Compounds, acid generators, compositions, cured products, methods for producing cured products, patterns, and methods for producing patterns.

Abstract

This invention provides a compound that exhibits excellent solubility in resin components and efficiently decomposes them to generate acid, thereby demonstrating excellent reactivity towards acid-reactive resin components. [Solution] Compound of formula (I) (wherein X: bond, O, CO, S, SO, SO2, etc. R 1 ~R 13 :H, halogen, CN, etc. Y - : Monovalent anion. JPEG2026084593000028.jpg72170

Description

[Technical Field]

[0001] The present invention relates to a compound which is a sulfonium salt, an acid generator containing the compound, a composition and a cured product thereof, as well as a method for producing a cured product using the composition, a pattern and a method for producing the pattern. [Background technology]

[0002] Sulfonium salt compounds are substances that generate acid when irradiated with energy rays such as light, and are used as photoacid generators in photolithography resist compositions used for forming electronic circuits such as semiconductors, and as cationic polymerization initiators in photopolymerizable compositions such as photopolymerization resin compositions, paints, coatings, and adhesives.

[0003] From the perspective of supporting high-resolution patterning and shortening processes, it is desirable to include a sufficient amount of acid generator in photoresists and cationic polymerization systems, or to use an acid generator with a good acid generation rate. Therefore, there is a demand for acid generators that have high solubility in resins and a sufficient acid generation rate. In addition, in applications such as transparent coatings, the color of the acid generator itself can be a problem. Photoacid generators, in particular, tend to have a yellowish tint due to their structure.

[0004] Patent Document 1 describes a thioxanthone-based sulfonium salt cationic polymerization initiator for surface coatings having a predetermined structure. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2003 / 072567 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, as described in Example 24 of the specification of the compound in Patent Document 1, it can be seen that it is "Slightly Yellow", that is, it has a yellowish tint.

[0007] An object of the present invention is to provide a compound that has excellent solubility in a resin component, shows excellent reactivity with an acid-reactive resin component by efficiently decomposing to generate an acid, and has a small change in transmittance at 430 nm even after photocuring.

Means for Solving the Problems

[0008] The present inventors have conducted intensive studies and found that a sulfonium salt compound having a predetermined structure has excellent solubility in a resin component, can lead to excellent reactivity in the curing reaction and decomposition reaction of a composition having an acid-reactive resin component by efficiently decomposing to generate an acid, and has a small change in transmittance at 430 nm even after photocuring.

[0009] That is, the present invention can be shown as follows. [1] A compound having a structure represented by the following general formula (I).

Chemical formula

[10] The composition according to [6], wherein the resin component is an acid-degradable resin component.

[11] A pattern comprising the composition described in

[10] .

[12]

[10] A step of forming a coating film using the composition described above, and generating an acid from the compound contained in the formed coating film, The process involves generating an acid from the compound, followed by developing a portion of the coating film to form a pattern, A method for manufacturing a pattern having the characteristics of a pattern. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide compounds, compositions, and cured products that have excellent solubility in resin components, efficiently decompose to generate acid, thereby leading to excellent reactivity in curing and decomposition reactions of compositions having acid-reactive resin components, and that show little change in transmittance at 430 nm even after photocuring. [Modes for carrying out the invention]

[0011] Embodiments of the present invention will be described below. Furthermore, unless otherwise specified, "1 to 10" represents a range from "1 or more" to "10 or less".

[0012] A. Compound First, the compounds of the present invention will be described. The compound disclosed herein is a compound having a structure represented by the following general formula (I) (hereinafter sometimes referred to as "Compound A").

[0013] [ka]

[0014] In the above general formula (I), X is a direct bond, C(R 14 )2, O, CO, S, SO, SO2 or NR 14 This represents,

[0015] R 1 , R 2 , R 3 , R 4 , R 5 , R6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 (Hereinafter referred to as “R 1 ~R 13 It is also written as ). Each of these independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a group represented by the following general formula (II). R 1 ~R 13 The hydrocarbon groups and heterocyclic groups used in the above are groups in which the hydrogen atoms in the group are not substituted, or in which one or more of the hydrogen atoms are replaced by a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH, -SO3H, an isocyanate group, or a hydrocarbon group having 1 to 10 carbon atoms, and in which case one or more of the methylene groups in the group may be replaced by a divalent group selected from the following <Group I>. R 1 ~R 13 At least one of them is a group represented by the following general formula (II),

[0016] Y - This represents a monovalent anion, <Group I>: -O-, -COO-, -OCO-, -CS-, -S-, -SO-, -SO2-, -NR 14 -, -NR 14 -CO-, -CO-NR 14 - or -NR 14 -COO- represents,

[0017] R 14 Each of these independently represents a hydrocarbon group having 1 to 20 carbon atoms in which one or more of the hydrogen atoms and methylene groups in the group may be substituted with a divalent group selected from Group I, or a heterocyclic group having 2 to 20 carbon atoms in which one or more of the methylene groups in the group may be substituted with a divalent group selected from Group I.

[0018] [ka]

[0019] In the above general formula (II), Z represents a divalent group selected from the above group <group I>, R 15 This represents a hydrocarbon group with 1 to 20 carbon atoms or a heterocyclic group with 2 to 20 carbon atoms. * indicates the bonding position with the general formula (I) above.

[0020] Compound A of this disclosure has excellent solubility in resin components and efficiently decomposes to generate acid, thereby leading to excellent reactivity in curing and decomposition reactions of compositions containing acid-reactive resin components, and exhibits minimal change in transmittance at 430 nm even after photocuring. As a result of the effects described above, compound A of this disclosure can be suitably used as a photoacid generator and a cationic polymerization initiator.

[0021] Compound A of this disclosure will be described in detail below.

[0022] In this disclosure, the number of carbon atoms in a group refers to the number of carbon atoms in the group after a substituent has replaced a hydrogen atom in the group. For example, in the case of a "hydrocarbon group having 1 to 20 carbon atoms," if it is a "group in which one or more hydrogen atoms have been replaced," then "1 to 20 carbon atoms" refers to the total number of carbon atoms in the group after the hydrogen atoms have been replaced, and not to the number of carbon atoms in the hydrocarbon group before the hydrogen atoms were replaced. Furthermore, in this disclosure, the number of carbon atoms in a group in which a methylene group in a group with a predetermined number of carbon atoms is substituted with a divalent group selected from the above-mentioned Group I defines the number of carbon atoms in the substituted group. For example, in this specification, the number of carbon atoms in a group in which one of the methylene groups (-CH2-) in an alkyl group having 20 carbon atoms is substituted with the divalent group "-O-" is 19. Furthermore, a hydrocarbon group in which one or more methylene groups are substituted with a divalent group selected from Group I does not have a structure in which multiple divalent groups are adjacent to each other. Nor does it have a structure in which all hydrocarbon groups are substituted with groups from Group I. For example, -CS- is not a hydrocarbon group with 1 carbon atom (a methylene group substituted with a divalent group selected from Group I (-S-)), but rather the divalent group selected from Group I itself (-CS-). Note that the multiple divalent groups selected from Group I may be the same or different. Where each form of compound A described below contains a hydrocarbon group or a heterocyclic group, this specification may include forms in which the methylene group in the hydrocarbon group or heterocyclic group is substituted with a divalent group selected from Group I, or in which the hydrogen atom in the hydrocarbon group or heterocyclic group is replaced with a substituent.

[0023] R in the above general formula (I) 1 ~R 13 Examples of hydrocarbon groups having 1 to 20 carbon atoms used include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, cycloalkylalkyl groups having 4 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or arylalkyl groups having 7 to 20 carbon atoms.

[0024] The alkyl group having 1 to 20 carbon atoms may be linear or branched. Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. Examples of branched alkyl groups include iso-propyl, sec-butyl, tert-butyl, iso-butyl, iso-pentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, iso-octyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl.

[0025] The cycloalkyl groups having 3 to 20 carbon atoms include saturated monocyclic alkyl groups, saturated polycyclic alkyl groups, and groups in which one or more hydrogen atoms in the ring of these groups are substituted with alkyl groups. Examples of saturated monocyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of saturated polycyclic alkyl groups include adamantyl, decahydronaphthyl, octahydropentalene, and bicyclo[1.1.1]pentanyl. Examples of alkyl groups that substitute hydrogen atoms in the ring of saturated monocyclic or saturated polycyclic alkyl groups include the groups exemplified above. Examples of groups in which one or more hydrogen atoms in the ring of a saturated polycyclic alkyl group are substituted with alkyl groups include bornyl.

[0026] The aforementioned cycloalkylalkyl group having 4 to 20 carbon atoms means a group in which one or more hydrogen atoms of the alkyl group are substituted with a cycloalkyl group. The cycloalkyl group in the cycloalkylalkyl group may be monocyclic or polycyclic. Examples of monocyclic cycloalkylalkyl groups include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononylethyl, and 2-cyclodecylethyl. Examples of polycyclic cycloalkylalkyl groups include 3-3-adamantylpropyl and decahydronaphthylpropyl.

[0027] The aforementioned alkenyl group having 2 to 20 carbon atoms is an internal alkenyl group having an unsaturated bond inside. It may be linear or branched. Examples of internal alkenyl groups include vinyl, 1-propenyl, 2-butenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, and 4,8,12-tetradecatrienylenylally.

[0028] The aryl group having 6 to 20 carbon atoms may be a monocyclic structure, a fused ring structure, or a structure in which two aromatic hydrocarbon rings are linked. The aryl group formed by linking two aromatic hydrocarbon rings may be a link between two monocyclic aromatic hydrocarbon rings, a link between a monocyclic aromatic hydrocarbon ring and a fused aromatic hydrocarbon ring, or a link between two fused aromatic hydrocarbon rings. Examples of linking groups for connecting two aromatic hydrocarbon rings include single bonds and carbonyl groups. Examples of monocyclic aryl groups include phenyl, tolyl, xylyl, ethylphenyl, and 2,4,6-trimethylphenyl. Examples of fused ring aryl groups include naphthyl, anthracenyl, phenanthryl, and pyrenyl. Examples of aryl groups in which two aromatic hydrocarbon rings are linked include biphenyl and benzoylphenyl. Furthermore, fused rings containing aromatic hydrocarbon rings such as fluorenyl and indenyl are also included in the aryl group.

[0029] The aforementioned arylalkyl group having 7 to 20 carbon atoms means a group in which one or more hydrogen atoms in the alkyl group are substituted with an aryl group. Examples of arylalkyl groups include benzyl, 9-fluorenylmethyl, α-methylbenzyl, phenylethyl, and naphthylpropyl groups.

[0030] R 1 ~R 13The hydrocarbon group used in [description] may have one or more hydrogen atoms in the group replaced by a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH, -SO3H, an isocyanate group, or a hydrocarbon group having 1 to 10 carbon atoms. When the hydrogen atom in the group is replaced, it is preferably replaced by a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms among others.

[0031] In this specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0032] R in the general formula (I) 1 ~R 13 Examples of the heterocyclic group-containing group having 2 to 20 carbon atoms used in [description] may have 2 to 20 carbon atoms, and include a group obtained by removing one hydrogen atom from an unsubstituted heterocyclic compound (hereinafter may be referred to as heterocyclic group I), a group in which one or more hydrogen atoms in the heterocyclic group I are substituted by a hydrocarbon group (hereinafter may be referred to as heterocyclic group II), or a group having a structure in which one or more hydrogen atoms in the unsubstituted heterocyclic group I or heterocyclic group II are substituted by a substituent. Examples of the hydrocarbon group that substitutes the hydrogen atom in the heterocyclic group I include those that satisfy the predetermined number of atoms defined in the heterocyclic group-containing group among the hydrocarbon groups having 1 to 20 carbon atoms used in R 1 ~R 13 and can be used. When the heterocyclic group II has a substituent, the substituent may be bonded to either the heterocyclic group or the hydrocarbon group.

[0033] The heterocyclic compound (hereinafter may be referred to as a heterocycle) may have a monocyclic structure or a condensed ring structure. Examples of the heterocycle having a condensed ring structure include a structure in which a heterocycle, a heterocycle, or a hydrocarbon ring is condensed, and a heterocyclic-containing condensed ring. Specific heterocyclic rings include monocyclic heterocyclic rings such as thiophene ring, furan ring, pyrrole ring, pyrrolidine ring, pyridine ring, piperidine ring, piperazine ring, morpholine ring, thiomorpholine ring, homopiperidine ring, homopiperazine ring, tetrahydropyridine ring, tetrahydrofuran ring, tetrahydropyran ring, caprolactam ring, isocyanuric ring, hydantoin ring, etc., and polycyclic heterocyclic rings such as tetrahydroquinoline ring, tetrahydroisoquinoline ring, dihydrobenzofuran ring, tetrahydrocarbazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, indole ring, indene ring, etc.

[0034] Examples of the substituent that replaces the hydrogen atom in the unsubstituted heterocyclic group I or heterocyclic group II include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH, -SO3H, an isocyanate group or a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms include those listed as the hydrocarbon group having 1 to 20 carbon atoms used in R 1 ~R 13 Among them, those satisfying a predetermined number of carbon atoms can be used.

[0035] R 14 Examples of the unsubstituted hydrocarbon group having 1 to 20 carbon atoms used in R 1 ~R 13 Among them, those satisfying a predetermined number of carbon atoms can be used, preferably having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 6 carbon atoms.

[0036] R 14 Examples of the unsubstituted heterocyclic group-containing group having 2 to 20 carbon atoms used in R 1 ~R 13 Among them, those satisfying a predetermined number of carbon atoms can be used, preferably having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 6 carbon atoms.

[0037] R 15 As for unsubstituted hydrocarbon groups with 1 to 20 carbon atoms used in this, R 1 ~R 13 Among the hydrocarbon groups with 1 to 20 carbon atoms used in the invention, those that satisfy the specified number of carbon atoms can be used.

[0038] R 15 As for unsubstituted heterocyclic groups with 2 to 20 carbon atoms used in this, R 1 ~R 13 Among the heterocyclic groups with 2 to 20 carbon atoms used in the formula, those that satisfy the specified number of carbon atoms can be used.

[0039] Y - Examples of monovalent anions used in this context include inorganic anions, tetraarylborate anions, monovalent organic sulfonic acid anions, organic fluorosulfonimide ions, or organic sulfonylmethide ions.

[0040] Inorganic anions include perchlorate anions, chlorate anions, thiocyanate anions, and hexafluoride phosphate anions (PF6). - ), antimony hexafluoride anion (SbF6 - ), arsenic hexafluoride anion, borate tetrafluoride anion (BF4 - Examples include fluorosulfonic acid anions.

[0041] As for tetraarylborate anions, [BR4] - (However, R is a phenyl group in which at least two of the hydrogen atoms in the group are replaced by fluorine atoms or trifluoromethyl groups.)

[0042] Examples of organic sulfonic acid anions include methanesulfonic acid anions, benzenesulfonic acid anions, toluenesulfonic acid anions, 1-naphthylsulfonic acid anions, 2-naphthylsulfonic acid anions, trifluoromethanesulfonic acid anions, pentafluoroethanesulfonic acid anions, heptafluoropropanesulfonic acid anions, nonafluorobutanesulfonic acid anions, undecafluoropentanesulfonic acid anions, tridecafluorohexanesulfonic acid anions, pentadecafluoroheptanesulfonic acid anions, heptadecafluorooctanesulfonic acid ions, perfluoro-4-ethylcyclohexanesulfonic acid ions, and N-alkyl Examples include aryl (or aryl)diphenylamine-4-sulfonic acid anions, 2-amino-4-methyl-5-chlorobenzenesulfonic acid anions, 2-amino-5-nitrobenzenesulfonic acid anions, sulfonic acid anions described in Japanese Patent Publication No. 2004-53799, camphor sulfonic acid anions, fluorobenzenesulfonic acid anions, difluorobenzenesulfonic acid anions, trifluorobenzenesulfonic acid anions, tetrafluorobenzenesulfonic acid anions, pentafluorobenzenesulfonic acid anions, 1,3,5-trimethylbenzenesulfonic acid anions, and 1,3,5-triisopropylbenzenesulfonic acid anions.

[0043] Examples of organic fluorosulfonimide ions include bis(trifluoromethanesulfone)imide ions, bis(pentafluoroethanesulfone)imide ions, and bis(heptafluoropropanesulfone)imide ions. Examples of organic sulfonylmethide ions include tris(trifluoromethanesulfonyl)methide ions and tris(methanesulfonyl)methide ions.

[0044] In this disclosure, X is a direct bond, C(R 14 )2, O, CO or NR 14 It is preferable that it be C(R 14 )2. Preferably, it is O or CO, and particularly preferably CO. Because of the aforementioned structure, compound A is easy to obtain as a raw material, easy to synthesize, has excellent solubility in resin components, efficiently decomposes to generate acid, and can lead to excellent reactivity in curing and decomposition reactions of compositions containing acid-reactive resin components, and is a compound that exhibits little change in transmittance at 430 nm even after photocuring.

[0045] In this disclosure, R 2 , R 4 , R 5 and R 7 At least one of the following is selected: It is preferable that the group is represented by the general formula (II) above, Among them, R 2 , R 4 , R 5 and R 7 Preferably, one of the selected groups is the group represented by the general formula (II), and the other three are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a hydrocarbon group having 1 to 20 carbon atoms. Especially R 2 , R 4 , R 5 or R 7 Preferably, one of these is a group represented by the general formula (II), and the other three are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon groups having 1 to 20 carbon atoms and the hydrocarbon groups having 1 to 10 carbon atoms are preferably alkyl groups. Because of the aforementioned structure, compound A is easy to obtain as a raw material, easy to synthesize, has excellent solubility in resin components, efficiently decomposes to generate acid, and can lead to excellent reactivity in curing and decomposition reactions of compositions containing acid-reactive resin components, and is a compound that exhibits little change in transmittance at 430 nm even after photocuring.

[0046] In this disclosure, R 1 , R 3 , R 6 and R 8 Each of them operates independently. It is preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a hydrocarbon group having 1 to 20 carbon atoms. In particular, hydrogen atoms, halogen atoms, nitro groups, or alkyl groups having 1 to 20 carbon atoms are preferred. In particular, it is preferable that the atom is a hydrogen atom, a nitro group, or an alkyl group having 1 to 6 carbon atoms. Of these, hydrogen atoms are particularly preferred. Because of the aforementioned structure, compound A is easy to obtain as a raw material, easy to synthesize, has excellent solubility in resin components, efficiently decomposes to generate acid, and can lead to excellent reactivity in curing and decomposition reactions of compositions containing acid-reactive resin components, and is a compound that exhibits little change in transmittance at 430 nm even after photocuring.

[0047] In this disclosure, R 9 ~R 13 Each of them operates independently. It is preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a hydrocarbon group having 1 to 20 carbon atoms. In particular, hydrogen atoms, halogen atoms, nitro groups, or alkyl groups having 1 to 20 carbon atoms are preferred. In particular, it is preferable that the atoms are hydrogen atoms, nitro groups, or alkyl groups having 1 to 6 carbon atoms. Of these, hydrogen atoms are particularly preferred. Because of the aforementioned structure, compound A is easy to obtain as a raw material, easy to synthesize, has excellent solubility in resin components, efficiently decomposes to generate acid, and can lead to excellent reactivity in curing and decomposition reactions of compositions containing acid-reactive resin components, and is a compound that exhibits little change in transmittance at 430 nm even after photocuring.

[0048] In this disclosure, Y - teeth, It is preferable that the anion be an inorganic anion or a tetraarylborate anion, and among these, an inorganic anion is preferred. For example, BF4 - PF6 - SbF6- or [BR4] - (However, R is preferably a phenyl group in which at least two of the hydrogen atoms in the group are substituted with fluorine atoms or trifluoromethyl groups.) Among them, BF4 - PF6 - Or SbF6 - It is preferable that this be the case. Especially PF6 - It is preferable that this be the case. Because of the aforementioned structure, compound A is easy to obtain as a raw material, easy to synthesize, has excellent solubility in resin components, efficiently decomposes to generate acid, and can lead to excellent reactivity in curing and decomposition reactions of compositions containing acid-reactive components, and is a compound that exhibits little change in transmittance at 430 nm even after photocuring.

[0049] In this disclosure, Z is, -O-, -COO-, -OCO- or -NR 14 - is preferable, In particular, -COO- or -OCO- is preferred. Because of the aforementioned structure, compound A is easy to obtain as a raw material, easy to synthesize, has excellent solubility in resin components, efficiently decomposes to generate acid, and can lead to excellent reactivity in curing and decomposition reactions of compositions containing acid-reactive resin components, and is a compound that exhibits little change in transmittance at 430 nm even after photocuring.

[0050] In this disclosure, R 15 Preferably, it is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. In particular, it is preferable that the group is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. It is particularly preferable that the alkyl group has 1 to 20 carbon atoms. In particular, alkyl groups having 1 to 8 carbon atoms are preferred. It is particularly preferable that the alkyl group has 3 to 8 carbon atoms. Because of the aforementioned structure, compound A is easy to obtain as a raw material, easy to synthesize, has excellent solubility in resin components, efficiently decomposes to generate acid, and can lead to excellent reactivity in curing and decomposition reactions of compositions containing acid-reactive resin components, and is a compound that exhibits little change in transmittance at 430 nm even after photocuring.

[0051] Examples of the specific structure of compound A include the following compounds.

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] In this disclosure, the molar extinction coefficient of compound A for light at a wavelength of 365 nm is given as 70 L·mol. -1 ·cm -1 Preferably, the amount is greater than or equal to 100 L·mol. -1 ·cm -1 It is preferable that the above conditions are met. Compound A is the compound disclosed in this disclosure because it exhibits excellent absorption of light at a wavelength of 365 nm and also has excellent photodegradation rates. The absorption coefficient is calculated by measuring the absorption spectrum at 365 nm using a UV-Vis spectrophotometer (JASCO Corporation, V-670) with a solution of the compound dissolved in acetonitrile placed in a lidded quartz cell. The compound concentration in the solution is 10 -3 mol / L ~ 10 -5 A mol / L concentration is preferred.

[0056] In this disclosure, the photodegradation rate of compound A to light at a wavelength of 365 nm is preferably 10 mol% or more, more preferably 20 mol% or more, and particularly preferably 30 mol% or more. This is because compound A, as disclosed in this disclosure, allows us to provide a compound with excellent photodegradation rates. The photodecomposition rate was measured by sealing the solution used for the absorption coefficient measurement and using a UV LED light source at 365 nm with a concentration of 500 mJ / cm². 2 The degradation rate of a compound is calculated by exposing the solution to light, measuring the solution before and after exposure using high-performance liquid chromatography (peak area ratio using the internal standard method), and determining the degradation rate of the compound. The measurement conditions for high-performance liquid chromatography are as follows: Column: Inertsil ODS column (φ5μm × 150mm) manufactured by GL Sciences Co., Ltd. Eluent: Acetonitrile / 10 mM n-octanesulfonic acid aqueous solution = volume ratio 8 / 2 Detector: UV-Vis detector, 230nm

[0057] As mentioned above, compound A is less prone to discoloration after exposure, making it possible to provide transparent compositions and cured products. For example, the transmittance of compound A at 430 nm after light irradiation is: It is preferable that it be 96% or higher. In particular, a percentage of 97% or higher is preferable. The transmittance measurement method involves dissolving compound A in acetonitrile and adjusting the concentration to 0.1 mmol / L. The adjusted sample is then placed in a lidded quartz cell and exposed to a high-pressure mercury lamp (illuminance 20 mW / cm²). 2 ·s), 1500 mJ / cm² 2The sample is irradiated with ), and the transmittance at 430 nm after irradiation is measured using an ultraviolet-visible spectrophotometer (JASCO Corporation, V-670).

[0058] Furthermore, it is preferable that the decrease in transmittance at 430 nm after irradiation with compound A is 4% or less, and more preferably 3% or less. The transmittance measurement method involves dissolving compound A in acetonitrile and adjusting the concentration to 0.1 mmol / L. The adjusted sample is then placed in a lidded quartz cell and exposed to a high-pressure mercury lamp (illuminance 20 mW / cm²). 2 ·s), 1500 mJ / cm² 2 The light is irradiated with a UV-Vis spectrophotometer (JASCO Corporation, V-670) and the transmittance at 430 nm before and after irradiation is measured. The reduction rate is then calculated from the transmittance before and after irradiation.

[0059] The method for producing compound A can be any method that yields a compound with the desired structure, and it can be synthesized by applying well-known chemical reactions. For example, compound A can be synthesized by reacting a precursor compound with an iodonium compound using the method shown in scheme A below. Examples of methods for producing compound 1 according to scheme A include schemes 1 and 2. There are no particular restrictions on reaction conditions such as reaction temperature, reaction time, and amount of raw materials used in the production method, and known conditions may be used.

[0060] Example of preparation method for compound A [ka] (X, Y, R 9 ~R 13 These are X, Y and R of the general formula (I) above. 9 ~R 13 The same applies to Z and R. 15 These are Z and R in the general formula (II) above. 15 The same applies to each of the following. 1A ~R 8A Aside from being a group other than general formula (II), R 1 ~R 8 These are similar, but [ZR 15 The group represented by ] is R 1A ~R8A It may be attached to any of these positions. (m represents a number greater than or equal to 1.)

[0061] [ka] (X is the same as X in the general formula (I) above. R 15 R in the above general formula (II) is 15 It is similar to this.

[0062] [ka] (X and Y are the same as X and Y in the general formula (I) above. 15 R in the above general formula (II) is 15 It is similar to this.

[0063] Compound A has the function of generating acid through the decomposition of a part of its structure. As a method for generating acid from compound A, methods commonly used for acid generators can be used. Specifically, these include methods of irradiation with energy rays (light), heat treatment, and methods of performing these methods simultaneously or sequentially. Examples of such energy rays include g-rays (436 nm), h-rays (405 nm), i-rays (365 nm), visible light, ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams. Other light sources include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halogen lamps, electron beam irradiation devices, X-ray irradiation devices, and lasers (argon lasers, dye lasers, nitrogen lasers, LEDs, helium-cadmium lasers, etc.). The heating temperature in the heat treatment is preferably, for example, 70°C to 450°C, more preferably 100°C to 400°C, particularly preferably 105°C to 370°C, and may also be 150°C or higher. The heating time in the heat treatment is preferably, for example, 1 minute to 100 minutes. This is because these heat treatment conditions can suppress color changes in the composition. Since compound A exhibits excellent absorption of light with wavelengths of 365 nm to 405 nm and also has excellent photodecomposition rates, it is preferable to use a method of generating acid by irradiating it with energy rays, particularly i-rays or h-rays, especially i-rays.

[0064] Applications of compound A include acid generators, more specifically, photoacid generators that generate acid by energy ray irradiation, and thermal acid generators that generate acid by heat treatment. Another application of acid generators is their use as additives to compositions containing resin components. Applications of the composition include, for example, optical filters, paints, coatings, linings, adhesives, printing plates, insulating varnishes, insulating sheets, laminates, printed circuit boards, sealing agents for semiconductor devices, LED packages, liquid crystal injection ports, organic EL displays, optical elements, electrical insulation, electronic components, and separator films, molding materials, putties, glass fiber impregnating agents, sealing agents, passivation films for semiconductors and solar cells, interlayer insulating films used in thin-film transistors (TFTs), liquid crystal displays, organic EL displays, printed circuit boards, etc., surface protective films, printed circuit boards, or Color televisions, PC monitors, personal digital assistants, color filters for CCD image sensors, electrode materials for plasma display panels, printing inks, dental compositions, resins for photopolymerization, both liquid and dry films, micro-mechanical parts, glass fiber cable coatings, holographic recording materials, magnetic recording materials, optical switches, plating masks, etching masks, stencils for screen printing, touch panels such as transparent conductive films, MEMS elements, nanoimprint materials, photofabrication such as two-dimensional and three-dimensional high-density mounting of semiconductor packages, decorative sheets, artificial nails, glass substitute optical films, electronic paper, optical discs, microlens arrays used in projectors and optical communication lasers, prism lens sheets used in backlights of liquid crystal display devices, Fresnel lens sheets used in screens such as projection televisions, lentigations It can be used in a wide range of applications, including the lens portion of lens sheets such as regular lens sheets, or backlights using such sheets, optical lenses such as microlenses and imaging lenses, optical elements, optical connectors, optical waveguides, insulating packings, heat-shrinkable rubber tubes, O-rings, sealants for display devices, protective materials, optical fiber protective materials, adhesives, die bonding agents, high heat dissipation materials, high heat-resistant sealants, components for solar cells, fuel cells, and secondary batteries, solid electrolytes for batteries, insulating coatings, photosensitive drums for copiers, gas separation membranes, civil engineering and construction materials such as concrete protective materials, linings, soil injection agents, sealing agents, thermal storage materials, glass coatings, and foams, as well as medical materials such as tubes, sealants, coating materials, sealants for sterilization equipment, contact lenses, and oxygen enrichment membranes, biochips, automotive parts, and various machine parts, with no particular restrictions on its use. From the viewpoint of more effectively demonstrating the effect of excellent acid generation sensitivity, the above-mentioned application is preferably for pattern-forming compositions, for example, for negative-type compositions used with acid-curable components (also called "acid-curable resin components"), for positive-type compositions used with acid-degradable components (also called "acid-degradable resin components"), and more specifically, for compositions used in forming interlayer insulating films and adhesives used in optical lenses, optical elements, optical connectors, optical waveguides, liquid crystal display devices, organic EL display devices, printed circuit boards, etc., which require high acid generation sensitivity.

[0065] B. Acid Generator The acid generator of the present invention (hereinafter sometimes referred to as "acid generator B") is characterized by containing the above compound A. According to the present invention, an acid generator, composition, and cured product can be provided that have excellent solubility in resin components, efficiently decompose them to generate acid, thereby leading to excellent reactivity in curing and decomposition reactions of compositions containing acid-reactive resin components, and that show little change in transmittance at 430 nm even after photocuring.

[0066] 1. Compound A As for compound A, the same compound as described in "A. Compound" above can be used, so its explanation is omitted here.

[0067] The content of compound A is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and most preferably 80 parts by mass or more, per 100 parts by mass of the non-solvent component of acid generator B. This content allows acid generator B to have excellent solubility in the resin component, efficiently decompose and generate acid, thereby leading to excellent reactivity in the curing and decomposition reactions of compositions having acid-reactive resin components, and also results in minimal change in transmittance at 430 nm even after photocuring. Furthermore, "non-solvent components" refers to the total amount of all components other than solvents. The definition of non-solvent components in this specification also applies to compositions that do not contain solvents.

[0068] The content of compound A is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, particularly preferably 50 parts by mass or more, and most preferably 80 parts by mass or more, per 100 parts by mass of acid generator B. This is because the above content allows acid generator B to have excellent solubility in resin components, efficiently decompose and generate acid, thereby leading to excellent reactivity in curing and decomposition reactions of compositions having acid-reactive resin components, and also results in minimal change in transmittance at 430 nm even after photocuring.

[0069] 2. Other acid generators The acid generator B may include acid generators other than compound A. Other acid generators that can be used include conventionally known photoacid generators and thermal acid generators.

[0070] For example, examples of photoacid generators include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts, thianthrenium salts, and thioxanthonium salts. Examples of commercially available products include CPI(R)-100P, CPI(R)-110P, CPI(R)-101A, CPI(R)-200K, CPI(R)-210S (all manufactured by Sunapro Co., Ltd.); Cyracure(R) Photocuring Initiator UVI-6990, Cyracure(R) Photocuring Initiator UVI-6992, Cyracure(R) Photocuring Initiator UVI-6976 (all manufactured by Dow Chemical Japan Ltd.); Adeka Arcluz SP-150, Adeka Arcluz SP-151, Adeka Arcluz SP-152, Adeka Arcluz SP-170, Adeka Arcluz SP-172, Adeka Arcluz SP-300 (all manufactured by AD Co., Ltd.) Examples include: EKA-made; CI-5102, CI-2855 (both manufactured by Nippon Soda Co., Ltd.); Sun-Aid(R) SI-60L, Sun-Aid(R) SI-80L, Sun-Aid(R) SI-100L, Sun-Aid(R) SI-110L, Sun-Aid(R) SI-180L, Sun-Aid(R) SI-110, Sun-Aid(R) SI-180 (all manufactured by Sanshin Chemical Industry Co., Ltd.); EsaCure(R) 1064, EsaCure(R) 1187 (both manufactured by Lamberti); Omnicat 550, Omnicat 250 (manufactured by IGM Resin Co., Ltd.); and RhodeSill Photoinitiator 2074 (manufactured by Rhodia Japan Co., Ltd.).

[0071] Examples of thermal acid generators include honate, triphenylsulfonium tetrafluoroborate, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate, bis(cyclohexylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, triphenylsulfonium trifluoromethanesulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-p-toluenesulfonate, and diphenyl-p-phenylthiophenylsulfonium hexafluorophosphate. Examples of commercially available products include the diazonium salt compounds AMERICURE series (manufactured by American Scan Corporation); iodonium salt compounds UVE series (manufactured by General Electric Corporation); FC series (manufactured by 3M Corporation); UV9310C (manufactured by GE Toshiba Silicone Corporation); WPI series and WPAG series (manufactured by Fujifilm Wako Pure Chemical Corporation); sulfonium salt compounds CYRACURE series (manufactured by Union Carbide Corporation); UVI series (manufactured by General Electric Corporation); CD series (manufactured by Sartomer Corporation); Optomer SP series and Optomer CP series (manufactured by ADEKA Corporation); San-Aid SI series (manufactured by Sanshin Chemical Industry Co., Ltd.); CI series (manufactured by Nippon Soda Co., Ltd.); and CPI series (manufactured by Sunapro Corporation).

[0072] The content of the aforementioned other acid generators is, per 100 parts by mass of compound A, Preferably, the amount is 0 to 30 parts by mass. In particular, it is preferable that the amount be 0 to 15 parts by mass. It is particularly preferable that the amount be 0 to 5 parts by mass. The aforementioned content allows acid generator B to have excellent solubility in resin components, efficiently decompose and generate acid, thereby leading to excellent reactivity in curing and decomposition reactions of compositions containing acid-reactive resin components, and also resulting in minimal change in transmittance at 430 nm even after photocuring.

[0073] 3. Solvent The acid generator B may contain a solvent. The aforementioned solvent is capable of dispersing or dissolving each component of acid generator B. Therefore, even when in liquid state at room temperature (25°C) and atmospheric pressure, compound A and other acid generators are not contained in the solvent. The aforementioned solvent can be either water or an organic solvent. In the present invention, it is preferable that the solvent is an organic solvent, because it facilitates the dissolution or dispersion of compound A.

[0074] Examples of the aforementioned organic solvents include carbonates such as propylene carbonate and diethyl carbonate; ketones such as acetone and 2-heptanone; polyhydric alcohols and their derivatives such as ethylene glycol, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and monomethyl ether or monophenyl ether of dipropylene glycol monoacetate; cyclic ethers such as dioxane; esters such as ethyl formate and 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene; and lactones such as γ-caprolactone and δ-caprolactone.

[0075] The solvent content in the acid generator B of the present invention is set appropriately according to the intended use of the acid generator B, and for example, it can be 1 part by mass or more and 99 parts by mass or less per 100 parts by mass of the composition.

[0076] 4. Other ingredients The acid generator B may contain other components as needed. Other components can be selected depending on the intended use of the composition, and examples include sensitizers, UV absorbers, antioxidants, surfactants, silane coupling agents, and the like. The content of these other components in the acid generator B of the present invention may be 50 parts by mass or less per 100 parts by mass of the acid generator B.

[0077] The uses of acid generator B may be the same as those described in section "A. Compounds" above.

[0078] As for the method of producing the acid generator B, any method that can mix each of the components in the desired proportions is acceptable, and known methods can be used. For example, one method is to dissolve or disperse compound A in a solvent, and then add other components to the solvent. As for the mixer, for example, a homodisper, homomixer, universal mixer, planetary mixer, kneader, three-roll mixer, etc. can be used.

[0079] C. Composition The composition of the present invention (hereinafter sometimes referred to as Composition C) is characterized by containing compound A.

[0080] 1. Compound A As for compound A, the same compound as described in "A. Compound" above can be used, so its explanation is omitted here.

[0081] The type of compound A used in composition C of the present invention can be any compound that exhibits a predetermined effect, and may consist of only one type or two or more types in composition C.

[0082] In the present invention, when compound A is used with an acid-reactive resin component, the content of compound A is not particularly limited, but it is preferably 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the acid-reactive resin component, more preferably 0.1 parts by mass or more and 5 parts by mass or less, and particularly preferably 0.1 parts by mass or more and 3 parts by mass or less. However, depending on factors such as the properties of the acid-reactive resin component, the intensity of light irradiation, the time required for the reaction, physical properties, and cost, it is possible to increase or decrease the amount used from the range mentioned above. With the aforementioned content, compound A dissolves in the resin component and efficiently decomposes to generate acid, leading to excellent reactivity in the curing and decomposition reactions of the acid-reactive resin component in composition C, and providing composition C and cured product with minimal change in transmittance at 430 nm even after photocuring.

[0083] The content of compound A in the composition of the present invention is preferably 0.05 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the non-solvent component of composition C, more preferably 0.2 parts by mass or more and 20 parts by mass or less, and particularly preferably 0.5 parts by mass or more and 10 parts by mass or less. With the aforementioned content, compound A dissolves in the resin component and efficiently decomposes to generate acid, leading to excellent reactivity in the curing and decomposition reactions of the acid-reactive resin component in composition C, and providing composition C and cured product with minimal change in transmittance at 430 nm even after photocuring.

[0084] The content of compound A in the composition of the present invention is preferably 0.01 parts by mass or more and 30 parts by mass or less per 100 parts by mass of composition C, more preferably 0.02 parts by mass or more and 20 parts by mass or less, and particularly preferably 0.1 parts by mass or more and 10 parts by mass or less. With the aforementioned content, compound A dissolves in the resin component and efficiently decomposes to generate acid, leading to excellent reactivity in the curing and decomposition reactions of the acid-reactive resin component in composition C, and providing composition C and cured product with minimal change in transmittance at 430 nm even after photocuring. The content of compound A, if it includes two or more types of compound A, indicates the total amount of compound A.

[0085] 2. Resin components Composition C may contain a resin component. As the resin component, a polymer compound or a component that can become a polymer compound can be used. Furthermore, the resin component may be an acid-reactive resin component having a structure that can react with the acid generated by the decomposition of compound A, or it may be a non-acid-reactive resin component that does not react with the acid generated from compound A, but it is preferable that the resin component is an acid-reactive resin component. Because the resin component is an acid-reactive resin component, composition C can exhibit excellent reactivity due to the acid generated when compound A decomposes.

[0086] Examples of such acid-reactive resin components include acid-curable resin components that polymerize or crosslink and harden due to the acid generated from compound A, or acid-degradable resin components whose solubility in the developer increases due to the acid generated from compound A.

[0087] Examples of the acid-curable resin component include cationic polymerizable compounds. Examples of cationic polymerizable compounds include epoxy compounds, cyclic ether compounds such as oxetane compounds, vinyl ether compounds, vinyl compounds, styrenes, spiroorthoesters, bicycloorthoesters, spiroorthocarbonates, lactones, oxazolines, aziridines, cyclosiloxanes, ketals, cyclic acid anhydrides, lactams, aryldialdehydes, and other polymerizable or crosslinkable polymers and oligomers having these polymerizable groups in their side chains. These may be used individually or in combination of two or more types. Specific examples of such cationic polymerizable compounds include, for example, compounds described as cationic polymerizable compounds in International Publication No. 2017 / 130896 (acid-reactive organic substances), International Publication No. 2014 / 084269, International Publication No. 2016 / 132413, etc.

[0088] As the acid-curable resin component, a mixture of a crosslinkable resin and a crosslinking agent can also be used. Examples of the crosslinkable resin include polyhydroxystyrene and its derivatives; polyacrylic acid and its derivatives; polymethacrylic acid and its derivatives; two or more copolymers selected and formed from hydroxystyrene, acrylic acid, methacrylic acid and their derivatives; two or more copolymers selected and formed from hydroxystyrene, styrene and their derivatives; three or more copolymers selected from cycloolefins and their derivatives, maleic anhydride, and acrylic acid and its derivatives; three or more copolymers selected from cycloolefins and their derivatives, maleimide, and acrylic acid and its derivatives; polynorbornene; one or more polymers selected from the group consisting of metathesis ring-opening polymers; polymers having alkoxysilyl groups; and polymers obtained by partially substituting these polymers with acid-unstable groups that have alkali-solubility control ability. Examples of polymers containing structural units derived from hydroxystyrene, such as polyhydroxystyrene, include the phenolic hydroxyl group-containing resin (QN) described in Japanese Patent Application Publication No. 2018-112670. The document lists novolac resins, polyhydroxystyrene, copolymers of hydroxystyrene, copolymers of hydroxystyrene and styrene, copolymers of hydroxystyrene, styrene and (meth)acrylic acid derivatives, phenol-xylylene glycol condensation resins, cresol-xylylene glycol condensation resins, polyimides containing phenolic hydroxyl groups, polyamic acids containing phenolic hydroxyl groups, and phenol-dicyclopentadiene condensation resins as examples of QN. As the crosslinkable resin, for example, the resist-based resin described in International Publication No. 2017 / 130896, the resin composition used in the negative-type resist material described in Japanese Patent Application Publication No. 2003-192665, claim 3 of Japanese Patent Application Publication No. 2004-323704, and the negative-type radiation-sensitive resin composition described in Japanese Patent Application Publication No. 10-10733 can also be used. As the polymer having the alkoxysilyl group, for example, a compound in which the alkoxysilyl group is not directly bonded to the aromatic ring can be used.

[0089] The crosslinking agent can be any agent capable of crosslinking the crosslinkable resins together in the presence of an acid. Such crosslinking agents can be compounds that react with acidic groups such as phenolic hydroxyl groups and carboxyl groups contained in the resins in the presence of an acid, such as epoxy group-containing compounds, hydroxyl group-containing compounds, alkoxy group-containing compounds, methylol group-containing compounds, and carboxymethyl group-containing compounds. More specifically, examples of the aforementioned crosslinking agents include those described in Japanese Patent Publication No. 2003-192665, Japanese Patent Publication No. 10-10733, Japanese Patent Publication No. 2016-169173, and Japanese Patent Publication No. 2018-112670.

[0090] The acid-degradable resin component can be any component whose solubility in the developer increases due to the acid generated from compound A. Examples include resins in which some or all of the hydrogen atoms of the acidic groups in a resin having acidic groups such as phenolic hydroxyl groups, carboxyl groups, sulfonyl groups, and silanol groups are protected with a protecting group. Examples of resins having such acidic groups include the crosslinkable resins used together with a crosslinking agent as an acid-curable resin component as described above. Positive-type chemically amplified resins described in Japanese Patent Application Publication No. 2018-112670 can also be used. The protecting group can be any group capable of protecting the acidic group, and examples include the protecting group described in Japanese Patent Publication No. 2016-169173, the acid-unstable group described in International Publication No. 2017 / 130896, and the acid-dissociable group described in Japanese Patent Publication No. 2018-112670. Furthermore, an example of a silanol group protected by a protecting group is an alkoxysilyl group. As a polymer having an alkoxysilyl group used as an acid-degradable resin component, for example, one described in Japanese Patent Publication No. 2019-66828 as "a polymer component (A) having a structural unit (I) comprising an aromatic ring and an alkoxysilyl group directly bonded to the aromatic ring, and a structural unit (II) comprising an acidic group" can be used. Furthermore, the developer mentioned above may be the developer described in section "G. Method for manufacturing a pattern" later.

[0091] The acid-reactive resin component can be an acid-reactive component in addition to the acid-curable resin component and the acid-degradable resin component. For example, a resin having alkali-soluble groups that becomes insoluble when exposed to acid can also be used. Specifically, examples of acid-insolubilable resins include those that undergo intramolecular or intermolecular crosslinking reactions by acid-catalyzed dehydration condensation of hydroxyl groups and carboxyl groups, or carboxyl groups as exemplified below. Examples of acid-insolubilable resins that undergo acid-catalyzed dehydration condensation of carboxyl groups include resins having a phthalic acid structure in which carboxyl groups undergo dehydration condensation with acid, as shown below.

[0092] [ka]

[0093] The non-acid-reactive resin component can be one that does not react with the acid generated from compound A, or more specifically, one that does not undergo curing, decomposition, or changes in solubility in alkaline developing solutions due to the acid generated from compound A. Examples include thermoplastic resins such as polyolefin resins, polybutadiene resins, polystyrene resins, polystyrene-butadiene resins, and polystyrene-olefin resins.

[0094] The content of the resin component in composition C of the present invention is sufficient to obtain the desired effect and is set appropriately according to the type of resin component used. The content of the resin component in composition C can be 20 parts by mass or more per 100 parts by mass of the non-solvent component of composition C, preferably 30 parts by mass or more and 99 parts by mass or less, and more preferably 40 parts by mass or more and 98 parts by mass or less. Composition C exhibits excellent reactivity in curing and decomposition reactions due to the acid generated by the efficient decomposition of compound A.

[0095] The content of the resin component in composition C of the present invention can be, for example, 30 parts by mass or more, preferably 40 parts by mass or more and 300 parts by mass or less, and more preferably 60 parts by mass or more and 200 parts by mass or less, based on 1 part by mass of compound A in composition C. Composition C exhibits excellent reactivity in curing and decomposition reactions due to the acid generated by the efficient decomposition of compound A.

[0096] The content of the resin component in composition C of the present invention can be, for example, 20 parts by mass or more per 100 parts by mass of composition C, preferably 30 parts by mass or more and 99 parts by mass or less, and more preferably 50 parts by mass or more and 98 parts by mass or less. Composition C exhibits excellent reactivity in curing and decomposition reactions due to the acid generated by the efficient decomposition of compound A.

[0097] 3. Solvent Composition C may contain a solvent. The solvent is capable of dispersing or dissolving each component in composition C. Therefore, even when liquid at room temperature (25°C) and atmospheric pressure, compound A and the resin component are not contained in the solvent. Either water or an organic solvent can be used as the solvent. In the present invention, it is preferable that the solvent is an organic solvent, because it facilitates the dissolution or dispersion of compound A.

[0098] Examples of the aforementioned organic solvents include carbonates such as propylene carbonate and diethyl carbonate; ketones such as acetone and 2-heptanone; polyhydric alcohols and their derivatives such as ethylene glycol, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and monomethyl ether or monophenyl ether of dipropylene glycol monoacetate; cyclic ethers such as dioxane; esters such as ethyl formate and 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene; and lactones such as γ-caprolactone and δ-caprolactone.

[0099] The solvent content in composition C of the present invention is set appropriately according to the intended use of composition C, for example, it can be 1 part by mass or more and 99 parts by mass or less per 100 parts by mass of the composition.

[0100] 4. Other ingredients The aforementioned composition C may optionally contain other components. Other components can be selected depending on the intended use of the composition, and include, for example, benzotriazole, triazine, and benzoate-based UV absorbers; phenolic, phosphorus, and sulfur-based antioxidants; antistatic agents consisting of cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, etc.; flame retardants such as halogen compounds, phosphate ester compounds, phosphate amide compounds, melamine compounds, fluororesins or metal oxides, (poly)melamine phosphate, and (poly)piperazine phosphate; and hydrocarbon, fatty acid, and aliphatic alcohols. Lubricants include aliphatic ester, aliphatic amide, or metallic soap types; colorants such as dyes, pigments, and carbon black; silicic acid-based inorganic additives such as fumed silica, fine silica particles, silica, diatomaceous earth, clay, kaolin, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar powder, vermiculite, attapulgite, talc, mica, minesoite, pyrophyllite, and silica; fillers such as glass fibers and calcium carbonate; crystallizing agents such as nucleating agents and crystallization accelerators; rubber elasticity imparting agents such as silane coupling agents and flexible polymers; and sensitizers. As long as the desired effect is not impaired, other acid-generating agents besides compound A may also be included. Furthermore, the other components may also include acid diffusion control agents such as amine compounds, amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds. Examples of the sensitizer include compounds described as spectrophotometric sensitizers in Japanese Patent Publication No. 2008-506749. Examples of the acid diffusion control agent include the compounds described as "[D] acid diffusion control agent" in Japanese Patent Publication No. 2019-8300. The content of these other components in the composition of the present invention may be 50 parts by mass or less per 100 parts by mass of composition C.

[0101] The uses of composition C may be the same as those described in section "A. Compounds" above.

[0102] The method for producing the composition C can be any method that allows the components to be mixed in the desired amounts, and known methods can be used. For example, one method is to dissolve or disperse compound A in a solvent, and then add a resin component to the solvent. As for the mixer, for example, a homodisper, homomixer, universal mixer, planetary mixer, kneader, three-roll mixer, etc. can be used.

[0103] D. Cured product The cured product of the present invention (hereinafter sometimes referred to as cured product D) is a cured product of composition C. Furthermore, the resin component contained in composition C is an acid-curable resin component.

[0104] According to the present invention, by using composition C, compound A is efficiently decomposed to generate acid, leading to excellent reactivity in the curing reaction, and a cured product can be provided that shows little change in transmittance at 430 nm even after photocuring.

[0105] 1. Composition Regarding composition C, the same composition as described in "C. Composition" above can be used, so its explanation is omitted here. Furthermore, the resin component is an acid-curable resin component, and the cured product D is the cured form of the acid-curable component, and includes a polymer formed by polymerization of acid-curable components or a crosslinked product formed by crosslinking of acid-curable components.

[0106] The planar shape of the cured product D can be appropriately set according to the intended use of the cured product, and can be a pattern such as a dot pattern or a line pattern.

[0107] The uses of the cured product D may be the same as those described in section "A. Compounds" above.

[0108] The method for producing the cured product D is not particularly limited as long as it is a method that can form the cured product of composition C into a desired shape. As an example of such a manufacturing method, the manufacturing method described in section "E. Method for Manufacturing Cured Products" below can be used.

[0109] E. Method for manufacturing cured products The method for producing the cured product D of the present invention will be described below. The method for producing the cured product D of the present invention is characterized by having a curing step for curing the composition C. Furthermore, the resin component contained in composition C is an acid-curable resin component.

[0110] According to the present invention, by using composition C, compound A is efficiently decomposed to generate acid, leading to excellent reactivity in the curing reaction, and making it possible to easily form a cured product in which the acid-curable resin component has sufficiently cured.

[0111] 1.Curing process The curing step in the present invention is a step of curing composition C. The method for curing composition C can be any method capable of curing an acid-curable resin component, and a method of generating acid from compound A can be used. The method for generating acid from compound A can be any method that allows compound A to decompose and generate a desired amount of acid. Examples include irradiation with energy rays, heat treatment, and methods that perform these simultaneously or sequentially. Such methods, such as irradiation with energy rays and heat treatment, can be the same as those described in the "A. Compound" section above. In this process, it is preferable that the method for generating the acid includes irradiating it with energy rays. This is because compound A has excellent light absorption and photodecomposition rates, allowing for efficient acid generation. Furthermore, composition C contains an acid-curable resin component as a resin component. The contents of such a composition can be the same as those described in section "C. Composition" above, so a detailed explanation is omitted here.

[0112] 2. Other processes The method for producing the cured product D of the present invention may include, as necessary, other steps in addition to the curing step. Other steps include a developing step to remove unpolymerized portions from the coating film of the composition after the curing step to obtain a patterned cured product, a pre-bake step to heat-treat the composition before the curing step to remove solvents from the composition, a step to form a coating film of the composition before the curing step, and a post-bake step to heat-treat the cured product after the curing step. In the present invention, it is preferable that the other steps include a post-bake step. This is because the acid generated from compound A can be effectively diffused, and it becomes easier to form a cured product in which the acid-curable resin component has sufficiently hardened.

[0113] One method for removing the unpolymerized portion in the development process is to apply a developer, such as an alkaline developer, to the unpolymerized portion. As the aforementioned alkaline developer, commonly used alkaline developers such as tetramethylammonium hydroxide (TMAH) aqueous solution, potassium hydroxide aqueous solution, or potassium carbonate aqueous solution can be used. Furthermore, as the developer, commonly used solvent developers such as propylene glycol monomethyl ether acetate (PEGMEA) or cyclohexanone can be used. As for the development method using the developer, any method that allows the area to be developed to come into contact with the developer is acceptable, and known methods such as the shower method, spray method, and immersion method can be used. The timing of the development process can be anytime after the curing process. The heating conditions in the post-bake process can be any conditions that can improve the strength of the hardened product obtained in the hardening process, for example, 200°C to 250°C for 20 to 90 minutes. The heating conditions in the pre-baking step can be any conditions that can remove the solvent from the composition, for example, 70°C to 150°C for 30 to 300 seconds. In the step of forming the coating film, known methods such as spin coaters, roll coaters, bar coaters, die coaters, curtain coaters, various printing methods, and dipping can be used to apply the composition. The aforementioned coating film can be formed on a substrate. The aforementioned substrate can be appropriately set according to the intended use of the cured product, and examples include soda glass, quartz glass, semiconductor substrates, wiring boards, metals, paper, plastics, and the like. Furthermore, the cured product may be used either after being formed on the substrate and then peeled off from the substrate, or transferred from the substrate to another adherend.

[0114] F. Pattern The pattern of the present invention includes the above composition C. Furthermore, the resin component contained in composition C is an acid-degradable resin component.

[0115] According to the present invention, by using composition C, compound A decomposes efficiently to generate acid, leading to excellent reactivity in the decomposition reaction and facilitating the decomposition of acid-degradable resin components. As a result, only the acid-degradable resin components are precisely decomposed and removed by solvent cleaning, etc., and the remaining resin that does not decompose can form a pattern with excellent dimensional accuracy.

[0116] The pattern of the present invention uses composition C. Furthermore, the resin component is an acid-degradable resin component. The pattern is formed by creating a coating film using composition C and then removing the unwanted portions. The contents of such compositions can be the same as those described in section "C. Composition" above, so a detailed explanation is omitted here.

[0117] The planar shape of the aforementioned pattern can be appropriately set according to the intended use of the pattern, and can be, for example, a dot pattern, a line pattern, or the like.

[0118] The applications of the aforementioned patterns may be the same as those described in section "A. Compounds" above.

[0119] The method for manufacturing the pattern is not particularly limited as long as it can form the composition C into a desired shape. As an example of such a manufacturing method, the manufacturing method described in section "G. Method for Manufacturing Patterns" below can be used.

[0120] G. Pattern Manufacturing Method Next, the method for manufacturing the pattern of the present invention will be described. The present invention provides a method for producing a pattern, comprising the steps of forming a coating film using composition C, generating an acid from compound A contained in the formed coating film, and developing a portion of the coating film after the step of generating an acid from compound A to form a pattern. The resin component contained in composition C is an acid-degradable resin component. The mechanism of pattern formation is as follows: Acid generated from compound A in composition C promotes the decomposition of the acid-degradable resin component, causing composition C to dissolve in the developer during development. The solubility of composition C in the developer changes depending on the type and presence of the acid generator containing compound A, and the conditions of the acid generation and development processes. This changes the degree to which composition C remains after development, and this difference forms a pattern. In the case of a photoacid generator, by irradiating light through a photomask on which a pattern is drawn, areas are created where light hits and areas where light is blocked by the photomask. Acid is generated only from the photoacid generator in the areas where light hits, so a pattern can be formed that follows the pattern drawn on the photomask.

[0121] According to the present invention, by using composition C, compound A is efficiently decomposed to generate acid, leading to excellent reactivity in the decomposition reaction and facilitating the decomposition of acid-degradable components. As a result, it becomes easier to form patterns with excellent dimensional accuracy and other properties.

[0122] 1. Process to generate acid The step of generating acid in the present invention is the step of generating acid from compound A contained in a coating film formed using composition C. In this process, any method that can generate acid from compound A by decomposing compound A to generate a desired amount of acid is acceptable. Examples include irradiation with energy rays, heat treatment, and performing these simultaneously or sequentially. Such methods, such as irradiation with energy rays and heat treatment, can be the same as those described in section "A. Compound". In this process, it is preferable that the method for generating the acid includes irradiating with energy rays. This is because compound A has excellent absorption of light and excellent photodegradation rate, allowing for efficient acid generation, leading to excellent reactivity in the decomposition reaction and facilitating the decomposition of acid-degradable components. As a result, it becomes easier to form patterns with excellent dimensional accuracy. Furthermore, in this process, it is preferable that the area in the coating film that generates acid is part of the coating film in a plan view. This is because it facilitates the process of forming the pattern described later. The plan view shape and thickness of the coating film are set appropriately according to the application of the patterned coating film. Furthermore, composition C contains an acid-degradable resin component as a resin component. The contents of such a composition can be the same as those described in section "C. Composition" above, so a detailed explanation is omitted here.

[0123] 2. Process of forming a pattern The step of forming a pattern in the present invention is to develop a portion of the coating film after generating an acid from compound A to form a pattern. One method of development in this process is to use a developing solution. The developing solution and developing method can be the same as those described in section E. Method for producing cured products.

[0124] 3. Other processes The method for manufacturing the pattern of the present invention includes the steps of generating the acid and forming the pattern, but may also include other steps as needed. Other such steps include a step of forming a coating film of composition C before the step of generating the acid, a pre-baking step of heat treatment to remove the solvent in the coating film after the step of forming the coating film, and a post-exposure bake step of effectively diffusing the generated acid and promoting the decomposition of acid-degradable components after the step of generating the acid. In the present invention, it is preferable that the other steps include a post-exposure bake step. This is because the acid generated from compound A can be effectively diffused, and the decomposition of acid-degradable components can be carried out more effectively. The steps for forming the coating film and pre-baking can be carried out in the same manner as described in section E. Method for producing cured products. Furthermore, the conditions for the post-exposure baking process can be, for example, 70°C to 150°C for 30 to 300 seconds.

[0125] 4. Others The patterns produced by the above manufacturing method and their uses may be the same as those described in section "A. Compounds" above.

[0126] The present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention. [Examples]

[0127] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0128] [Synthesis Example 1] Synthesis of Compound No. 1 Precursor 4.00 g of thioxanthone-4-carboxylic acid, 2.53 g of carbonyldiimidazole, and 24.38 g of N,N-dimethylformamide (DMF) were charged into a 100 mL four-necked flask, and the temperature was raised to 100°C. After reacting for 3 hours, 1.74 g of 1-butanol was added dropwise, and the mixture was reacted at 70°C for 5 hours. Deionized water was added to quench the mixture, and ethyl acetate was added to separate the oil and water. After four washes by oil-water separation, 、 The solvent was removed using magnesium sulfate, and the residue was purified using silica gel column chromatography (eluent: chloroform) to obtain a white powder with a yield of 3.10 g and a yield of 66%. The peak purity by high-performance liquid chromatography (HPLC) was 99.9%. 1 The target substance was confirmed by 1H-NMR. The measurement conditions for HPLC were as follows (the same conditions were used in synthesis examples 2-5). Column: Inertsil ODS column (φ5μm × 150mm) manufactured by GL Sciences Co., Ltd. Eluent: Acetonitrile / 10 mM n-octanesulfonic acid aqueous solution = volume ratio 8 / 2 Detector: UV-Vis detector, 230nm

[0129] [ka]

[0130] [Synthesis Example 2] Synthesis of Compound No. 1 In a 100 mL four-necked flask, 4.09 g of diphenyliodonium hexafluorophosphate, 3.00 g of thioxanthone-4-carboxylate butyl ester synthesized in Synthesis Example 1, 0.088 g of copper benzoate, and 20.53 g of chlorobenzene were charged, and the mixture was heated to 120°C while stirring. After reacting for 6 hours, the disappearance of the iodonium peak was confirmed by HPLC. After quenching and washing with water by oil-water separation, the solvent was removed by vacuum distillation to obtain an orange viscous substance with a crude yield of 4.84 g and a crude yield of 94%. After column purification with ethyl acetate, crystallization was performed with an acetone / hexane = 3 / 2 volume mixed solution to obtain a white powder with a yield of 1.73 g and a yield of 34%. The peak purity by HPLC (detector absorbance at 230 nm) was >99.9%. 1 The target substance was confirmed by 1H-NMR.

[0131] [ka]

[0132] [Synthesis Example 3] Synthesis of Compound No. 2 In a 100 mL four-necked flask, 1.12 g of compound No. 1, 8.94 g of 15% ammonium tetrakis(pentafluorophenyl) borate aqueous solution, 24 g of EDC (1,2-dichloroethane), and 12 g of deionized water were charged and stirred at room temperature for 3 hours. After oil-water separation, the mixture was washed three times with a water / methanol mixed solution in a 1 / 2 volume ratio. Drying and desolvation with magnesium sulfate yielded a pale yellow powder with a yield of 2.25 g and a yield of 95%. The peak purity by HPLC (detector absorbance 230 nm, cation + anion) was 99.2%.

[0133] [ka]

[0134] [Synthesis Example 4] Synthesis of Compound No. 3 Precursor 1.50 g of thioxanthone-2-carboxylic acid, 0.95 g of carbonyldiimidazole, and 9.14 g of DMF were charged into a 100 mL four-necked flask, and the temperature was raised to 100°C. After reacting for 7 hours, 0.65 g of 1-butanol was added dropwise, and the mixture was reacted for 2.5 hours. Deionized water was added to quench the mixture, and ethyl acetate was added to separate the oil and water. The mixture was washed four times by the oil-water separation process. 、 The sample was dried and desolvated with magnesium sulfate, yielding an orange solid with a crude yield of 1.08 g and a crude yield of 59.0%. Purification by column chromatography (eluent: hexane / ethyl acetate = volume ratio 90 / 10) yielded a white powder with a yield of 1.01 g and a yield of 55%. Peak purity by HPLC (detector absorbance at 230 nm) was 99.8%. 1 The target substance was confirmed by 1H-NMR.

[0135] [ka]

[0136] [Synthesis Example 5] Synthesis of Compound No. 3 In a 100 mL four-necked flask, thioxanthone-2-carboxylate butyl ester synthesized in Synthesis Example 4, 0.95 g of diphenyliodonium hexafluorophosphate, 0.03 g of copper benzoate, and 6.50 g of chlorobenzene were charged and the mixture was heated to 120 °C and reacted for 3.5 hours. The disappearance of the iodonium peak was confirmed by HPLC. Deionized water was added to quench the mixture, followed by oil-water separation and washing with water. The mixture was dried and desolvated with magnesium sulfate to obtain a yellow viscous substance with a crude yield of 1.19 g and a crude yield of 73%. Purification by column chromatography (eluent hexane / ethyl acetate = volume ratio 80 / 20) yielded a pale yellow powder with a yield of 0.31 g and a yield of 19%. The peak purity by HPLC (detector absorbance 230 nm) was 99.0%. 1 The target substance was confirmed by 1H-NMR.

[0137] [ka]

[0138] Compounds No. 1-31 The measurement results of 1H-NMR are shown in Table 1.

Table 1

[0139]

Chemical formula

[0140] [Evaluation: Transmittance before and after exposure] The acid-generating compounds (Compound Nos. 1 to 3, Comparative Compound Nos. 1 to 5) were dissolved in acetonitrile and adjusted so that the compound concentration became 0.1 mmol / L. The adjusted sample was placed in a quartz cell with a lid, and a high-pressure mercury lamp (irradiance: 20 mW / (cm 2 ·s), exposure dose: 1500 mJ / cm 2 ) was irradiated, and the transmittance at 430 nm before and after light irradiation was measured with an ultraviolet-visible spectrophotometer (V-670, manufactured by JASCO Corporation).

[0141]

Table 2

[0142] As shown in Table 2, the transmittance change of the example compounds of the present invention at 430 nm after light irradiation was small. Since the lower the transmittance value at 430 nm, the more yellowish it is, it was found that the example compounds of the present invention have little yellowing.

[0143] [Evaluation: Solubility in resin] Weighed 0.1 g of the acid-generating compounds (Compound Nos. 1 to 3, Comparative Compound Nos. 1 to 5) into a screw tube, and adjusted the addition amount of each resin monomer so that the ratio of the acid-generating compound in the total amount of the acid-generating compound and the resin monomer (liquid) was 50 wt% (acid-generating compound / resin monomer = 0.1 g / 0.1 g, 50 wt%), 40 wt%, 30 wt%, 20 wt%, 10 wt%, 5 wt%, 3 wt%, 1 wt%, and stirred at 25°C for 1 hour. After 1 hour, the insoluble matter was visually confirmed, and the highest concentration at which it dissolved was taken as the solubility. The resin monomers are as follows: Epoxy compound 1: 2-(2-phenoxyethoxy)oxirane Epoxy compound 2: THI-DE (manufactured by ENEOS Corporation) alicyclic epoxy resin Oxetane compound: OXT-101 (manufactured by Toagosei Co., Ltd.)

[0144] [Table 3]

[0145] As shown in Table 3, the example compounds of the present invention were found to exhibit excellent solubility with respect to each resin monomer. Even considering the typical amount of acid-generating compounds added, the fact that the example compounds of the present invention have a solubility of 3 wt% or more relative to the individual resin monomers indicates excellent solubility.

[0146] [Rating: Sensitivity] 1) Phenyl glycidyl ether / acid-generating compounds (compounds No. 1-3, comparative compounds No. 1-5) were mixed and adjusted to a ratio of 100 g / 1 mmol to prepare a sample for curing. 2) Using a micropipette, 30 μL of the curing sample prepared in 1) was placed into an aluminum pan (Open Sample Pan φ5 Aluminum). 3) Aluminum pans containing the samples were placed in a petri dish and exposed to 365nm, 385nm, 395nm, and 405nm LED lamps (illuminance: 20mW / cm²). 2 ·s), exposure: 500 mJ / cm² 2 ) 4) The exposed aluminum pan was placed in a screw tube, covered, and heated in an 80°C oven for 30 minutes. 5) Dissolve the entire sample in the aluminum pan in heavy DMSO. 1 1H-NMR (400 MHz, DMSO-d6, at.rt) was measured. 6) Based on the signal of the phenyl group (7.3 ppm), the epoxy group consumption rate in phenyl glycidyl ether was calculated from the integration ratio of the signals of the epoxy groups (2.7, 2.8 ppm). The higher the epoxy group consumption rate, the more efficiently the acid-generating compound decomposes to release acid, indicating that the released acid reacts with the epoxy group and the polymerization reaction proceeds.

[0147] [Table 4]

[0148] It was found that the example compounds of the present invention showed a high epoxy group consumption rate regardless of the wavelength of light irradiated and were excellent in sensitivity.

[0149] [Evaluation: Resin Composition Evaluation] According to the formulation in Table 5 below, a photocurable resin composition was prepared. The addition amounts of each component in Table 5 are in parts by mass.

[0150] [Table 5]

[0151] Each component in Table 5 is as follows. A-1: Alicyclic epoxy resin THI-DE manufactured byENEOS Corporation B-2: ETERNACOLL (registered trademark) OXBP manufactured by UBE Industries, Ltd. B-3: OXT-221 manufactured by Toagosei Co., Ltd. C-1: Bisphenol A type epoxy resin D-1: Compound No. 1 D-2: Compound No. 3 D-3: Comparative Compound No. 6 D-4: Comparative Compound No. 7 E-1: UVS-2171 (diethoxyanthracene) F-1: KBM-403 manufactured by Shin-Etsu Silicone Co., Ltd.

[0152] [Chemical formula]

[0153] One ml of the photocurable resin composition prepared in the examples and comparative examples in Table 5 above was placed in a bottomed cylindrical container with an inner diameter of 8 mm, and illuminated with an LED at a wavelength of 365 nm and an illuminance of 1000 mW / cm². 2 • Irradiated for 2 seconds (exposure amount: 2J / cm²) 2 The change in elastic modulus over time after light irradiation (after 2 seconds of irradiation is complete = 0 seconds) was measured using a rheometer (manufacturer: Anton Paar, model number: MR302) with a cylindrical plunger with a tip diameter of 3 mm and a gap of 0.3 mm. A faster increase in elastic modulus indicates that polymerization is progressing more rapidly and that the material has high curability. The results of the measurement of elastic modulus over time are shown in Table 6.

[0154] [Table 6]

[0155] The results shown in Table 6 indicate that the example compounds of the present invention exhibit an increased elastic modulus immediately after irradiation, suggesting that the polymerization reaction proceeds quickly upon irradiation and that they have excellent curability.

[0156] [Evaluation: Storage stability] 100 mg each of the acid-generating compounds (compounds No. 1-3, comparative compounds No. 1-3) were weighed into screw-cap tubes, and bisphenol A type epoxy resin was added to adjust the total sample volume to 10 g. The samples were left to stand in the dark at 40°C for 24 hours, then dissolved in acetonitrile at a concentration of 1000 ppm, and the area of ​​the acid-generating compounds was measured by HPLC. The degradation rate of the acid-generating compounds was determined from the area ratio of the acid-generating compounds in the samples before and after standing at 40°C for 24 hours (internal standard method). A lower degradation rate indicates higher storage stability. The measurement conditions for HPLC were as follows: Column: Inertsil ODS column (φ5μm × 150mm) manufactured by GL Sciences Co., Ltd. Eluent: Acetonitrile / 10 mM n-octanesulfonic acid aqueous solution = volume ratio 8 / 2 Detector: UV-Vis detector, 230nm

[0157] [Table 7]

[0158] As shown in Table 7, the example compounds of the present invention were found to have excellent storage stability.

Claims

1. A compound having a structure represented by the following general formula (I). 【Chemistry 1】 (In the formula, X is a direct bond, C(R) １４ ) ２ ,O,CO,S,SO,SO ２ Or NR １４ This represents, R １ 、R ２ 、R ３ 、R ４ 、R ５ 、R ６ 、R ７ 、R ８ 、R ９ 、R １０ 、R １１ 、R １２ and R １３ each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a group represented by the following general formula (II). R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ and R １３ The hydrocarbon groups and heterocyclic groups used in these products either have no substituted hydrogen atoms in the group, or one or more of the hydrogen atoms are halogen atoms, cyano groups, nitro groups, hydroxyl groups, thiol groups, -COOH, -SO4. ３ The group is replaced by H, an isocyanate group, or a hydrocarbon group having 1 to 10 carbon atoms, and one or more methylene groups in the group may be replaced by a divalent group selected from the following <Group I>. R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ and R １３ At least one of them is a group represented by the following general formula (II), Y － This represents a monovalent anion, <Group I>: -O-, -COO-, -OCO-, -CS-, -S-, -SO-, -SO ２ -, -NR １４ -, -NR １４ -CO-, -CO-NR １４ - or - NR １４ -COO- represents, R １４ Each of these independently represents a hydrocarbon group having 1 to 20 carbon atoms, in which one or more of the hydrogen atoms and methylene groups in the group may be substituted with a divalent group selected from Group I, or a heterocyclic group having 2 to 20 carbon atoms, in which one or more of the methylene groups in the group may be substituted with a divalent group selected from Group I. 【Chemistry 2】 (In the formula, Z represents a divalent group selected from the above-mentioned group I, R １５ This represents a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms. * indicates the bonding position with the general formula (I) above.

2. R ２ , R ４ , R ５ and R ７ The compound according to claim 1, wherein at least one selected from is a group represented by the general formula (II).

3. X is CO, The compound according to claim 1, wherein Z is -COO- or -OCO-.

4. Y － BF ４ － , PF ６ － SbF ６ － or [BR ４ ] － The compound according to claim 1. (However, R is a phenyl group in which at least two of the hydrogen atoms in the group are replaced by fluorine atoms or trifluoromethyl groups.)

5. An acid generator containing the compound described in any one of claims 1 to 4.

6. A compound according to any one of claims 1 to 4, Resin components and A composition containing the following:

7. The composition according to claim 6, wherein the resin component is an acid-curable resin component.

8. A cured product of the composition according to claim 6 or 7.

9. A method for producing a cured product, comprising the step of curing the composition according to claim 6 or 7.

10. The composition according to claim 6, wherein the resin component is an acid-degradable resin component.

11. A pattern comprising the composition according to claim 10.

12. A step of forming a coating film using the composition described in claim 10, and generating an acid from the compound contained in the formed coating film, The process involves generating an acid from the compound, followed by developing a portion of the coating film to form a pattern, A method for manufacturing a pattern having the characteristics of a pattern.

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