] [Non-Patent Document 1] "Latest Trends in UV / EB Curing Technology," supervised by Mitsuru Ueda, edited by Radtech Research Group, Chapter 2: Trends in Material Development, 3. Photopolymerization Initiators, CMC Publishing (2006). [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] The first object of the present invention is to provide a novel photoacid generator comprising a sulfonylimide salt compound that has high photosensitivity to i-rays and excellent storage stability when combined with cationic polymerizable compounds such as epoxy compounds. A second object of the present invention is to provide an energy ray curable composition and a cured product utilizing the above-mentioned photoacid generator. A third object of the present invention is to provide a chemically amplified positive-type photoresist composition utilizing the above-mentioned photoacid generator and a method for producing the same. A fourth object of the present invention is to provide a chemically amplified negative-type photoresist composition and a cured product thereof utilizing the above-mentioned photoacid generator. [Means for solving the problem]

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

[0011] [ka]

[0012] [In formula (1), X + This is a sulfonium cation represented by the following general formulas (2), (3), (4), (5), or (6).

[0013] [ka]

[0014] [In formula (2), R 1 ~R 4 These independently represent a hydroxyl group, alkoxy group, alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy(poly)alkyleneoxy group, optionally substituted silyl group, optionally substituted amino group, cyano group, nitro group, or halogen atom, and m1 to m4 are each R 1 ~R 4 This represents the number of elements, where m1, m3, and m4 are integers from 0 to 5, and m2 is an integer from 0 to 4, with at least one of m1 to m4 being 1.

[0015] [ka]

[0016] [In formula (3), R 5 R represents an alkyl group or aryl group. 6 ~R 9 These independently represent an alkyl group, hydroxyl 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, cyano group, nitro group, or halogen atom, and m5 to m8 are each R 6 ~R 9 This represents the number of elements, where m5 and m6 are integers from 0 to 4, and m7 and m8 are integers from 0 to 5.

[0017] [ka]

[0018] [In formula (4), R 10 ~R 15 These independently represent an alkyl group, hydroxyl 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, cyano group, nitro group, or halogen atom, and m9 to m14 are each R 10 ~R 15 The numbers represent the number of elements, with m9, m12, and m14 representing integers from 0 to 5, and m10, m11, and m13 representing integers from 0 to 4.

[0019] [ka]

[0020] [In formula (5), R 16 ~R 21 R independently represents an alkyl group, hydroxyl 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, cyano group, nitro group, or halogen atom. 22 ~R 25 The terms independently represent an alkyl group, alkoxy group, aryl group, aryloxy group, halogen atom, or hydrogen atom, and m15 to m20 are each R 16 ~R 21 The numbers represent the number of elements, with m15, m17, and m18 representing integers from 0 to 4, m16 and m19 representing integers from 0 to 3, and m20 representing integers from 0 to 5.

[0021] [ka]

[0022] [In formula (6), R 26 ~R 31 R independently represents an alkyl group, hydroxyl 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, cyano group, nitro group, or halogen atom. 26 ~R 31Each of these independently represents an alkyl group, alkoxy group, aryl group, aryloxy group, halogen atom, or hydrogen atom, and m21 to m26 are each R 26 ~R 31 This represents the number of elements, where m21, m23, and m24 are integers from 0 to 4, m22 and m25 are integers from 0 to 3, and m26 is an integer from 0 to 5.

[0023] Furthermore, the present invention is an energy ray curable composition characterized by containing the above-mentioned photoacid generator and a cationic polymerizable compound.

[0024] Furthermore, the present invention is a cured body characterized by being obtained by curing the above-mentioned energy ray curable composition.

[0025] Furthermore, the present invention is a chemically amplified positive-type photoresist composition comprising a component (A) containing the above-mentioned photoacid generator and a component (B) which is a resin whose solubility in alkali increases due to the action of acid.

[0026] Furthermore, the present invention is a method for producing a resist pattern, characterized by comprising: a lamination step of laminating a photoresist layer with a thickness of 5 to 150 μm made of the above-mentioned chemically amplified positive-type photoresist composition 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.

[0027] Furthermore, the present invention provides a chemically amplified negative-type photoresist composition comprising a component (E) containing the above-mentioned photoacid generator, a component (F) which is an alkali-soluble resin having phenolic hydroxyl groups, and a crosslinking agent component (G).

[0028] Furthermore, the present invention is a cured body characterized by being obtained by curing the above-mentioned chemically amplified negative-type photoresist composition. [Effects of the Invention]

[0029] The photoacid generator containing the sulfonylimide salt compound of the present invention exhibits excellent photosensitivity to active energy rays such as visible light, ultraviolet light, electron beams, and X-rays, high compatibility with solvents and cationic polymerizable compounds such as epoxy compounds, and excellent storage stability in formulations with cationic polymerizable compounds such as epoxy compounds. The photoacid generator of the present invention exhibits excellent curing properties under the action of ultraviolet light, particularly i-rays, when used for curing cationic polymerizable compounds, and can cure cationic polymerizable compounds. The energy-ray curable composition of the present invention contains the above-mentioned photoacid generator and can therefore be cured with 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, thus offering excellent cost and workability. The chemically amplified positive-type photoresist composition and the chemically amplified negative-type photoresist composition of the present invention contain the above-mentioned photoacid generator, making it possible to obtain a resist that is highly sensitive to i-rays (pattern formation is possible with a lower exposure amount compared to conventional resists). Furthermore, the chemically amplified positive-type photoresist composition and the chemically amplified negative-type photoresist composition of the present invention have high storage stability and good resist pattern shape. [Modes for carrying out the invention]

[0030] Embodiments of the present invention will be described in detail below.

[0031] The photoacid generator of the present invention contains a sulfonylimide salt compound represented by the following general formula (1).

[0032] [ka]

[0033] [In formula (1), X + This is a sulfonium cation represented by the following general formulas (2), (3), (4), (5), or (6).

[0034] [ka]

[0035] [In formula (2), R 1 ~R 4 These independently represent a hydroxyl group, alkoxy group, alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy(poly)alkyleneoxy group, optionally substituted silyl group, optionally substituted amino group, cyano group, nitro group, or halogen atom, and m1 to m4 are each R 1 ~R 4 This represents the number of elements, where m1, m3, and m4 are integers from 0 to 5, and m2 is an integer from 0 to 4, with at least one of m1 to m4 being 1.

[0036] [ka]

[0037] [In formula (3), R 5 R represents an alkyl group or aryl group. 6 ~R 9 These independently represent an alkyl group, hydroxyl 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, cyano group, nitro group, or halogen atom, and m5 to m8 are each R 6 ~R 9 This represents the number of elements, where m5 and m6 are integers from 0 to 4, and m7 and m8 are integers from 0 to 5.

[0038] [ka]

[0039] [In formula (4), R 10 ~R 15 These independently represent an alkyl group, hydroxyl 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, cyano group, nitro group, or halogen atom, and m9 to m14 are each R 10 ~R 15 The numbers represent the number of elements, with m9, m12, and m14 representing integers from 0 to 5, and m10, m11, and m13 representing integers from 0 to 4.

[0040] [ka]

[0041] [In formula (5), R 16 ~R 21 R independently represents an alkyl group, hydroxyl 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, cyano group, nitro group, or halogen atom. 22 ~R 25 The terms independently represent an alkyl group, alkoxy group, aryl group, aryloxy group, halogen atom, or hydrogen atom, and m15 to m20 are each R 16 ~R 21The numbers represent the number of elements, with m15, m17, and m18 representing integers from 0 to 4, m16 and m19 representing integers from 0 to 3, and m20 representing integers from 0 to 5.

[0042] [ka]

[0043] [In formula (6), R 26 ~R 31 R independently represents an alkyl group, hydroxyl 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, cyano group, nitro group, or halogen atom. 26 ~R 31 Each of these independently represents an alkyl group, alkoxy group, aryl group, aryloxy group, halogen atom, or hydrogen atom, and m21 to m26 are each R 26 ~R 31 This represents the number of elements, where m21, m23, and m24 are integers from 0 to 4, m22 and m25 are integers from 0 to 3, and m26 is an integer from 0 to 5.

[0044] In equation (2), R 1 ~R 4 Examples of alkoxy groups include linear alkoxy groups having 1 to 18 carbon atoms, or branched alkoxy groups having 3 to 18 carbon atoms (such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy, and octadecyloxy).

[0045] In equation (2), R 1 ~R 4Examples of alkoxycarbonyl groups include linear alkoxycarbonyl groups having 2 to 19 carbon atoms or branched alkoxycarbonyl groups having 4 to 19 carbon atoms (such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, and octadecyloxycarbonyl).

[0046] In equation (2), R 1 ~R 4 Among these, examples of aryloxycarbonyl groups include aryloxycarbonyl groups having 7 to 11 carbon atoms (such as phenoxycarbonyl and naphthoxycarbonyl).

[0047] In equation (2), R 1 ~R 4 Examples of arylthiocarbonyl groups include arylthiocarbonyl groups having 7 to 11 carbon atoms (such as phenylthiocarbonyl and naphthoxythiocarbonyl).

[0048] In equation (2), R 1 ~R 4 Examples of acyloxy groups include linear acyloxy groups having 2 to 19 carbon atoms or branched acyloxy groups having 4 to 19 carbon atoms (such as acetoxy, ethyl carbonyloxy, propyl carbonyloxy, isopropyl carbonyloxy, butyl carbonyloxy, isobutyl carbonyloxy, sec-butyl carbonyloxy, tert-butyl carbonyloxy, octyl carbonyloxy, tetradecyl carbonyloxy, and octadecyl carbonyloxy).

[0049] In equation (2), R 1 ~R 4Among these, arylthio groups include arylthio groups with 6 to 20 carbon atoms (phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4-[4-(phenylthio)benzoyl]phenylthio, 4-[4-(phenylthio) phenyl Examples include [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, etc.

[0050] In equation (2), R 1 ~R 4 Examples of alkylthio groups include linear alkylthio groups having 1 to 18 carbon atoms or branched alkylthio groups having 3 to 18 carbon atoms (such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, and isooctadecylthio).

[0051] In equation (2), R 1 ~R 4Among these, examples of aryloxy groups include aryloxy groups with 6 to 10 carbon atoms (such as phenoxy and naphthyloxy).

[0052] In equation (2), R 1 ~R 4 Examples of alkylsulfinyl groups include linear alkylsulfinyl groups having 1 to 18 carbon atoms or branched sulfinyl groups having 3 to 18 carbon atoms (such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, and isooctadecylsulfinyl).

[0053] In equation (2), R 1 ~R 4 Examples of arylsulfinyl groups include arylsulfinyl groups having 6 to 10 carbon atoms (such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl).

[0054] In equation (2), R 1 ~R 4 Examples of alkylsulfonyl groups include linear alkylsulfonyl groups having 1 to 18 carbon atoms or branched alkylsulfonyl groups having 3 to 18 carbon atoms (such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl, and octadecylsulfonyl).

[0055] In equation (2), R 1 ~R 4Among them, examples of the arylsulfonyl group include arylsulfonyl groups having 6 to 10 carbon atoms (such as phenylsulfonyl, tolylsulfonyl (tosyl group), and naphthylsulfonyl, etc.).

[0056] In formula (2), R 1 ~R 4 Among them, examples of the hydroxy(poly)alkyleneoxy group include hydroxy(poly)alkyleneoxy groups represented by formula (7), etc. HO(-AO)q- (7) [AO represents an ethyleneoxy group and / or a propyleneoxy group, and q represents an integer of 1 to 5.]

[0057] In formula (2), R 1 ~R 4 Among them, examples of the optionally substituted silyl group include silyl and substituted silyl groups having 1 to 18 carbon atoms (such as methylsilyl, dimethylsilyl, trimethylsilyl, phenylsilyl, methylphenylsilyl, dimethylphenylsilyl, diphenylsilyl, diphenylmethylsilyl, triphenylsilyl, etc.), etc.

[0058] In formula (2), R 1 ~R 4 Among them, examples of the optionally substituted amino group include an amino group (-NH2) and substituted amino groups having 1 to 15 carbon atoms (such as 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, etc.), etc.

[0059] In formula (2), R 1 ~R 4 Among them, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, etc.

[0060] In formula (2), R 1 ~R 4 are independent of each other, and thus may be the same as or different from each other.

[0061] In formula (2), among R 1 ~R 4 preferably an alkoxy group, an aryloxy group, a silyl group and a halogen atom, more preferably a methoxy group, a phenoxy group, a trimethylsilyl group, a chlorine atom and a bromine atom, particularly preferably a methoxy group and a phenoxy group.

[0062] In formula (2), m1 to m4 each represent the number of R 1 ~R 4 m1 is an integer of 0 to 5, preferably 0 to 2, more preferably 0 or 1, particularly preferably 0. m2 is an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1, particularly preferably 1. m3 is an integer of 0 to 5, preferably 0 to 2, more preferably 0 or 1, particularly preferably 0. m4 is an integer of 0 to 5, preferably 0 to 2, more preferably 0 or 1, particularly preferably 1. Note that at least one of m1 to m4 is 1. When m1 to m4 are within these preferred ranges, the photosensitivity of the photoacid generator containing the sulfonylimide salt compound is further improved.

[0063] In formula (3), R 5 is an alkyl group or an aryl group, preferably a methyl group and a phenyl group.

[0064] In formula (3), R 6 ~R 9Examples of alkyl groups 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.).

[0065] In equation (3), R 6 ~R 9 Examples of alkylcarbonyl groups include linear or branched alkylcarbonyl groups having 2 to 18 carbon atoms (such as acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanol, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, and octadecanoyl).

[0066] In equation (3), R 6 ~R 9 Examples of arylcarbonyl groups include arylcarbonyl groups having 7 to 11 carbon atoms (such as benzoyl and naphthoyl).

[0067] In equation (3), R 6 ~R 9 Among these, examples of aryl groups include aryl groups having 6 to 12 carbon atoms (phenyl, tolyl, dimethylphenyl, naphthyl, and biphenylyl, etc.).

[0068] In equation (3), R 6 ~R 9Among these, heterocyclic hydrocarbon groups 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).

[0069] In equation (3), R 6 ~R 9 Among these, alkoxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, arylthiocarbonyl groups, acyloxy groups, arylthio groups, alkylthio groups, aryloxy groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, hydroxy(poly)alkyleneoxy groups, substituted silyl groups, substituted amino groups, and halogen atoms are, in formula (2), R 1 ~R 4 The following are equivalent to alkoxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, arylthiocarbonyl groups, acyloxy groups, arylthio groups, alkylthio groups, aryloxy groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, hydroxy(poly)alkyleneoxy groups, silyl groups that may be substituted, amino groups that may be substituted, and halogen atoms.

[0070] In equation (3), R 6 ~R 9 They are mutually independent and therefore may be identical or different from one another.

[0071] In equation (3), m5 to m8 are R 6 ~R 9The numbers represent the number of integers, where m5 and m6 are integers from 0 to 4, and m7 and m8 are integers from 0 to 5. m5 to m8 are preferably from 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0072] In equation (4), R 10 ~R 15 Among these, alkyl groups, alkoxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, arylthiocarbonyl groups, acyloxy groups, arylthio groups, alkylthio groups, aryl groups, heterocyclic hydrocarbon groups, aryloxy groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, hydroxy(poly)alkyleneoxy groups, substituted silyl groups, substituted amino groups, and halogen atoms are, in formula (3), R 6 ~R 9 This is the same as alkyl groups, alkoxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, arylthiocarbonyl groups, acyloxy groups, arylthio groups, alkylthio groups, aryl groups, heterocyclic hydrocarbon groups, aryloxy groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, hydroxy(poly)alkyleneoxy groups, silyl groups that may be substituted, amino groups that may be substituted, and halogen atoms.

[0073] In equation (4), R 10 ~R 15 They are mutually independent and therefore may be identical or different from one another.

[0074] In equation (4), R 10 ~R 15 Of these, alkyl groups and alkoxy groups are preferred, and methyl groups, tert-butyl groups and methoxy groups are more preferred.

[0075] In equation (4), m9 to m14 are R 10 ~R 15The numbers represent the number of integers, where m9, m12, and m14 are integers from 0 to 5, and m10, m11, and m13 are integers from 0 to 4. m9 to m14 are preferably from 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0076] In equation (5), R 16 ~R 21 Among these, alkyl groups, alkoxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, arylthiocarbonyl groups, acyloxy groups, arylthio groups, alkylthio groups, aryl groups, heterocyclic hydrocarbon groups, aryloxy groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, hydroxy(poly)alkyleneoxy groups, substituted silyl groups, substituted amino groups, and halogen atoms are, in formula (3), R 6 ~R 9 This is the same as alkyl groups, alkoxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, arylthiocarbonyl groups, acyloxy groups, arylthio groups, alkylthio groups, aryl groups, heterocyclic hydrocarbon groups, aryloxy groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, hydroxy(poly)alkyleneoxy groups, silyl groups that may be substituted, amino groups that may be substituted, and halogen atoms.

[0077] In equation (5), R 16 ~R 21 They are mutually independent and therefore may be identical or different from one another.

[0078] In equation (5), R 16 ~R 21 Of these, alkyl groups, alkoxy groups, alkylcarbonyl groups, and arylcarbonyl groups are preferred, more preferably alkylcarbonyl groups and arylcarbonyl groups, and particularly preferably acetyl groups and benzoyl groups.

[0079] In equation (5), m15 to m20 are R 16 ~R 21 The numbers represent the values ​​of m15, m17, and m18, where m15, m17, and m18 are integers from 0 to 4; m16 and m19 are integers from 0 to 3; and m20 is an integer from 0 to 5. m15 to m20 are preferably from 0 to 2, and more preferably 0 or 1.

[0080] In equation (5), R 22 ~R 25 Among these, the alkyl group, alkoxy group, aryl group, aryloxy group, and halogen atom are R in formula (3). 6 ~R 9 This is similar to alkyl groups, alkoxy groups, aryl groups, aryloxy groups, and halogen atoms in the above.

[0081] In equation (5), R 22 ~R 25 They are mutually independent and therefore may be identical or different from one another.

[0082] In equation (5), R 22 ~R 25 Of these, alkyl groups, alkoxy groups, and hydrogen atoms are preferred, more preferably alkyl groups and hydrogen atoms, and particularly preferably methyl groups.

[0083] In equation (6), R 26 ~R 31 Among these, alkyl groups, alkoxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, arylthiocarbonyl groups, acyloxy groups, arylthio groups, alkylthio groups, aryl groups, heterocyclic hydrocarbon groups, aryloxy groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, hydroxy(poly)alkyleneoxy groups, substituted silyl groups, substituted amino groups, and halogen atoms are, in formula (3), R 6 ~R 9This is the same as alkyl groups, alkoxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, arylthiocarbonyl groups, acyloxy groups, arylthio groups, alkylthio groups, aryl groups, heterocyclic hydrocarbon groups, aryloxy groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, hydroxy(poly)alkyleneoxy groups, silyl groups that may be substituted, amino groups that may be substituted, and halogen atoms.

[0084] In equation (6), R 26 ~R 31 They are mutually independent and therefore may be identical or different from one another.

[0085] In equation (6), R 26 ~R 31 Of these, alkyl groups and alkoxy groups are preferred, more preferably methyl groups, tert-butyl groups and methoxy groups, and particularly preferred methyl groups and tert-butyl groups.

[0086] In equation (6), m21 to m26 are R 26 ~R 31 The numbers represent the values ​​of the integers, where m21 and m24 are integers from 0 to 4, m22 and m25 are integers from 0 to 3, and m21, m24, m22, and m25 are preferably from 0 to 2. m23 is an integer from 0 to 4, preferably from 0 to 2, more preferably 0 or 2, and particularly preferably 2. m26 is an integer from 0 to 5, preferably from 0 to 2, more preferably 0 or 2, and particularly preferably 2.

[0087] 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.

[0088] If other photoacid generators are included, the content (mol%) of the other photoacid generators is preferably 0.1 to 100, and more preferably 0.5 to 50, relative to the total number of moles of the sulfonylimide salt compound represented by general formula (1) of the present invention.

[0089] Other photoacid generators include conventionally known ones such as onium salts (sulfonium, iodonium, selenium, ammonium, and phosphonium, etc.) and salts of transition metal complex ions with anions.

[0090] When using the photoacid generator of the present invention, it may be dissolved in a solvent that does not inhibit polymerization, crosslinking, deprotection reactions, etc., in order to facilitate dissolution in cationic polymerizable compounds and chemically amplified resist compositions.

[0091] 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 monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether of dipropylene glycol monoacetate; and dioxane. Examples include 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.

[0092] When using a solvent, the solvent is preferably used in an amount of 15 to 1000 parts by weight, and more preferably 30 to 500 parts by weight, per 100 parts by weight of the photoacid generator containing the sulfonyliimide salt compound of the present invention. The solvent used may be used alone or in combination of two or more types.

[0093] The energy ray curable composition of the present invention comprises the above-mentioned photoacid generator and a cationic polymerizable compound.

[0094] Cationic polymerizable compounds that are components of energy-ray curable compositions include cyclic ethers (epoxides and oxetanes, etc.), ethylenically unsaturated compounds (vinyl ethers and styrenes, etc.), bicyclo-orthoesters, spiro-orthocarbonates, and spiro-orthoesters {Japanese Patent Publication No. 11-060996, Japanese Patent Publication No. 09-302269, Japanese Patent Publication No. 2003-026993, etc.}.

[0095] As epoxides, known types can be used, and include aromatic epoxides, alicyclic epoxides, and aliphatic epoxides.

[0096] Examples of aromatic epoxides include glycidyl ethers of monovalent or polyvalent phenols (phenol, bisphenol A, phenol novolac, and alkylene oxide adducts thereof) having at least one aromatic ring.

[0097] Examples of alicyclic epoxides include compounds obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (e.g., 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate).

[0098] Examples of aliphatic epoxides include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof (e.g., 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether), polyglycidyl esters of aliphatic polybasic acids (e.g., diglycidyl tetrahydrophthalate), and epoxidized products of long-chain unsaturated compounds (e.g., epoxidized soybean oil and epoxidized polybutadiene).

[0099] As the oxetane, known substances can be used, such as 3-ethyl-3-hydroxymethyl oxetane, 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.

[0100] As ethylenically unsaturated compounds, known cationic polymerizable monomers can be used, and include aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrenes, and cationic polymerizable nitrogen-containing monomers.

[0101] Examples of aliphatic monovinyl ethers include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.

[0102] Examples of aromatic monovinyl ethers include 2-phenoxyethyl vinyl ether, phenyl vinyl ether, and p-methoxyphenyl vinyl ether.

[0103] Examples of polyfunctional vinyl ethers include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.

[0104] Examples of styrenes include styrene, α-methylstyrene, p-methoxystyrene, and p-tert-butoxystyrene.

[0105] Examples of cationic polymerizable nitrogen-containing monomers include N-vinylcarbazole and N-vinylpyrrolidone.

[0106] Examples of bicyclo-orthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane and 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo-[2.2.2]octane.

[0107] Examples of spiro-oth carbonates include 1,5,7,11-tetraoxaspiro[5.5]undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5.5]undecane.

[0108] Examples of spiroolthoesters 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.

[0109] Furthermore, polyorganosiloxanes having at least one cationic polymerizable group in one molecule can be used (as described in Japanese Patent Publication 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 mixtures thereof.

[0110] Among these cationic polymerizable compounds, epoxides, oxetanes, and vinyl ethers are preferred, more preferably epoxides and oxetanes, and particularly preferably alicyclic epoxides and oxetanes. These cationic polymerizable compounds may be used individually or in combination of two or more.

[0111] The amount 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 cationic polymerizable compound. Within this range, polymerization of the cationic polymerizable compound becomes even more sufficient, and the physical properties of the cured product become even better. This amount is determined by considering various factors such as the properties of the cationic polymerizable compound, the type and amount of energy rays, temperature, curing time, humidity, and thickness of the coating film, and is not limited to the above range.

[0112] The energy ray curable composition of the present invention may optionally contain known additives (such as sensitizers, pigments, fillers, antistatic agents, flame retardants, defoamers, flow regulators, light stabilizers, antioxidants, adhesion promoters, ion scavenging agents, color inhibitors, solvents, non-reactive resins, and radical polymerizable compounds).

[0113] As sensitizers, publicly known sensitizers (such as those described in Japanese Patent Publication No. 11-279212 and Japanese Patent Publication No. 09-183960) can be used, including 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; tetrapropyl alcohol Tracene; Coronene; Thioxanthones {thioxanthones, 2-methylthioxanthones, 2-ethylthioxanthones, 2-chlorothioxanthones, 2-isopropylthioxanthones and 2,4-diethylthioxanthones, etc.}; Phenothiazines {phenothiazines, N-methylphenothiazines, N-ethylphenothiazines, N-phenylphenothiazines, etc.}; Xanthones; Naphthalenes {1-naphthol, 2-naphthol, 1-methylthioxanthones} Examples include toxiconaphthalene, 2-methoxynaphthalene, 1,4-dihydroxynaphthalene, and 4-methoxy-1-naphthol; ketones (dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, and 4-benzoyl-4'-methyldiphenyl sulfide); carbazoles (N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole, and N-glycidylcarbazole); chrysenes (1,4-dimethoxychrysene and 1,4-di-α-methylbenzyloxychrysene); and phenanthrenes (9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, and 9-hydroxy-10-ethoxyphenanthrene).

[0114] If a sensitizer is included, the amount of 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.

[0115] As pigments, known pigments can be used, including inorganic pigments (titanium dioxide, iron oxide, and carbon black, etc.) and organic pigments (azo pigments, cyanine pigments, phthalocyanine pigments, and quinacridone pigments, etc.).

[0116] If a pigment is included, the pigment content 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.

[0117] As fillers, known fillers can be used, including fused silica, crystalline silica, calcium carbonate, aluminum oxide, aluminum hydroxide, zirconium oxide, magnesium carbonate, mica, talc, calcium silicate, and lithium aluminum silicate.

[0118] If a filler is included, the filler content 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.

[0119] As antistatic agents, known antistatic agents can be used, including nonionic antistatic agents, anionic antistatic agents, cationic antistatic agents, amphoteric antistatic agents, and polymeric antistatic agents.

[0120] If an antistatic agent is included, the amount 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.

[0121] As flame retardants, 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, and calcium aluminate, etc.}; bromine flame retardants {tetrabromophthalic anhydride, hexabromobenzene, and decabromoviphenyl ether, etc.}; and phosphate ester flame retardants {tris(tribromophenyl) phosphate, etc.}.

[0122] If a flame retardant is included, the amount 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.

[0123] As defoaming agents, 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.

[0124] As flow modifiers, known flow modifiers can be used, including hydrogenated castor oil, polyethylene oxide, organic bentonite, colloidal silica, amide wax, metal soap, and acrylic acid ester polymers. As light stabilizers, known light stabilizers can be used, including ultraviolet absorbing stabilizers {benzotriazole, benzophenone, salicylate, cyanoacrylate and their derivatives, etc.}; radical scavenging stabilizers {hindered amines, etc.}; and quenching stabilizers {nickel complexes, etc.}. As antioxidants, known antioxidants can be used, including phenolic antioxidants (monophenolic, bisphenolic, and polymeric phenolic, etc.), sulfur-based antioxidants, and phosphorus-based antioxidants. As adhesion-improving agents, known adhesion-improving agents can be used, including coupling agents, silane coupling agents, and titanium coupling agents. As ion scavengers, known ion scavengers can be used, such as organoaluminum (alkoxyaluminum and phenoxyaluminum, etc.). As a color inhibitor, known color inhibitors can be used, and generally antioxidants are effective. Examples include phenolic antioxidants (monophenolic, bisphenolic, and polymeric phenolic, etc.), sulfur-based antioxidants, and phosphorus-based antioxidants. However, these have little effect in preventing coloring during heat resistance tests at high temperatures.

[0125] When the present invention contains an antifoaming agent, a flow regulator, a light stabilizer, an antioxidant, an adhesion promoter, an ion scavenger, or a color inhibitor, the amount 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.

[0126] As a solvent, there are no restrictions as long as it can be used for dissolving cationic polymerizable compounds or adjusting the viscosity of energy ray curable compositions; those listed above as solvents for photoacid generators can be used.

[0127] If a solvent is present, the solvent content 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.

[0128] Examples of non-reactive resins include polyester, polyvinyl acetate, polyvinyl chloride, polybutadiene, polycarbonate, polystyrene, polyvinyl ether, polyvinyl butyral, polybutene, styrene-butadiene block copolymer hydrogenation, copolymers of (meth)acrylic acid esters, and polyurethane. The number-average molecular weight of these resins is preferably 1,000 to 500,000, more preferably 5,000 to 100,000 (the number-average molecular weight is a value measured by a general method such as GPC).

[0129] If a non-reactive resin is included, the amount of 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.

[0130] When including a non-reactive resin, it is desirable to dissolve the non-reactive resin in a solvent beforehand to facilitate its dissolution with cationic polymerizable compounds, etc.

[0131] As radical polymerizable compounds, publicly known radical polymerizable compounds such as those listed in "Photopolymer Handbook" (1989, Kogyo Chosakai) edited by the Photopolymer Discussion Group, "UV / EB Curing Technology" (1982, Kogyo Chosakai) edited by the Comprehensive Technology Center, and "UV / EB Curing Materials" (1992, CMC) edited by the Radtech Research Group can be used, and include monofunctional monomers, difunctional monomers, polyfunctional monomers, epoxy (meth)acrylates, polyester (meth)acrylates, and urethane (meth)acrylates.

[0132] When a radical polymerizable compound is included, the amount of the radical 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.

[0133] When a radical polymerizable compound is included, it is preferable to use a radical polymerization initiator that initiates polymerization by heat or light in order to increase the molecular weight of these compounds by radical polymerization.

[0134] Known radical polymerization initiators can be used, including thermal radical polymerization initiators (organic peroxides, azo compounds, etc.) and photoradical polymerization initiators (acetophenone initiators, benzophenone initiators, Michler ketone initiators, benzoin initiators, thioxanthone initiators, acylphosphine initiators, etc.).

[0135] If a radical polymerization initiator is included, the amount of 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.

[0136] The energy ray curable composition of the present invention can be prepared by uniformly mixing and dissolving a cationic polymerizable compound, a photoacid generator, and optionally additives at room temperature (approximately 20-30°C) or, if necessary, by heating (approximately 40-90°C), or by further kneading with a three-roll mill or the like.

[0137] The energy-ray curable composition of the present invention can be cured by irradiation with energy rays to obtain a cured body. Any energy ray may be used as long as it has the energy to induce the decomposition of the photoacid generator of the present invention, but energy rays in the ultraviolet to visible light region (wavelength: approximately 100 to approximately 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, or F2 lasers are preferred. High-energy radiation such as electron beams or X-rays can also be used as the energy ray.

[0138] The irradiation time for energy rays is affected by the intensity of the energy rays and the permeability of the energy rays to the energy ray-curable composition, but 0.1 to 10 seconds at room temperature (around 20-30°C) is usually sufficient. However, if the permeability of the energy rays is low or if the film thickness of the energy ray-curable composition is thick, it may be preferable to irradiate for a longer time. If necessary, after irradiation with energy rays, the material may be heated at room temperature (around 20-30°C) to 200°C for several seconds to several hours for after curing.

[0139] Specific applications of the energy-ray curable composition of the present invention include paints, coatings, various coating materials (hard coats, stain-resistant coatings, anti-fogging coatings, corrosion-resistant coatings, optical fibers, etc.), back treatment agents for adhesive tapes, release coatings for release sheets for adhesive labels (release paper, release plastic film, release metal foil, etc.), printing plates, dental materials (dental compounding, 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, and negative resists (permanent film materials such as surface protective films, interlayer insulating films, and planarization films for semiconductor elements, etc.). Examples include resists for MEMS, positive-type photosensitive materials, negative-type photosensitive materials, various adhesives (temporary fixing agents for various electronic components, adhesives for HDDs, adhesives for pickup lenses, adhesives for functional films for FPDs (polarizing plates, anti-reflective coatings, etc.)), holographic resins, FPD materials (color filters, black matrices, partition materials, photospacers, ribs, alignment films for liquid crystals, sealants for FPDs, etc.), optical components, molding materials (for building materials, optical components, lenses), casting materials, putties, glass fiber impregnating agents, sealing materials, encapsulating materials, optoelectronic semiconductor (LED) encapsulating materials, optical waveguide materials, nanoimprint materials, materials for stereolithography, and materials for micro-stereolithography.

[0140] Since the photoacid generator of the present invention generates a strong acid upon light irradiation, it can also be used as a photoacid generator for chemically amplified resist materials, as is known (Japanese Patent Publication No. 2003-267968, Japanese Patent Publication No. 2003-261529, Japanese Patent Publication No. 2002-193925, etc.).

[0141] Chemically amplified resist materials include: (1) a two-component chemically amplified positive resist comprising a resin that becomes soluble in an alkaline developer by the action of an acid and a photoacid generator as essential components; (2) a three-component chemically amplified positive resist comprising a resin soluble in an alkaline developer, a dissolution inhibitor that becomes soluble in an alkaline developer by the action of an acid and a photoacid generator as essential components; and (3) a chemically amplified negative resist comprising a resin soluble in an alkaline developer, a crosslinking agent that crosslinks the resin and makes it insoluble in an alkaline developer by heat treatment in the presence of an acid and a photoacid generator as essential components.

[0142] The chemically amplified positive-type photoresist composition of the present invention is characterized by containing a component (A) comprising the photoacid generator of the present invention, which is a compound that generates acid upon irradiation with light or radiation, and a resin component (B) whose solubility in alkali is increased by the action of the acid.

[0143] In the chemically amplified positive-type 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, sulfonic acid ester compounds, sulfonimide compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oximesulfonate compounds, hydrazine sulfonate compounds, triazine compounds, nitrobenzyl compounds, as well as organic halides, disulfones, and the like.

[0144] As other conventionally known photoacid generators, one or more of the following are preferred: onium compounds, sulfonimide compounds, diazomethane compounds, and oximesulfonate compounds.

[0145] When using other conventionally known photoacid generators in combination, the proportion of use is arbitrary, but typically, the other photoacid generator is used in proportion to 100 parts by weight of the total sulfonylimide salt compound represented by the general formula (1) above, with a ratio of 10 to 900 parts by weight, preferably 25 to 400 parts by weight.

[0146] The content of component (A) is preferably 0.05 to 5% by weight of the solid content of the chemically amplified positive photoresist composition.

[0147] <Resin component (B) whose solubility in alkali increases due to the action of acid> The "resin (B) whose solubility in alkali increases by the action of an acid" (hereinafter referred to 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 novolac resin (B1), polyhydroxystyrene resin (B2), and acrylic resin (B3), or a mixture of these resins or copolymers.

[0148] [Novolac resin (B1)] As the novolac resin (B1), a resin represented by the following general formula (b1) can be used.

[0149] [ka]

[0150] In formula (b1), R 1b R represents an acid dissociation inhibitory group. 2b , R 3b Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents the number of repeating units in the structure within the parentheses.

[0151] Furthermore, the above R 1b Preferred acid-dissociation-inhibiting groups represented by are linear alkyl groups having 1 to 6 carbon atoms, branched alkyl groups having 3 to 6 carbon atoms, cyclic alkyl groups having 3 to 6 carbon atoms, tetrahydropyranyl groups, tetrahydrofuranyl groups, or trialkylsilyl groups.

[0152] Here, the above R 1b Specific examples of acid-dissociative dissolution inhibitory groups represented by include methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, isobutoxyethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methylethyl group, 1-ethoxy-1-methylethyl group, tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, trimethylsilyl group, and tri-tert-butyldimethylsilyl group.

[0153] [Polyhydroxystyrene resin (B2)] As the polyhydroxystyrene resin (B2), the resin represented by the following general formula (b2) can be used.

[0154] [ka]

[0155] In formula (b2), R 4b R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 5b represents an acid-dissociation-inhibiting group, and n represents the number of repeating units of the structure in parentheses.

[0156] The above C1-C6 alkyl groups are linear alkyl groups having C1-C6, branched alkyl groups having C3-C6, or cyclic alkyl groups having C3-C6. Examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl groups. Examples of cyclic alkyl groups include cyclopentyl and cyclohexyl groups.

[0157] The above R 5b The acid dissociation inhibitory group represented by the above R is 1b An acid-dissociation-inhibiting group similar to that exemplified can be used.

[0158] Furthermore, polyhydroxystyrene resin (B2) may contain other polymerizable compounds as constituent units for the purpose of appropriately controlling its physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anionic polymerizable compounds. For example, monocarboxylic acids such as acrylic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having carboxyl groups and ester bonds such as 2-methacryloyloxyethyl succinic acid; alkyl (meth)acrylate esters such as methyl (meth)acrylate; hydroxyalkyl (meth)acrylate 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.

[0159] [Acrylic resin (B3)] As the acrylic resin (B3), resins represented by the following general formulas (b3) to (b8) can be used.

[0160] [ka]

[0161] [ka]

[0162] In formulas (b3) to (b5), R 6b ~R 13b Each of these independently represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a fluorine atom, 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 bIt forms a hydrocarbon ring with 5 to 20 carbon atoms together with the carbon atoms to which it is bonded, Y b represents an aliphatic cyclic group or alkyl group which may have substituents, n represents the number of repeating units of the structure in parentheses, p is an integer from 0 to 4, and q is 0 or 1.

[0163] In equations (b6) to (b8), R 14b ~R 17b R independently represents a hydrogen atom or a methyl group, and in formula (b6), each R 15b These are independently of each other: a hydrogen atom, a hydroxyl group, a cyano group, or COOR 19b Base (however, R 19b R 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. ) represents, and in formula (b8), each R 18b Each of these independently represents 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 R 18b At least one of them is the alicyclic hydrocarbon group or a derivative thereof, or any two of R 18b These atoms bond to each other, and together with the common carbon atom to which they are bonded, they form a divalent alicyclic hydrocarbon group with 4 to 20 carbon atoms or a derivative thereof, and the remaining R 18b This represents a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 to 4 carbon atoms, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a derivative thereof.

[0164] Among the above components (B), it is preferable to use acrylic resin (B3).

[0165] 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 using such a weight-average molecular weight, the resin properties of the resist become excellent.

[0166] Furthermore, component (B) is preferably a resin with a dispersion degree of 1.05 or higher. Here, "dispersion degree" refers to the value obtained by dividing the weight-average molecular weight by the number-average molecular weight. By achieving such a dispersion degree, the resist will have excellent plating resistance and resin properties.

[0167] The content of component (B) is preferably 5 to 60% by weight of the solid content of the chemically amplified positive photoresist composition.

[0168] <Alkali-soluble resin (C)> The chemically amplified positive photoresist composition of the present invention preferably further contains an alkali-soluble resin (hereinafter referred to as "component (C)") in order to improve the resin properties of the resist. Component (C) is preferably at least one selected from the group consisting of novolac resin, polyhydroxystyrene resin, acrylic resin, and polyvinyl resin.

[0169] 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.

[0170] <Acid diffusion control agent (D)> The chemically amplified positive photoresist composition of the present invention preferably further contains an acid diffusion control agent (D) (hereinafter referred to as "component (D)") in order to improve the resist pattern shape, settling stability, etc. Component (D) is preferably a nitrogen-containing compound, and may further optionally contain an organic carboxylic acid, a phosphorus oxoacid, or a derivative thereof.

[0171] Furthermore, the chemically amplified positive-type photoresist composition of the present invention may further contain an adhesion aid to improve adhesion to the substrate. A functional silane coupling agent is preferred as the adhesion aid used.

[0172] Furthermore, the chemically amplified positive-type photoresist composition of the present invention may further contain a surfactant to improve the coatability, defoaming properties, leveling properties, and other characteristics.

[0173] Furthermore, the chemically amplified positive photoresist composition of the present invention may further contain an acid, an acid anhydride, or a high-boiling point solvent in order to fine-tune its solubility in an alkaline developer.

[0174] Furthermore, while the chemically amplified positive photoresist composition of the present invention does not fundamentally require a sensitizer, a sensitizer may be included as needed to complement the sensitivity. Conventionally known sensitizers can be used, and the aforementioned examples are specific.

[0175] 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 sulfonylimid salt compound represented by the general formula (1) above.

[0176] Furthermore, the chemically amplified positive-type photoresist composition of the present invention may contain organic solvents as appropriate for viscosity adjustment. Specific examples of organic solvents include those mentioned above.

[0177] The amount of these organic solvents used is preferably in a range where the solid content concentration is 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 (for example, by spin coating) is 5 μm or more.

[0178] The chemically amplified positive photoresist composition of the present invention can be prepared, for example, by simply mixing and stirring the above components in a conventional manner. If necessary, the components may be dispersed and mixed using a disperser such as a dissolver, homogenizer, or three-roll mill. After mixing, the mixture may be further filtered using a mesh, membrane filter, or the like.

[0179] The chemically amplified positive-type photoresist composition of the present invention is suitable for forming a photoresist layer on a support with a film thickness of typically 5 to 150 μm, more preferably 10 to 120 μm, and even more preferably 10 to 100 μm. This photoresist laminate is formed by laminating a photoresist layer made of the chemically amplified positive-type photoresist composition of the present invention on a support.

[0180] The support material is not particularly limited and conventionally known materials can be used, for example, substrates for electronic components or substrates on which a predetermined wiring pattern has been 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 resist pattern well even on a copper substrate. Examples of materials used for the wiring pattern include copper, solder, chromium, aluminum, nickel, and gold.

[0181] The above-mentioned photoresist laminate can be manufactured, for example, as follows: A solution of the chemically amplified positive-type photoresist composition prepared as described above is applied to a support, and the solvent is removed by heating to form the desired coating film. Methods such as spin coating, slit coating, roll coating, screen printing, and applicator coating can be used for coating the support. The pre-bake 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 usually 70 to 150°C, preferably 80 to 140°C, for about 2 to 60 minutes.

[0182] The film thickness of the photoresist layer is usually in the range of 5 to 150 μm, preferably 10 to 120 μm, and more preferably 10 to 100 μm.

[0183] To form a resist pattern using the thus obtained photoresist laminate, the obtained photoresist layer may be selectively irradiated (exposed) with light or radiation, such as ultraviolet light or visible light having a wavelength of 300 to 500 nm, through a mask having a predetermined pattern.

[0184] Here, the “light” may be any light that activates the photoacid generator to generate an acid, including ultraviolet light, visible light, and far ultraviolet light, and the “radiation” means X-rays, electron beams, ion beams, etc. As the source of light or radiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, an LED lamp, etc. can be used. Also, the radiation exposure dose varies depending on the type and blending amount of each component in the composition, the film thickness of the coating film, etc. For example, when using an ultra-high-pressure mercury lamp, it is 50 to 10,000 mJ / cm 2 is.

[0185] After exposure, heating is performed using a known method to promote the diffusion of the acid and change the alkali solubility of the photoresist layer in the exposed portion. Then, for example, using a predetermined alkaline aqueous solution as a developer, unnecessary portions are dissolved and removed to obtain a predetermined resist pattern.

[0186] The development time varies depending on the type and blending ratio of each component of the composition and the dry film thickness of the composition, but is usually 1 to 30 minutes. Also, the development method may be any of the puddle method, dipping method, paddle method, spray development method, etc. After development, running water washing is performed for 30 to 90 seconds, and drying is performed using an air gun, an oven, etc.

[0187] By embedding a conductor such as metal in the non-resist portion (the portion removed by the alkaline developer) of the resist pattern obtained in this way, for example by plating, connection terminals such as metal posts and bumps can be formed. The plating method is not particularly limited, and various conventionally known methods can be used. Solder plating, copper plating, gold plating, and nickel plating solutions are particularly suitable as plating solutions. Finally, the remaining resist pattern is removed using a stripping solution or the like according to a standard procedure.

[0188] The chemically amplified positive photoresist composition of the present invention can also be used as a dry film. This dry film has protective films formed on both sides of a layer made of the chemically amplified positive photoresist composition of the present invention. The thickness of the layer made of the chemically amplified positive photoresist composition is usually in the range of 10 to 150 μm, preferably 20 to 120 μm, and more preferably 20 to 80 μm. Furthermore, the protective film is not particularly limited, and resin films conventionally used for dry films can be used. For example, one side can be a polyethylene terephthalate film, and the other side can be one selected from the group consisting of polyethylene terephthalate film, polypropylene film, and polyethylene film.

[0189] The chemically amplified positive-type dry film described above can be manufactured, for example, as follows: A solution of the chemically amplified positive-type photoresist composition prepared as described above is applied to one protective film, and the solvent is removed by heating to form the desired coating. The drying conditions vary depending on the type and proportion of each component in the composition, the coating thickness, etc., but usually 60 to 100°C for about 5 to 20 minutes is sufficient.

[0190] To form a resist pattern using the chemically amplified dry film obtained in this way, one protective film of the chemically amplified positive dry film is peeled off, and the exposed surface is laminated onto the support with the support facing the support side to obtain a photoresist layer. After that, the resist is dried by pre-baking, and then the other protective film is peeled off.

[0191] A resist pattern can be formed on the photoresist layer obtained on the support in this manner, using the same method as described above for a photoresist layer formed by direct coating onto the support.

[0192] The chemically amplified negative photoresist composition of the present invention is characterized by containing a component (E) comprising the photoacid generator of the present invention, which is a compound that generates acid upon irradiation with light or radiation, an alkali-soluble resin (F) having a phenolic hydroxyl group, and a crosslinking agent (G).

[0193] Alkali-soluble resin (F) having phenolic hydroxyl groups In the present invention, examples of "alkali-soluble resin having phenolic hydroxyl groups" (hereinafter referred to as "phenol resin (F)") include novolac resin, polyhydroxystyrene, copolymers of polyhydroxystyrene, copolymers of hydroxystyrene and styrene, copolymers of hydroxystyrene, styrene and (meth)acrylic acid derivatives, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, and phenol-dicyclopentadiene condensation resin. Among these, novolac resin, polyhydroxystyrene, copolymers of polyhydroxystyrene, copolymers of hydroxystyrene and styrene, copolymers of hydroxystyrene, styrene and (meth)acrylic acid derivatives, and phenol-xylylene glycol condensation resin are preferred. These phenol resins (F) may be used individually or as a mixture of two or more.

[0194] Furthermore, the phenolic resin (F) may contain a phenolic low-molecular-weight compound as part of its components. Examples of the above-mentioned phenolic low molecular weight compounds include 4,4'-dihydroxydiphenylmethane and 4,4'-dihydroxydiphenyl ether.

[0195] Crosslinking agent (G) The "crosslinking agent" in the present invention (hereinafter also referred to as "crosslinking agent (G)") is not particularly limited as long as it acts as a crosslinking component (curing component) that reacts with the phenol 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 benzenes as a backbone in the molecule, oxirane ring-containing compounds, thiirane ring-containing compounds, oxetanyl group-containing compounds, isocyanate group-containing compounds (including blocked ones), and the like.

[0196] 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 compounds having at least two alkyl etherified amino groups in the molecule and oxirane ring-containing compounds in combination.

[0197] The amount of crosslinking agent (G) in the present invention is preferably 1 to 100 parts by weight, and more preferably 5 to 50 parts by weight, per 100 parts by weight of the phenolic resin (F). When the amount of 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 good pattern shape, and is preferable because it has excellent heat resistance and electrical insulation properties. Furthermore, when using a compound having an alkyl etherified amino group and an oxirane ring-containing compound in combination, the content of the oxirane ring-containing compound is preferably 50% by weight or less, more preferably 5 to 40% by weight, and particularly preferably 5 to 30% by weight, when the total of the compound having an alkyl etherified amino group and the oxirane ring-containing compound is taken as 100% by weight. In this case, the resulting cured film is preferable because it exhibits excellent chemical resistance without compromising high resolution.

[0198] 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.

[0199] The average particle size of the crosslinked fine particles (H) is typically 30 to 500 nm, preferably 40 to 200 nm, and more preferably 50 to 120 nm. The method for controlling the particle size of these cross-linked microparticles (H) is not particularly limited, but for example, when synthesizing cross-linked microparticles by emulsion polymerization, the particle size can be controlled by controlling the number of micelles during emulsion polymerization by controlling the amount of emulsifier used. Furthermore, the average particle size of the cross-linked microparticles (H) is the value measured by diluting the dispersion of cross-linked microparticles according to a standard method using a light scattering flow distribution measuring device or the like.

[0200] The amount of crosslinked fine particles (H) 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) is 0.5 to 50 parts by weight, the compatibility and dispersibility with other components are excellent, and the thermal shock resistance and heat resistance of the resulting cured film can be improved.

[0201] Adhesion enhancer Furthermore, the chemically amplified negative photoresist composition of the present invention may contain an adhesion aid to improve adhesion to the substrate. Examples of the adhesion promoter include functional silane coupling agents having reactive substituents such as carboxyl group, methacryloyl group, isocyanate group, epoxy group, etc.

[0202] The blending amount of the adhesion promoter is preferably 0.2 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the phenolic resin (F). When the blending amount of this adhesion promoter is 0.2 to 10 parts by weight, it is preferable because it has excellent storage stability and can obtain good adhesion.

[0203] Solvent In addition, the chemically amplified negative photoresist composition of the present invention can contain a solvent in order to improve the handleability of the resin composition or to adjust the viscosity and storage stability. The above solvent is not particularly limited, and specific examples include those described above.

[0204] In addition, the chemically amplified negative photoresist composition of the present invention can contain a sensitizer if necessary. As such a sensitizer, conventionally known ones can be used, and specifically, those described above can be mentioned.

[0205] The amount of these sensitizers used is 5 to 500 parts by weight, preferably 10 to 300 parts by weight, based on 100 parts by weight of the total weight of the sulfonylimide salt compound represented by the above general formula (1).

[0206] In addition, the chemically amplified negative photoresist composition of the present invention can contain other additives to such an extent that the properties of the present invention are not impaired, if necessary. Examples of such other additives include inorganic fillers, quenchers, leveling agents / surfactants, etc.

[0207] The method for preparing the chemically amplified negative photoresist composition of the present invention is not particularly limited, and it can be prepared by a known method. Also, it can be prepared by putting each component into a sample bottle with a complete stopper and stirring it on a wave rotor.

[0208] The cured product in the present invention is characterized by being obtained by curing the chemically amplified negative-type photoresist composition. The chemically amplified negative photoresist composition according to the present invention, as described above, has a high residual film rate and excellent resolution, and its cured product has excellent electrical insulation and thermal shock resistance. Therefore, its cured product can be suitably used as a surface protective film, planarization film, interlayer insulating film material, etc., for electronic components such as semiconductor elements and semiconductor packages.

[0209] To form the cured product of the present invention, first, the chemically amplified negative photoresist composition according to the present invention described above is coated onto a support (such as resin-coated copper foil, copper-clad laminate, silicon wafer or alumina substrate with a metal sputtered film attached), and dried to evaporate the solvent and other substances to form a coating film. Then, exposure is performed through a desired mask pattern, and a heat treatment (hereinafter referred to as "PEB") is performed to promote the reaction between the phenolic resin (F) and the crosslinking agent (G). Next, the film is developed with an alkaline developer to dissolve and remove the unexposed areas, thereby obtaining the desired pattern. Furthermore, a heat treatment is performed to exhibit insulating film properties, thereby obtaining a cured film.

[0210] For example, coating methods such as dipping, spraying, bar coating, roll coating, or spin coating can be used to apply the resin composition to a support. The thickness of the coated film can be appropriately controlled by adjusting the coating means, the solid content concentration, and the viscosity of the composition solution. Examples of radiation used for exposure include ultraviolet rays and electron beams from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-ray steppers, h-ray steppers, i-ray steppers, gh-ray steppers, and ghi-ray steppers, as well as laser beams. The exposure dose is selected appropriately depending on the light source used and the resin thickness, but for example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the exposure dose is 100 to 50,000 J / m for a resin thickness of 1 to 50 μm. 2 It is to that extent.

[0211] After exposure, the above-mentioned PEB treatment is performed to promote the curing reaction between the phenolic resin (F) and the crosslinking agent (G) due to the generated acid. The PEB conditions vary depending on the amount of resin composition used and the film thickness used, but are usually 70 to 150°C, preferably 80 to 120°C, for about 1 to 60 minutes. After that, the desired pattern is formed by developing with an alkaline developer to dissolve and remove the unexposed areas. In this case, development methods include shower development, spray development, immersion development, and paddle development. The development conditions are usually 20 to 40°C for about 1 to 10 minutes.

[0212] Furthermore, to fully develop its insulating film properties after development, the material can be sufficiently cured by heat treatment. While there are no particular limitations on these 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 material. Alternatively, heating can be performed in two stages to ensure sufficient curing and prevent deformation of the resulting pattern shape. For example, in the first stage, the material can be heated at a temperature of 50 to 120°C for approximately 5 minutes to 2 hours, followed by further heating at a temperature of 80 to 250°C for approximately 10 minutes to 10 hours. Under these curing conditions, general ovens or infrared furnaces can be used as heating equipment. [Examples]

[0213] The present invention will be further described below with reference to examples, but the present invention is not intended to be limited thereto. Unless otherwise specified below, parts refer to parts by weight, and % refers to % by weight.

[0214] (Synthesis Example 1) Synthesis of photoacid generator (a1) 2.1 parts of (2-methoxyphenyl)phenyl sulfoxide, 2.0 parts of (2-methoxyphenyl)phenyl sulfide, and 23.3 parts of methanesulfonic acid were charged, and 2.8 parts of acetic anhydride were added dropwise at room temperature. The mixture was then stirred at 60°C for 6 hours, and after the reaction solution was cooled to room temperature, it was added to 200 parts of deionized water and extracted with 100 parts of dichloromethane. The aqueous layer was washed with deionized water until the pH became neutral. Next, under stirring, 1.8 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer, and the mixture was stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with deionized water by liquid-liquid extraction, and the solvent was removed by distillation in a rotary evaporator to obtain a1. The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0215] [ka]

[0216] (Synthesis Example 2) Synthesis of photoacid generator (a2) 89.0 parts of a dichloromethane solution containing 32.0 parts of (4-phenylthio)phenyldiphenylsulfonium trifluoromethanesulfonate were added dropwise to a suspension of 36.8 parts aluminum chloride, 12.0 parts acetyl chloride, and 200 parts dichloromethane under stirring and cooling conditions, ensuring the system temperature did not exceed 10°C. After the addition was complete, the mixture was stirred at room temperature for 2 hours, and the reaction solution was added to 300 parts of cold water under stirring conditions. The upper layer was removed, and the dichloromethane layer was washed with deionized water until the pH of the aqueous layer became neutral. Then, under stirring conditions, 12.1 parts of lithium bis(fluorosulfonyl)imide were added to the dichloromethane layer, and the mixture was stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with deionized water by liquid-liquid separation, and the solvent was removed by distillation in a rotary evaporator to obtain a2. The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0217] [ka]

[0218] (Synthesis Example 3) Synthesis of photoacid generator (a3) a3 was obtained in the same manner as in Example 4, except that 12.0 parts of acetyl chloride were replaced with 19.4 parts of benzyl chloride. The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0219] [ka]

[0220] (Synthesis Example 4) Synthesis of photoacid generator (a4) 1.1 parts of 4-[(phenyl)sulfinyl]biphenyl, 1.1 parts of 4-(phenylthio)biphenyl, 1.2 parts of acetic anhydride, 0.7 parts of trifluoromethanesulfonic acid, and 6.5 parts of acetonitrile were charged and stirred at 60°C for 2 hours. The reaction solution was cooled to room temperature, added to 30 parts of deionized water, extracted with 30 parts of dichloromethane, and washed with deionized water until the pH of the aqueous layer became neutral. Next, under stirring, 0.8 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer and stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with deionized water by liquid-liquid extraction and transferred to a rotary evaporator to remove the solvent by distillation to obtain a4. The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0221] [ka]

[0222] (Synthesis Example 5) Synthesis of photoacid generator (a5) a5 was obtained in the same manner as in Example 4, except that 1.1 parts of 4-[(phenyl)sulfinyl]biphenyl was replaced with 1.3 parts of 4-[(2-tert-butylphenyl)sulfinyl]biphenyl and 1.1 parts of 4-(phenylthio)biphenyl was replaced with 1.5 parts of 4-[(2-tert-butylphenyl)thio]biphenyl. The product was 1 H-NMR, 19Identified by 1F-NMR.

[0223] [ka]

[0224] (Synthesis Example 6) Synthesis of photoacid generator (a6) a6 was obtained in the same manner as in Example 4, except that 1.1 parts of 4-[(phenyl)sulfinyl]biphenyl was replaced with 1.2 parts of 4-[(2-methoxyphenyl)sulfinyl]biphenyl and 1.1 parts of 4-(phenylthio)biphenyl was replaced with 1.3 parts of 4-[(2-methoxyphenyl)thio]biphenyl. The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0225] [ka]

[0226] (Synthesis Example 7) Synthesis of photoacid generator (a7) 0.9 parts of 2-[(phenyl)sulfinyl]fluorene, 1.0 part of 2-(phenylthio)fluorene, 2.0 parts of acetic anhydride, and 1.6 parts of methanesulfonic acid were charged and stirred at 65°C for 3 hours. The reaction solution was cooled to room temperature, added to 5.0 parts of deionized water, extracted with 5.0 parts of dichloromethane, and washed with deionized water until the pH of the aqueous layer became neutral. Next, under stirring, 0.6 parts of lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer and stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with deionized water by liquid-liquid extraction and transferred to a rotary evaporator to remove the solvent by distillation to obtain a7. The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0227] [ka]

[0228] (Synthesis Example 8) Synthesis of photoacid generator (a8) a8 was obtained in the same manner as in Example 7, except that 0.9 parts of 2-[(phenyl)sulfinyl]fluorene were replaced with 1.0 part of 2-[(phenyl)sulfinyl]-9,9-dimethylfluorene and 1.0 part of 2-(phenylthio)fluorene was replaced with 1.1 parts of 2-(phenylthio)-9,9-dimethylfluorene. The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0229] [ka]

[0230] (Synthesis Example 9) Synthesis of photoacid generator (a9) 7.6 parts of acetyl chloride, 15.5 parts of aluminum chloride, and 27.3 parts of dichloromethane were charged and cooled to 5°C under stirring. To this solution, a mixture of 15.0 parts of {4-[2-(9,9-dimethylfluorenyl)thio]phenyl}[2-(9,9-dimethylfluorenyl)]phenylsulfonium methanesulfonate and 27.0 parts of dichloromethane was slowly added dropwise. After stirring for 1 hour, the reaction solution was added to 100 parts of deionized water and washed with deionized water until the pH of the aqueous layer became neutral. Next, under stirring, 3.9 parts of lithium bis(fluorosulfonyl)imide were added to the dichloromethane layer and stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with deionized water by liquid-liquid extraction and transferred to a rotary evaporator to remove the solvent by distillation to obtain a9. The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0231] [ka]

[0232] (Synthesis Example 10) Synthesis of photoacid generator (a10) a10 was obtained in the same manner as in Example 9, except that 7.6 parts of acetyl chloride were replaced with 13.6 parts of benzoyl chloride. The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0233] [ka]

[0234] (Synthesis Example 11) Synthesis of photoacid generator (a11) 4.5 parts of 2-[(phenyl)sulfinyl]thioxanthone, 4.3 parts of 2-(phenylthio)thioxanthone, 4.1 parts of acetic anhydride, and 110 parts of acetonitrile were charged, and 2.4 parts of trifluoromethanesulfonic acid were slowly added dropwise, and the mixture was stirred at 45°C for 1 hour. The reaction solution was cooled to room temperature, added to 150 parts of deionized water, extracted with 50 parts of dichloromethane, and washed with deionized water until the pH of the aqueous layer became neutral. The dichloromethane layer was transferred to a rotary evaporator to remove the solvent, then 50 parts of toluene were added and dispersed in toluene using an ultrasonic cleaner. This process was repeated three times, allowing to stand for 15 minutes and then removing the supernatant, to wash the resulting solid. Next, the solid was dissolved in 50 parts of dichloromethane, 2.7 parts of lithium bis(fluorosulfonyl)imide were added, and the mixture was stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with deionized water by liquid-liquid separation, and the solvent was removed by distillation in a rotary evaporator to obtain a11. The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0235] [ka]

[0236] (Synthesis Example 12) Synthesis of photoacid generator (a12) a12 was obtained in the same manner as in Example 11, except that 4.5 parts of 2-[(phenyl)sulfinyl]thioxanthone were replaced with 4.7 parts of 2-[(3-methylphenyl)sulfinyl]thioxanthone and 4.3 parts of 2-(phenylthio)thioxanthone were replaced with 4.5 parts of 2-[(3-methylphenyl)thio]thioxanthone. The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0237] [ka]

[0238] (Synthesis Example 13) Synthesis of photoacid generator (a13) a13 was obtained in the same manner as in Example 11, except that 4.5 parts of 2-[(phenyl)sulfinyl]thioxanthone were replaced with 5.0 parts of 2-[(3-tert-butylphenyl)sulfinyl]thioxanthone and 4.3 parts of 2-(phenylthio)thioxanthone were replaced with 5.3 parts of 2-[(3-tert-butylphenyl)thio]thioxanthone. The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0239] [ka]

[0240] (Synthesis Example 14) Synthesis of photoacid generator (a14) a14 was obtained in the same manner as in Example 11, except that 4.5 parts of 2-[(phenyl)sulfinyl]thioxanthone were replaced with 4.9 parts of 2-[(3,5-dimethylphenyl)sulfinyl]thioxanthone and 4.3 parts of 2-(phenylthio)thioxanthone were replaced with 4.7 parts of 2-[(3,5-dimethylphenyl)thio]thioxanthone. The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0241] [ka]

[0242] (Synthesis Example 15) Synthesis of photoacid generator (a15) a15 was obtained in the same manner as in Example 11, except that 4.5 parts of 2-[(phenyl)sulfinyl]thioxanthone were replaced with 4.9 parts of 2-[(2,5-dimethylphenyl)sulfinyl]thioxanthone and 4.3 parts of 2-(phenylthio)thioxanthone were replaced with 4.7 parts of 2-[(2,5-dimethylphenyl)thio]thioxanthone. The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0243] [ka]

[0244] (Synthesis Example 16) Synthesis of photoacid generator (a16) a16 was obtained in the same manner as in Example 11, except that 4.5 parts of 2-[(phenyl)sulfinyl]thioxanthone were replaced with 5.4 parts of 2-[(5-tert-butyl-2-methylphenyl)sulfinyl]thioxanthone and 4.3 parts of 2-(phenylthio)thioxanthone were replaced with 5.2 parts of 2-[(5-tert-butyl-2-methylphenyl)thio]thioxanthone. The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0245] [ka]

[0246] (Synthesis Example 17) Synthesis of photoacid generator (a17) Synthesis of 4-[(2-tert-butoxyphenyl)thio]benzophenone 3.0 parts 4-bromobenzophenone, 2.2 parts 2-tert-butoxythiophenol, 1.2 parts potassium hydroxide (85% purity), and 7.0 parts N-methylpyrrolidone were mixed and stirred at 120°C for 1 hour to achieve homogeneous dissolution. The mixture was then reacted at 180°C for 5 hours. After cooling the reaction solution to room temperature (approximately 25°C), 7.0 parts dichloromethane were added and dissolved, and the mixture was washed with 6.5 parts deionized water until the pH was neutral. The dichloromethane layer was transferred to a rotary evaporator to remove the solvent, then 20 parts isopropanol was added and heated to 70°C to achieve homogeneous dissolution. Crystals were then precipitated by cooling to room temperature. The crystals were filtered off to obtain 4-[(2-tert-butoxyphenyl)thio]benzophenone in 65% yield. The product is 1 Identified by 1H-NMR.

[0247] 2.9 parts of synthesized 4-[(2-tert-butoxyphenyl)thio]benzophenone, 10 parts of acetonitrile, 0.04 parts of sulfuric acid, and 0.39 parts of 35% aqueous hydrogen peroxide were homogeneously mixed and reacted at 65°C for 3 hours. The reaction mixture was transferred to a rotary evaporator and the solvent was removed by distillation to obtain a mixture containing 47% 4-[(2-tert-butoxyphenyl)sulfinyl]benzophenone and 53% 4-[(2-tert-butoxyphenyl)thio]benzophenone. The content was calculated from the peak area ratio obtained by HPLC analysis of the mixture. This mixture was dissolved in 15 parts dichloromethane and washed with deionized water until the pH of the aqueous layer became neutral. Then, under stirring, 1.8 parts lithium bis(fluorosulfonyl)imide was added to the dichloromethane layer and stirred at room temperature for 1 hour. The dichloromethane layer was washed three times with deionized water by liquid-liquid extraction and transferred to a rotary evaporator to remove the solvent by distillation to obtain a17. The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0248] [ka]

[0249] (Synthesis Example 18) Synthesis of photoacid generator (a18) a18 was obtained in the same manner as in Synthesis Example 17, except that "2.2 parts of 2-tert-butoxythiophenol" was changed to "1.9 parts of 2-tert-butylthiophenol". The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0250] [ka]

[0251] (Synthesis Example 19) Synthesis of photoacid generator (a19) a19 was obtained in the same manner as in Example 1, except that 2.1 parts of (2-methoxyphenyl)phenyl sulfoxide were replaced with 11.8 parts of diphenyl sulfoxide and 2.0 parts of (2-methoxyphenyl)phenyl sulfide were replaced with 1.7 parts of diphenyl sulfide. The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0252] [ka]

[0253] (Synthesis Example 20) Synthesis of photoacid generator (a20) a20 was obtained in the same manner as in Example 1, except that 2.1 parts of (2-methoxyphenyl)phenyl sulfoxide were replaced with 11.8 parts of diphenyl sulfoxide, 2.0 parts of (2-methoxyphenyl)phenyl sulfide were replaced with 1.7 parts of diphenyl sulfide, and 1.8 parts of lithium bis(fluorosulfonyl)imide were replaced with 1.8 parts of potassium trifluoromethanesulfonate. The product was 1 H-NMR, 19 Identified by 1F-NMR.

[0254] [ka]

[0255] Examples 1-20, Comparative Examples 1-6 [Preparation and evaluation of energy ray-curable compositions] <Preparation of curable composition> Each component listed in Table 1 below was blended according to the blending composition (unit: parts by weight), and a uniform, transparent energy-ray curable composition was obtained by stirring and mixing at room temperature using a rotary-orbit mixer (Examples 1-20, Comparative Examples 1-6). The obtained energy-ray curable compositions were evaluated according to the following evaluation method.

[0256] [Curability] 0.04 mm spacers were placed at both ends of a glass slide, and an energy-ray curable composition was dropped into the center. The adhesive was spread to a thickness of 0.04 mm using a squeegee, and light irradiation was performed using a high-pressure mercury lamp under the following conditions. After light irradiation, the material was heated at 100°C for 5 minutes to obtain a cured product. The tackiness of the surface of the obtained cured material was determined by palpation, and the curability was evaluated according to the following criteria. Evaluation Criteria ○: The surface was not tacky, and there was no change in the surface shape of the hardened material upon palpation. △: The surface does not exhibit tackiness, but the surface shape of the hardened material changed upon palpation. ×: Surface has tackiness <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 (manufactured by Kenko Optical Co., Ltd.) Irradiation intensity (measured with a 365nm illuminometer): 100mW / cm² 2 Cumulative irradiation dose: 1000 mJ / cm² 2

[0257] [Adhesiveness] 0.04mm spacers were placed at both ends of the microscope slide, and adhesive was dripped into the center. Using a squeegee, the adhesive was spread to a thickness of 0.03mm, and an epoxy resin cube (outer diameter: 4mm x 4mm x 1mm, inner diameter: 3.7mm x 3.7mm x 0.8mm, bonding area: 2.3mm) was placed on top. 2 The device was set up, and light irradiation was performed in the same manner as described above. After light irradiation, samples were heated at 100°C for 5 minutes. The adhesion of these samples was evaluated using a die shear tester (product name "4000PXY", manufactured by DAGE) under the following conditions, based on the weight (kgf) at which the epoxy resin cube peeled off. Five samples were prepared, and the average value was used for evaluation. A higher weight indicates better adhesion. Adhesion measurement conditions Share height: 0.65mm Share speed: 500 μm / s

[0258] [Table 1]

[0259] <Cationic polymerizable compounds> Celoxide 2021P: 3,4-Epoxycyclohexylmethyl(3,4-Epoxy)cyclohexanecarboxylate, manufactured by Daicel Corporation. THI-DE: Diepoxylated tetrahydroindene, manufactured by ENEOS Corporation. jER 828: Bisphenol A diglycidyl ether, manufactured by Mitsubishi Chemical Corporation. jER YX8000: Hydrogenated bisphenol A diglycidyl ether, manufactured by Mitsubishi Chemical Corporation. TECHMORE VG3101L: 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-[2,3-epoxypropoxy]phenyl]ethyl]phenyl]propane, manufactured by Printec Co., Ltd. SR-NPG: Neopentyl glycol diglycidyl ether, manufactured by Sakamoto Pharmaceutical Co., Ltd. OXT-121: Xylylene bisoxetane, manufactured by Toagosei Co., Ltd. OXT-221: 3-ethyl-3{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane, manufactured by Toagosei Co., Ltd. X-22-169: End-alligable epoxy-modified silicone oligomer, manufactured by Shin-Etsu Chemical Co., Ltd. Denacol EX-146: p-tert-butylphenylglycidyl ether, manufactured by Nagase ChemteX Corporation. <Photoacid Generator> a1~a20: Compounds obtained in synthesis examples 1~20 <Coupling agent> KBM-403:3-Glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. <Antifoaming agent> BYK-1790: Manufactured by Big Chemie Japan Co., Ltd. <Leveling agent> LS-460: Polyether-modified silicone, manufactured by Kusumoto Kasei Co., Ltd.

[0260] The evaluation results are shown in Table 1. As can be seen from Table 1, the energy ray curable composition of the present invention exhibits excellent curability and thermal stability.

[0261] Examples 21-38, Comparative Examples 7-9 [Evaluation of chemically amplified positive-type photoresist compositions] <Preparation of evaluation samples> As shown in Table 2 below, 1 part by weight of component (A), which is 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 novolac 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), filtered through a membrane filter with a pore size of 1 μm, and chemically amplified positive photoresist compositions (Examples 21-38, Comparative Examples 7-9) with a solid content concentration of 40% by weight were prepared. The prepared chemically amplified positive photoresist compositions were evaluated according to the following evaluation method.

[0262] <Sensitivity Evaluation> Chemically amplified positive resist compositions prepared in Examples 21-38 and Comparative Examples 7-9 were spin-coated onto a silicon wafer substrate, and then dried to obtain a photoresist layer with a thickness of approximately 20 μm. This resist layer was pre-baked on a hot plate at 130°C for 6 minutes. After pre-baking, pattern exposure (i-line) was performed using a TME-150RSC (Topcon Corporation), followed by post-exposure heating (PEB) on a hot plate at 75°C for 5 minutes. Subsequently, development was performed for 5 minutes by immersion using a 2.38 wt% tetramethylammonium hydroxide aqueous solution, followed by washing with running water and blowing with nitrogen to obtain a 10 μm line-and-space (L&S) pattern. Furthermore, the minimum exposure amount below which no residue of this pattern was observed, i.e., the minimum essential exposure amount required to form the resist pattern (corresponding to sensitivity), was measured. A smaller essential exposure amount indicates better photoreactivity of the positive resist composition, i.e., superior photosensitivity of the sulfonylimid salt compound.

[0263] <Storage Stability Assessment> Furthermore, using the chemically amplified positive resist composition prepared above, the photosensitivity (sensitivity) was evaluated immediately after preparation and after storage at 40°C for one month, as described above, and the storage stability was determined according to the following criteria. ○: Sensitivity change after 1 month of storage at 40°C is less than 5% of the sensitivity immediately after preparation. ×: Sensitivity change after 1 month of storage at 40°C is 5% or more of the sensitivity immediately after preparation.

[0264] <Pattern Shape Evaluation> Following the above procedure, the dimensions La at the bottom edge and Lb at the top edge of the cross-section of a 10 μm L&S pattern formed on a silicon wafer substrate were measured using a scanning electron microscope, and the pattern shape was judged 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

[0265] [Table 2]

[0266] [ka]

[0267] [ka]

[0268] The evaluation results are shown in Table 2. As can be seen from Table 2, the chemically amplified positive-type photoresist compositions of Examples 21 to 38 are more sensitive and have better storage stability and pattern shape than those using conventional photoacid generators, as in Comparative Examples 7 to 9.

[0269] Examples 39-56, Comparative Examples 10-12 [Evaluation of chemically amplified negative photoresist compositions] <Preparation of evaluation samples> As shown in Table 3 below, the composition includes 1 part by weight of component (E), which is a photoacid generator; 100 parts by weight of component (F), which is a phenolic resin, consisting of a copolymer (Mw=10,000) with a p-hydroxystyrene / styrene = 80 / 20 (molar ratio); 20 parts by weight of component (G), which is a crosslinking agent, consisting of hexamethoxymethylmelamine (manufactured by Sanwa Chemical Co., Ltd., trade name "Nicalac MW-390"); and component (H), which is a crosslinked fine particle, consisting of butadiene / acrylonitrile / hydroxybutyl methylmelamine. A copolymer consisting of taacrylate / methacrylic acid / divinylbenzene = 64 / 20 / 8 / 6 / 2 (wt%) (average particle size = 65 nm, Tg = -38°C) was uniformly dissolved in 145 wt parts of solvent-2 (ethyl lactate) to prepare the chemically amplified negative photoresist compositions of the present invention (Examples 39-56, Comparative Examples 10-12). The prepared chemically amplified negative photoresist compositions were evaluated according to the following evaluation method.

[0270] <Sensitivity Evaluation> Each composition was spin-coated onto a silicon wafer substrate, and then heated and dried on a hot plate at 110°C for 3 minutes to obtain a resin coating with a thickness of approximately 20 μm. Subsequently, pattern exposure (i-line) was performed using a TME-150RSC (Topcon Corporation), followed by post-exposure heating (PEB) on a hot plate at 110°C for 3 minutes. After that, development was performed for 2 minutes by immersion in a 2.38 wt% tetramethylammonium hydroxide aqueous solution, rinsed with running water, and blown with nitrogen to obtain a 10 μm line and space pattern. Furthermore, the minimum required exposure amount (corresponding to sensitivity) necessary to form a pattern with a residual film rate of 95% or more, which indicates the ratio of residual film before and after development, was measured.

[0271] <Storage Stability Assessment> Furthermore, using the chemically amplified negative resist composition prepared above, the photosensitivity (sensitivity) was evaluated immediately after preparation and after storage at 40°C for one month, as described above, and the storage stability was determined according to the following criteria. ○: Sensitivity change after 1 month of storage at 40°C is less than 5% of the sensitivity immediately after preparation. ×: Sensitivity change after 1 month of storage at 40°C is 5% or more of the sensitivity immediately after preparation.

[0272] <Pattern Shape Evaluation> Following the above procedure, the dimensions La at the bottom edge and Lb at the top edge of the cross-section of a 20 μm L&S pattern formed on a silicon wafer substrate were measured using a scanning electron microscope, and the pattern shape was judged according to the following criteria. The results are shown in Table 6. ◎: 0.90≦La / Lb≦1 ○: 0.85≦La / Lb<0.90 ×: La / Lb < 0.85

[0273] [Table 3]

[0274] The evaluation results are shown in Table 3. As can be seen from Table 3, the chemically amplified negative photoresist compositions of Examples 39 to 56 require a lower minimum exposure than those using conventional photoacid generators, as in Comparative Examples 10 to 12. In other words, the photoacid generator of the present invention is more sensitive than the comparative photoacid generators and also exhibits superior storage stability and pattern shape. [Industrial applicability]

[0275] The photoacid generator containing the sulfonylimide salt compound of the present invention is used in paints, coatings, various coating materials (hard coats, stain-resistant coatings, anti-fogging coatings, corrosion-resistant coatings, optical fibers, etc.), back 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 formulations, 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 permanent film materials such as surface protective films, interlayer insulating films, and planarization films for semiconductor elements, etc.), and MEMS resists. It is suitably used as a photoacid generator in dysts, positive-type photosensitive materials, negative-type photosensitive materials, various adhesives (temporary fixing agents for various electronic components, adhesives for HDDs, adhesives for pickup lenses, adhesives for functional films for FPDs (polarizing plates, anti-reflective coatings, etc.), holographic resins, FPD materials (color filters, black matrices, partition materials, photospacers, ribs, alignment films for liquid crystals, sealants for FPDs, etc.), optical components, molding materials (for building materials, optical components, lenses), casting materials, putties, glass fiber impregnating agents, sealing materials, encapsulating materials, optoelectronic semiconductor (LED) encapsulating materials, optical waveguide materials, nanoimprint materials, materials for stereolithography, and materials for micro-stereolithography.

Claims

1. A photoacid generator containing a sulfonylimide salt compound represented by the following general formula (1). 【Chemistry 1】 [In formula (1), X ＋ This is a sulfonium cation represented by the following general formula (4). 【Chemistry 2】 [In formula (4), R １０ ~R １５ These independently represent an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, 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 optional silyl group, an optional amino group, a cyano group, a nitro group, or a halogen atom, and m9 to m14 are each R １０ ~R １５ This represents the number of elements, where m9, m12, and m14 represent integers from 0 to 5, and m10, m11, and m13 represent integers from 0 to 4.

2. In formula (4), R １０ ~R １５ The photoacid generator according to claim 1, wherein each of the groups is independently an alkyl group or an alkoxy group.

3. An energy ray curable composition comprising the photoacid generator described in claim 1 or 2 and a cationic polymerizable compound.

4. A cured body characterized by being obtained by curing the energy ray curable composition described in claim 3.

5. A chemically amplified positive-type photoresist composition comprising a component (A) containing the photoacid generator described in claim 1 or 2, and a component (B) which is a resin whose solubility in alkali increases due to the action of an acid.

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

7. A chemically amplified positive photoresist composition according to claim 5 or 6, further comprising an alkali-soluble resin (C) and an acid diffusion control agent (D).

8. 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 a chemically amplified positive-type photoresist composition according to any one of claims 5 to 7, 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.

9. A chemically amplified negative-type photoresist composition comprising a component (E) containing the photoacid generator described in claim 1 or 2, a component (F) which is an alkali-soluble resin having a phenolic hydroxyl group, and a crosslinking agent component (G).

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

11. A cured body characterized by being obtained by curing the chemically amplified negative photoresist composition described in claim 9 or 10.

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