TW202302528A - Compound, acid generator, composition, cured product, method for producing cured product, pattern, and method for producing pattern - Google Patents

Abstract

Provided is a compound having a structure represented by general formula (A). (In formula (A), Ar is a C5-20 aromatic ring group constituting a ring, R31 represents a group represented by general formula (1), and R32 is a group represented by a formula selected from general formulas (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg), and (IVh); see description for definitions of R33 and a to c.) (See description for disclosures in formulas) (see disclosures in description for symbols in formulas.).

Description

Compound, acid generator, composition, cured product, method for producing cured product, pattern, and method for producing pattern

The present invention relates to a compound suitable for use as an acid generator, an acid generator containing the compound, a composition and its cured product, a method for producing a cured product using the composition, a pattern and a method for producing the pattern.

The acid generator is a substance that generates acid by irradiation of energy rays such as light or heat treatment. Patent Document 1 and Patent Document 2 disclose a photoacid generator or a thermal acid generator containing a sulfonic acid derivative compound as an acid generator. Also, according to Patent Document 1 and Patent Document 2, acid generators are used together with negative-type photoresists, positive-type photoresists, etc., and the above-mentioned negative-type photoresists form chemical bonds such as polymerization or cross-linking due to the acid generated by the acid generator. And so on, so that the solubility in the developer will decrease, and the above-mentioned positive photoresist will increase the solubility in the developer because the chemical bond of the ester group or acetal group is cut off due to the action of acid. Moreover, as specific applications, semiconductors, overcoat coating agents, paints, adhesives, ink applications, and the like are disclosed. prior art literature patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2016-169173 Patent Document 2: US20200183271A1

[Problem to be solved by the invention]

However, these acid generators have room for improvement in acid generation sensitivity.

Therefore, an object of the present invention is to provide a compound excellent in acid generation sensitivity. [Technical means to solve the problem]

The inventors of the present invention conducted earnest research to solve the above-mentioned problems, and as a result, found that an oxime sulfonate compound having a specific structure is excellent in acid generation sensitivity, and completed the present invention.

That is, the present invention is a compound (hereinafter, may be referred to as compound A) having a structure represented by the following general formula (A).

(式中，Ar為構成環之碳原子數為5～20之芳香族環基， R ³¹表示下述通式(1)所表示之基， R ³²為選自下述通式(IVa)、(IVb)、(IVc)、(IVd)、(IVe)、(IVf)、(IVg)及(IVh)中之式所表示之基， R ³³表示鹵素原子、硝基、氰基、-OR ³⁴、-COR ³⁴、-OCOR ³⁴、-COOR ³⁴、-SR ³⁴、-SOR ³⁴、-SO ₂R ³⁴、-NR ³⁵R ³⁶、-NR ³⁵COR ³⁶、-CONR ³⁵R ³⁶、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ia中之二價基而成之基， 於存在複數個R ³¹、R ³²或R ³³之情形時，其等可相同，亦可不同， R ³⁴、R ³⁵及R ³⁶分別獨立地表示氫原子、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ia中之二價基而成之基，於存在複數個R ³⁴、R ³⁵或R ³⁶之情形時，其等可相同，亦可不同， 取代上述具有取代基之烴基及上述具有取代基之含有雜環之基中之1個以上氫原子的取代基為選自下述群IIa中之原子或基， a表示1～20之整數， b表示1～20之整數， c表示0～18之整數， a、b及c之合計為21以下) [化2]

(式中，R ¹表示碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ia中之二價基而成之基， R ²表示氫原子、鹵素原子、硝基、氰基、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ia中之二價基而成之基， 取代上述具有取代基之烴基及上述具有取代基之含有雜環之基中之1個以上氫原子的取代基為選自下述群IIa中之原子或基， *表示鍵結部位) [化3]

(式中，R ⁵¹表示OR ⁸¹、NR ⁸²R ⁸³或碳原子數2～20之未經取代或具有取代基之含有雜環之基， R ⁵²及R ⁵³分別獨立地表示R ⁸¹或OR ⁸¹，R ⁵²與R ⁵³可鍵結而形成環， R ⁵⁵、R ⁵⁶、R ⁵⁸、R ⁵⁹、R ⁶¹、R ⁶²、R ⁶⁴、R ⁶⁵、R ⁷¹及R ⁷³表示碳原子數6～20之未經取代或具有取代基之芳基， R ⁵⁴、R ⁵⁷、R ⁶⁰、R ⁶³、R ⁶⁶、R ⁶⁷及R ⁷²分別獨立地表示碳原子數6～20之未經取代或具有取代基之伸芳基或單鍵， R ⁶⁸表示碳原子數1～20之未經取代或具有取代基之烴基， R ⁶⁹及R ⁷⁰分別獨立地表示R ⁸¹或OR ⁸¹， R ⁸¹、R ⁸²及R ⁸³分別獨立地表示氫原子或碳原子數1～20之未經取代或具有取代基之烴基， *表示鍵結部位) (群Ia：-O-、-COO-、-OCO-、-CO-、-CO-CO-、-CO-CO-O-、-CS-、-S-、-SO-、-SO ₂-、-NR'-、-NR'-CO-、-CO-NR'-、-NR'-COO-、-OCO-NR'-或-SiR'R''-。 群IIa：鹵素原子、氰基、硝基、-CO-H、-OH、-SH、-NH ₂、-COOH或-SO ₃H。 R'及R''分別獨立地表示氫原子或碳原子數1～20之未經取代之脂肪族烴基，於存在複數個R'或R''之情形時，其等可相同，亦可不同) [chemical 1]

(In the formula, Ar is an aromatic ring group with 5 to 20 carbon atoms constituting the ring, R ³¹ represents a group represented by the following general formula (1), R ³² is selected from the following general formula (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) and (IVh) in the group represented by the formula, R ³³ represents a halogen atom, nitro, cyano, -OR ³⁴ , -COR ³⁴ , -OCOR ³⁴ , -COOR ³⁴ , -SR ³⁴ , -SOR ³⁴ , -SO ₂ R ³⁴ , -NR ³⁵ R ³⁶ , -NR ³⁵ COR 36 , -CONR 35 R ³⁶ , -CONR ³⁵ R ³⁶ , carbon number 1～ 20 unsubstituted or substituted hydrocarbon groups, unsubstituted or substituted heterocyclic ring-containing groups having 2 to 20 carbon atoms, or one or more methylene groups among the above-mentioned hydrocarbon groups or the above-mentioned heterocyclic ring-containing groups The group is substituted with a divalent group selected from the following group Ia. When there are a plurality of R ³¹ , R ³² or R ³³ , they may be the same or different, R ³⁴ , R ³⁵ and ^R36 independently represent a hydrogen atom, an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group with 2 to 20 carbon atoms, or the above-mentioned A hydrocarbon group or a group in which at least one methylene group is substituted with a divalent group selected from the group Ia below, when there are multiple R ³⁴ , R ³⁵ or R ³⁶ , which may be the same or different, and the substituents substituting one or more hydrogen atoms in the above-mentioned hydrocarbon group with substituents and the above-mentioned heterocyclic ring-containing group with substituents are atoms or groups selected from the following group IIa , a represents an integer of 1 to 20, b represents an integer of 1 to 20, c represents an integer of 0 to 18, and the total of a, b and c is 21 or less) [Chemical 2]

(wherein, R ¹ represents an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group with 2 to 20 carbon atoms, or the above hydrocarbon group or the above A group in which one or more methylene groups in a group containing a heterocycle is substituted with a divalent group selected from the following group Ia, ^R2 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, and the number of carbon atoms Unsubstituted or substituted hydrocarbon groups with 1 to 20 carbon atoms, unsubstituted or substituted heterocycle-containing groups with 2 to 20 carbon atoms, or one or more of the above-mentioned hydrocarbon groups or the above-mentioned heterocycle-containing groups A substituent in which a methylene group is substituted with a divalent group selected from the following group Ia, substituting one or more hydrogen atoms in the above-mentioned hydrocarbon group with a substituent and the above-mentioned heterocyclic ring-containing group with a substituent is an atom or group selected from the following group IIa, * represents a bonding site) [Chem. 3]

(In the formula, R ⁵¹ represents OR ⁸¹ , NR ⁸² R ⁸³ or an unsubstituted or substituted heterocyclic group with 2 to 20 carbon atoms, R ⁵² and R ⁵³ independently represent R ⁸¹ or OR ⁸¹ , R ⁵² and R ⁵³ can be bonded to form a ring, R ⁵⁵ , R ⁵⁶ , R ⁵⁸ , R ⁵⁹ , R ⁶¹ , R ⁶² , R ⁶⁴ , R ⁶⁵ , R ⁷¹ and R ⁷³ represent carbon atoms of 6 to 20 For an unsubstituted or substituted aryl group, R ⁵⁴ , R ⁵⁷ , R ⁶⁰ , R ⁶³ , R ⁶⁶ , R ⁶⁷ and R ⁷² each independently represent an unsubstituted or substituted aryl group with 6 to 20 carbon atoms. An aryl group or a single bond, R ⁶⁸ represents an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, R ⁶⁹ and R ⁷⁰ independently represent R ⁸¹ or OR ⁸¹ , R ⁸¹ , R ⁸² and R ⁸³ Each independently represents a hydrogen atom or an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, and * represents a bonding site) (Group Ia: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO ₂ -, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R''-. Group IIa: Halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH ₂ , - COOH or -SO ₃ H. R' and R'' each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group with 1 to 20 carbon atoms. When there are multiple R' or R'', the can be the same or different)

Also, the present invention provides an acid generator containing the above compound, a composition of the above compound, a cured product of the composition, a method for producing a cured product that hardens the composition, a pattern using the composition, and a method for producing the pattern. [Effect of Invention]

According to the present invention, a compound excellent in acid generation sensitivity can be provided. In addition, the compound of the present invention is also excellent in that the transmittance of light in the visible light region is high in a pattern produced from a composition using the same. Furthermore, the present invention provides an acid generator having a high acid generation sensitivity using the compound, a composition of the compound, a cured product of the composition, a method for producing a cured product obtained by curing the composition, and a pattern using the composition and methods of making patterns.

The present invention relates to a compound, an acid generator, a composition, a cured product, a method for producing the cured product, a pattern and a method for producing the pattern. Hereinafter, the present invention will be described in detail.

A. Compound First, the compounds of the present invention will be described. One of the characteristics of the compound of the present invention is that it has a structure represented by the following general formula (A). In the present embodiment, the compound of the present invention is represented by the following general formula (A).

(式中，Ar為構成環之碳原子數為5～20之芳香族環基， R ³¹表示下述通式(1)所表示之基， R ³²為選自下述通式(IVa)、(IVb)、(IVc)、(IVd)、(IVe)、(IVf)、(IVg)及(IVh)中之式所表示之基， R ³³表示鹵素原子、硝基、氰基、-OR ³⁴、-COR ³⁴、-OCOR ³⁴、-COOR ³⁴、-SR ³⁴、-SOR ³⁴、-SO ₂R ³⁴、-NR ³⁵R ³⁶、-NR ³⁵COR ³⁶、-CONR ³⁵R ³⁶、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ia中之二價基而成之基， 於存在複數個R ³¹、R ³²或R ³³之情形時，其等可相同，亦可不同， R ³⁴、R ³⁵及R ³⁶分別獨立地表示氫原子、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ia中之二價基而成之基，於存在複數個R ³⁴、R ³⁵或R ³⁶之情形時，其等可相同，亦可不同， 取代上述具有取代基之烴基及上述具有取代基之含有雜環之基中之1個以上氫原子的取代基為選自下述群IIa中之原子或基， a表示1～20之整數， b表示1～20之整數， c表示0～18之整數， a、b及c之合計為21以下) [chemical 4]

(In the formula, Ar is an aromatic ring group with 5 to 20 carbon atoms constituting the ring, R ³¹ represents a group represented by the following general formula (1), R ³² is selected from the following general formula (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) and (IVh) in the group represented by the formula, R ³³ represents a halogen atom, nitro, cyano, -OR ³⁴ , -COR ³⁴ , -OCOR ³⁴ , -COOR ³⁴ , -SR ³⁴ , -SOR ³⁴ , -SO ₂ R ³⁴ , -NR ³⁵ R ³⁶ , -NR ³⁵ COR 36 , -CONR 35 R ³⁶ , -CONR ³⁵ R ³⁶ , carbon number 1～ 20 unsubstituted or substituted hydrocarbon groups, unsubstituted or substituted heterocyclic ring-containing groups having 2 to 20 carbon atoms, or one or more methylene groups among the above-mentioned hydrocarbon groups or the above-mentioned heterocyclic ring-containing groups The group is substituted with a divalent group selected from the following group Ia. When there are a plurality of R ³¹ , R ³² or R ³³ , they may be the same or different, R ³⁴ , R ³⁵ and ^R36 independently represent a hydrogen atom, an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group with 2 to 20 carbon atoms, or the above-mentioned A hydrocarbon group or a group in which at least one methylene group is substituted with a divalent group selected from the group Ia below, when there are multiple R ³⁴ , R ³⁵ or R ³⁶ , which may be the same or different, and the substituents substituting one or more hydrogen atoms in the above-mentioned hydrocarbon group with substituents and the above-mentioned heterocyclic ring-containing group with substituents are atoms or groups selected from the following group IIa , a represents an integer from 1 to 20, b represents an integer from 1 to 20, c represents an integer from 0 to 18, and the total of a, b and c is 21 or less)

(式中，R ¹表示碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ia中之二價基而成之基， R ²表示氫原子、鹵素原子、硝基、氰基、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ia中之二價基而成之基， 取代上述具有取代基之烴基及上述具有取代基之含有雜環之基中之1個以上氫原子的取代基為選自下述群IIa中之原子或基， *表示鍵結部位) [化6]

(式中，R ⁵¹表示OR ⁸¹、NR ⁸²R ⁸³或碳原子數2～20之未經取代或具有取代基之含有雜環之基， R ⁵²及R ⁵³分別獨立地表示R ⁸¹或OR ⁸¹，R ⁵²與R ⁵³可鍵結而形成環， R ⁵⁵、R ⁵⁶、R ⁵⁸、R ⁵⁹、R ⁶¹、R ⁶²、R ⁶⁴、R ⁶⁵、R ⁷¹及R ⁷³表示碳原子數6～20之未經取代或具有取代基之芳基， R ⁵⁴、R ⁵⁷、R ⁶⁰、R ⁶³、R ⁶⁶、R ⁶⁷及R ⁷²分別獨立地表示碳原子數6～20之未經取代或具有取代基之伸芳基或單鍵， R ⁶⁸表示碳原子數1～20之未經取代或具有取代基之烴基， R ⁶⁹及R ⁷⁰分別獨立地表示R ⁸¹或OR ⁸¹， R ⁸¹、R ⁸²及R ⁸³分別獨立地表示氫原子或碳原子數1～20之未經取代或具有取代基之烴基， *表示鍵結部位) (群Ia：-O-、-COO-、-OCO-、-CO-、-CO-CO-、-CO-CO-O-、-CS-、-S-、-SO-、-SO ₂-、-NR'-、-NR'-CO-、-CO-NR'-、-NR'-COO-、-OCO-NR'-或-SiR'R''-。 群IIa：鹵素原子、氰基、硝基、-CO-H、-OH、-SH、-NH ₂、-COOH或-SO ₃H。 R'及R''分別獨立地表示氫原子或碳原子數1～20之未經取代之脂肪族烴基，於存在複數個R'或R''之情形時，其等可相同，亦可不同) [chemical 5]

(wherein, R ¹ represents an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group with 2 to 20 carbon atoms, or the above hydrocarbon group or the above A group in which one or more methylene groups in a group containing a heterocycle is substituted with a divalent group selected from the following group Ia, ^R2 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, and the number of carbon atoms Unsubstituted or substituted hydrocarbon groups with 1 to 20 carbon atoms, unsubstituted or substituted heterocycle-containing groups with 2 to 20 carbon atoms, or one or more of the above-mentioned hydrocarbon groups or the above-mentioned heterocycle-containing groups A substituent in which a methylene group is substituted with a divalent group selected from the following group Ia, substituting one or more hydrogen atoms in the above-mentioned hydrocarbon group with a substituent and the above-mentioned heterocyclic ring-containing group with a substituent is an atom or group selected from the following group IIa, * represents a bonding site) [Chem. 6]

(In the formula, R ⁵¹ represents OR ⁸¹ , NR ⁸² R ⁸³ or an unsubstituted or substituted heterocyclic group with 2 to 20 carbon atoms, R ⁵² and R ⁵³ independently represent R ⁸¹ or OR ⁸¹ , R ⁵² and R ⁵³ can be bonded to form a ring, R ⁵⁵ , R ⁵⁶ , R ⁵⁸ , R ⁵⁹ , R ⁶¹ , R ⁶² , R ⁶⁴ , R ⁶⁵ , R ⁷¹ and R ⁷³ represent carbon atoms of 6 to 20 For an unsubstituted or substituted aryl group, R ⁵⁴ , R ⁵⁷ , R ⁶⁰ , R ⁶³ , R ⁶⁶ , R ⁶⁷ and R ⁷² each independently represent an unsubstituted or substituted aryl group with 6 to 20 carbon atoms. An aryl group or a single bond, R ⁶⁸ represents an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, R ⁶⁹ and R ⁷⁰ independently represent R ⁸¹ or OR ⁸¹ , R ⁸¹ , R ⁸² and R ⁸³ Each independently represents a hydrogen atom or an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, and * represents a bonding site) (Group Ia: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO ₂ -, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R''-. Group IIa: Halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH ₂ , - COOH or -SO ₃ H. R' and R'' each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group with 1 to 20 carbon atoms. When there are multiple R' or R'', the can be the same or different)

According to the present invention, the above-mentioned compound A has a diketone group, etc. selected from the above-mentioned general formulas (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) and (IVh) (hereinafter , also referred to as the group represented by the formula in "Formula (IVa)～(IVh)") (hereinafter, sometimes described as "IVa group, etc.") and the group represented by the above-mentioned general formula (1), so the acid generates Excellent sensitivity. Here, the reason why the acid generation sensitivity is excellent is not clear, but it is estimated as follows. The above-mentioned compound A includes a structure (hereinafter, sometimes referred to as a specific structure) having an IVa group etc. and a group represented by the above-mentioned general formula (1), so the light absorption efficiency near 365 nm is increased. Furthermore, the structure of the formula (1) corresponding to an acid generating site is excellent in acid generating ability. Therefore, Compound A is excellent in acid generation efficiency. Compared with the compound which does not have the combination of IVa group etc. and the group represented by the said general formula (1) with the said specific structure, desired sensitivity can be acquired even if it adds a small amount. As a result, the above composition was excellent in acid generation sensitivity. In addition, the above-mentioned compound A has a high transmittance of light in the visible light region due to the presence of the IVa group and the like. Therefore, it can be suitably used for the resin composition for member formation which requires transparency.

Hereinafter, the compound A of this invention is demonstrated in detail.

As a halogen atom in the said general formula (A), a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

Carbon atoms in the above general formula (A), formula (1), formula (IVa) to (IVh), (Ara), (Arb), (Ara1) and (Arb1), and the following (A1) to (A3) The hydrocarbon group of 1 to 20 is a hydrocarbon group not containing an aromatic hydrocarbon ring or a heterocycle, and may have a substituent. The hydrocarbon group having a substituent is a group having a structure in which one or more hydrogen atoms in the hydrocarbon group are replaced by substituents. As the unsubstituted hydrocarbon group, for example, preferably an aliphatic hydrocarbon group, specifically, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkenyl group having 3 carbon atoms Cycloalkyl with ∼20 carbon atoms, cycloalkylalkyl with 4 to 20 carbon atoms. In addition, as the above-mentioned hydrocarbon group having a substituent, one or more hydrogen atoms in the above-mentioned unsubstituted hydrocarbon group are substituted by a substituent, etc., and the substituent is, for example, selected from the above-mentioned group IIa, Atoms or groups in group IIb or group IIc, ie halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH ₂ , -COOH or -SO ₃ H.

The above-mentioned alkyl group having 1 to 20 carbon atoms may be linear or branched. As a linear alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a heptyl group, and an octyl group are mentioned. Examples of branched alkyl groups include isopropyl, second-butyl, third-butyl, isobutyl, isopentyl, third-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, isoheptyl, third heptyl, isooctyl, third octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, deca Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, etc.

The alkenyl group having 2 to 20 carbon atoms may be linear or branched. Also, it may be a terminal alkenyl group having an unsaturated bond at the end, or an internal alkenyl group having an unsaturated bond inside. As a terminal alkenyl group, a vinyl group, an allyl group, 2-methyl-2-propenyl group, 3-butenyl group, 4-pentenyl group, 5-hexenyl group etc. are mentioned, for example. Examples of internal alkenyl include: 2-butenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptene 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl and 4,8,12-tetradecatrienyl allyl Base etc.

Examples of the aforementioned cycloalkyl group having 3 to 20 carbon atoms include saturated monocyclic alkyl groups having 3 to 20 carbon atoms, saturated polycyclic alkyl groups having 3 to 20 carbon atoms, and combinations thereof. A group having 4 to 20 carbon atoms in which one or more hydrogen atoms in the ring are substituted with an alkyl group. As said saturated monocyclic alkyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group etc. are mentioned, for example. As said saturated polycyclic alkyl group, an adamantyl group, a decahydronaphthyl group, an octahydropentadiene group, a bicyclo[1.1.1]pentyl group, etc. are mentioned. As the alkyl group substituting the hydrogen atom in the ring of the saturated monocyclic or saturated polycyclic alkyl group, those exemplified as the above-mentioned alkyl group having 1 to 20 carbon atoms may be mentioned. The group in which one or more hydrogen atoms in the ring of the saturated polycyclic alkyl group is substituted with an alkyl group includes, for example, a thiol group and the like.

The aforementioned cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which hydrogen atoms of the alkyl group are substituted with cycloalkyl groups. The cycloalkyl group in the cycloalkylalkyl group may be monocyclic or polycyclic. The cycloalkyl group is a monocyclic cycloalkylalkyl group having 4 to 20 carbon atoms, for example: cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4- Cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononylethyl, 2-cyclodecanylethyl, etc. As the cycloalkyl group, a polycyclic cycloalkylalkyl group having 4 to 20 carbon atoms may, for example, be 3-3-adamantylpropyl or decahydronaphthylpropyl.

Examples of groups in which one or more hydrogen atoms in the unsubstituted hydrocarbon group are replaced by substituents and the substituents are halogen atoms include: trifluoromethyl, pentafluoroethyl, 2-chloroethyl, 2- Bromoethyl, heptafluoropropyl, 3-bromopropyl, nonafluorobutyl, tridecafluorohexyl, heptadecafluorooctyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl , 1,1-difluoropropyl, 1,1,2,2-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 7H -Alkyl halides such as dodecafluorohexyl; nor-1,1-difluoroethyl, nor-1,1-tetrafluoroethyl, adamantane-1,1,2,2-tetrafluoropropyl, bicyclo[2.2 .1] heptane-tetrafluoromethyl and other halogenated cycloalkyl groups or halogenated cycloalkylalkyl groups, etc.

Furthermore, in this specification, as the unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R' and R'', there may be exemplified the same as those mentioned above as the hydrocarbon group having 1 to 20 carbon atoms. The bases of the examples are the same bases.

In the present invention, regarding the number of carbon atoms in a group, when a hydrogen atom in the group is replaced by a substituent, the number of carbon atoms in the substituted group is specified. For example, when the hydrogen atom of the above-mentioned alkyl group with 1 to 20 carbon atoms is replaced, the number of carbon atoms with 1 to 20 refers to the number of carbon atoms after the hydrogen atom is replaced, not the carbon number before the hydrogen atom is replaced. atomic number. Also, in the present invention, regarding the carbon number of a group in which a methylene group is substituted with a divalent group in a group having a specific number of carbon atoms, the number of carbon atoms of the group before the substitution is specified. For example, in this specification, the number of carbon atoms in a group in which the methylene group in an alkyl group with 1 to 20 carbon atoms is replaced by a divalent group is considered to satisfy 1 regardless of the number of carbon atoms after the substitution. ~20 regulations. Among them, it is preferred that the number of carbon atoms of the group substituted with methylene meet the requirement of the number of carbon atoms of the group before substitution.

Carbon atoms in the above general formula (A), formula (1), formula (IVa) to (IVh), (Ara), (Arb), (Ara1) and (Arb1), and the following (A1) to (A3) The heterocyclic ring-containing group numbered from 2 to 20 is a heterocyclic group or a group in which a heterocyclic ring is bonded to a hydrocarbon group, and may have an aromatic hydrocarbon ring-containing group, an aliphatic hydrocarbon group, or a substituent. In a group in which a heterocyclic ring is bonded to a hydrocarbon group, the bonding bond may exist on the heterocyclic ring or on the hydrocarbon group. The heterocycle-containing group having a substituent is a group having a structure in which one or more hydrogen atoms in the heterocycle-containing group are substituted with substituents. The definition of "2 to 20 carbon atoms" means the total number of carbon atoms in a group containing a heterocyclic ring. In the case of a group formed by bonding a heterocyclic ring and a hydrocarbon group, not only the heterocyclic ring but also the carbon atoms of the hydrocarbon group are included. The number is counted in.

Examples of unsubstituted heterocycle-containing groups include pyridyl, quinolinyl, thiazolyl, tetrahydrofuryl, dioxolanyl, tetrahydropyranyl, thiolinylfuryl, thienyl, methyl Base thienyl, hexyl thienyl, benzothienyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolinyl, piperidinyl, piperyl, pyrimidinyl , furyl, thienyl, benzoxazol-2-yl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxazolyl and other heterocyclic groups, and one or more hydrogen atoms of the alkyl group are replaced A group formed by substituting a heterocyclic ring, etc. In addition, as the above-mentioned heterocycle-containing group having a substituent, a group in which one or more hydrogen atoms in the above-mentioned unsubstituted above-mentioned heterocycle-containing group is substituted with a substituent, etc., as the substituent, Examples thereof include a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH ₂ , -COOH, or -SO ₃ H and the like.

Furthermore, the unsubstituted heterocycle-containing group may be one in which a heterocycle is linked to an aromatic hydrocarbon ring of a monocyclic structure, or one in which a heterocycle is linked to an aromatic hydrocarbon ring of a condensed ring structure. As a linking group which connects two aromatic hydrocarbon rings, a single bond, a carbonyl group, etc. are mentioned. Examples of the heterocyclic ring-containing group in which a heterocyclic ring is linked to an aromatic hydrocarbon ring of a monocyclic structure include benzothiophene and the like.

Above-mentioned general formula (A), formula (1), formula (IVa)～(IVh), (Ara), (Arb), (Ara1) and (Arb1), the above-mentioned hydrocarbyl in following (A1)～(A3) Or a group in which one or more methylene groups in the group containing a heterocyclic ring is substituted by a divalent group selected from the group Ia, Ib or Ic above does not have a structure in which a plurality of the divalent groups are adjacent . The plurality of divalent groups referred to here may be the same or different.

One or more methylene groups as the above-mentioned hydrocarbon group are substituted with a divalent group selected from the group Ia, Ib, or Ic above, for example, the methylene group in the thiol group as the hydrocarbon group is substituted The base formed for -CO- is 10-camphor base.

Examples of the unsubstituted aryl group having 6 to 20 carbon atoms in the formulas (IVa) to (IVh) include phenyl, methylphenyl, ethylphenyl, naphthyl and the like. The unsubstituted arylylene group having 6 to 20 carbon atoms in the formulas (IVa) to (IVh) may, for example, be phenylene, methylphenylene, ethylphenylene or naphthylene. As the substituent in the aryl group having a substituent and the substituent in the aryl group, a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH ₂ , -COOH or -SO may be mentioned. ₃ H et al.

In the above general formula (A) that compound A has, a is preferably 1-20, more preferably 1-10, still more preferably 1 or 2, most preferably 1. This is because compound A becomes a compound more excellent in acid generation sensitivity by making a into the said number. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity. b in the above-mentioned general formula (A) that compound A has is preferably 1-20, more preferably 1-10, still more preferably 1 or 2, most preferably 1. This is because compound A becomes a compound more excellent in acid generation sensitivity by setting b to the said number. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity. In the above-mentioned general formula (A) that compound A has, c is preferably 0-18, more preferably 0-10, still more preferably 0-3, still more preferably 0 or 1. This is because compound A becomes a compound more excellent in acid generation sensitivity by making c into the said number. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity. The total of a, b, and c is preferably 21 or less, more preferably 10 or less, still more preferably 5 or less, most preferably 2 or more and 3 or less, on the premise that the number that can be bonded to the aromatic ring group Ar is used. This is because compound A becomes a compound more excellent in acid generation sensitivity by setting the total of a, b, and c to the above-mentioned number. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

In formula (A), R ³¹ , R ³² and R ³³ are all bonded to the aromatic ring constituting the aromatic ring group. In the present invention, R ³¹ is a group represented by the above general formula (1). The substituent substituting one or more hydrogen atoms in the above-mentioned hydrocarbon group having a substituent represented by R in the above-mentioned general formula ( ¹ ) and the above-mentioned heterocyclic ring-containing group having a substituting group is preferably a halogen atom, more preferably fluorine atom. The reason for this is that it is easy to form an acid generator excellent in acid generation sensitivity. R ¹ of the above-mentioned general formula (1) is preferably an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, or one or more methylene groups in the above-mentioned hydrocarbon group are substituted to be selected from the following group Ia Among them, it is preferably a hydrocarbon group with a substituent having 1 to 20 carbon atoms, particularly preferably a hydrocarbon group with a substituent having 1 to 20 carbon atoms, and it replaces the above-mentioned substituent The substituent of one or more hydrogen atoms of the hydrocarbon group is a halogen atom. This is because it is easy to synthesize, and it is easy to form an acid generator excellent in acid generation sensitivity. The hydrocarbon group represented by R ¹ of the above general formula (1) is preferably a straight-chain or branched-chain alkyl group. The number of carbon atoms of the group represented by R ¹ in the general formula (1) is preferably 1-10, and among them, 1-5 are more preferable. This is because it is easy to synthesize, and it is easy to form an acid generator excellent in acid generation sensitivity. Among them, in the present invention, R in the above general formula ( ¹ ) is preferably a group in which more than one hydrogen atom in an alkyl group with 1 to 20 carbon atoms is replaced by a halogen atom, that is, a group with 1 to 20 carbon atoms. 20. The halogenated alkyl group of 20, among them, the group wherein at least one hydrogen atom in the alkyl group having 1 to 10 carbon atoms is substituted with a halogen atom is preferably a halogenated alkyl group having 1 to 10 carbon atoms, More preferably, all hydrogen atoms in an alkyl group with 1 to 5 carbon atoms are replaced by halogen atoms, that is, a perhaloalkyl group with 1 to 5 carbon atoms, most preferably an alkane with 1 to 5 carbon atoms A group in which all hydrogen atoms in the group are replaced by fluorine atoms is a perfluoroalkyl group with 1 to 5 carbon atoms. This is because compound A is a compound particularly excellent in acid generation sensitivity by having such a structure for R ¹ . Also, among them, in the present invention, R in the above general formula ( ¹ ) is preferably a perfluoroalkyl group having 1 to 4 carbon atoms, particularly preferably Among the perfluoroalkyl groups having 1 to 2 carbon atoms, trifluoromethyl groups which are perfluoroalkyl groups having 1 carbon atoms are particularly preferred.

The substituent substituting one or more hydrogen atoms in the above-mentioned hydrocarbon group having a substituent represented by R in the general formula ( ¹ ) and the above-mentioned heterocyclic ring-containing group having a substituting group is preferably a halogen atom, more preferably fluorine Atom or chlorine atom, more preferably fluorine atom. The reason for this is that it is easy to form an acid generator excellent in acid generation sensitivity. R of the above-mentioned general formula ( ¹ ) is more preferably a cyano group, an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, or one or more methylene groups of the above-mentioned hydrocarbon group are substituted to be selected from the group Ia above The group formed by the divalent group among them is more preferably a cyano group, an unsubstituted hydrocarbon group with 1 to 20 carbon atoms or a halogen atom as a substituent, or the above-mentioned unsubstituted hydrocarbon group or a halogen atom as a substituent A group in which one or more methylene groups are substituted with -COO-, among them, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms having a halogen atom as a substituent, or the above-mentioned unsubstituted or A group in which one or more methylene groups in a hydrocarbon group having a halogen atom as a substituent is substituted with -COO-, particularly preferably a cyano group or a hydrocarbon group having a halogen atom as a substituent having 1 to 20 carbon atoms, wherein , particularly preferably a hydrocarbon group having 1 to 20 carbon atoms having a halogen atom as a substituent. The reason for this is that it is easy to form an acid generator excellent in acid generation sensitivity. The hydrocarbon group represented by R ² of the above general formula (1) is preferably a linear or branched chain alkyl group. The number of carbon atoms of the group represented by R ² in the general formula (1) is preferably 1-10, and among them, 1-5 are more preferable. This is because it is easy to synthesize, and it is easy to form an acid generator excellent in acid generation sensitivity. Among them, in the present invention, R in the above general formula (1) is preferably a group in which more than one hydrogen atom in an alkyl group with 1 to 20 carbon atoms is replaced by a halogen atom, that is ^, a group with 1 to 20 carbon atoms. 20. The halogenated alkyl group of 20, among them, the group wherein at least one hydrogen atom in the alkyl group having 1 to 10 carbon atoms is substituted with a halogen atom is preferably a halogenated alkyl group having 1 to 10 carbon atoms, More preferably, a group in which all hydrogen atoms in an alkyl group with 1 to 5 carbon atoms are replaced by halogen atoms is a perhaloalkyl group with 1 to 5 carbon atoms, and more preferably a perhaloalkyl group with 1 to 5 carbon atoms. A group in which all the hydrogen atoms in the alkyl group are substituted with chlorine atoms or fluorine atoms, and among them, a perfluoroalkyl group having 1 to 5 carbon atoms is preferable. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity by making R ² such a structure. Also, among them, in the present invention, R in the above-mentioned general formula ( ¹ ) is preferably a perfluoroalkyl group having 1 to 3 carbon atoms, particularly preferably Among the perfluoroalkyl groups having 1 to 2 carbon atoms, trifluoromethyl groups which are perfluoroalkyl groups having 1 carbon atoms are particularly preferred.

R ³² is preferably a group represented by a formula selected from the above general formulas (IVa), (IVf) and (IVh), particularly preferably a group represented by general formula (IVf). The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity. R ⁶⁷ of the above general formula (IVf) is preferably a single bond. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity. In addition, ^R68 is preferably an unsubstituted or substituted hydrocarbon group with 1 to 10 carbon atoms, among which, it is preferably an unsubstituted or substituted hydrocarbon group with 1 to 5 carbon atoms, especially preferably It is an unsubstituted or substituted hydrocarbon group having 1 to 3 carbon atoms, preferably an unsubstituted hydrocarbon group having 1 to 3 carbon atoms. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity. In addition, at least one of R ³³ is preferably an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or one of the above-mentioned hydrocarbon groups from the viewpoint of easily imparting various functions to the compound (A). One or more methylene groups are substituted with divalent groups selected from Group Ia below.

The aromatic ring in the aromatic ring group Ar having 5 to 20 carbon atoms constituting the ring may be a single ring with five to seven members or a condensed ring. Examples of the monocyclic ring include monocyclic cycloalkanes such as cyclopentane, cyclohexane, and cyclopentene, monocyclic aromatic rings such as benzene, pyrrolidine, pyrrole, piperidine, thiophene, and thiophene. Monocyclic heterocycles such as morphine, tetrahydropyridine, lactone ring and lactamide ring. The condensed ring may, for example, be naphthalene, anthracene, carbazole or fennel. The aromatic ring group Ar may have a linked ring structure in which a plurality of aromatic rings are linked by direct bonds or -S-, -O-, nitrogen atoms, and the like. For example, in the case of linking rings, the number of hydrocarbons constituting the rings of 5 to 20 is the total number of carbon atoms constituting all the rings included in Ar. For example, the number of carbon atoms constituting the carbazole ring is 12, and the number of carbon atoms constituting the oxene ring is 13. When the aromatic ring group Ar has a condensed ring, it is preferable that R ³¹ , R ³² , and R ³³ are bonded to the same fused ring.

The aromatic ring group Ar is preferably an aromatic ring group having a structure represented by the following general formula (Ara) or (Arb). The reason for this is that Compound A becomes a compound more excellent in acid generation sensitivity.

(式中，X ¹為單鍵、無鍵、氧原子、硫原子、硒原子、CR ⁴¹R ⁴²、CO、NR ⁴³或PR ⁴⁴， X ²為氧原子、硫原子、硒原子、CR ⁴¹R ⁴²、CO、NR ⁴³或PR ⁴⁴， X ³為NR ⁵³， R ⁴¹、R ⁴²、R ⁴³及R ⁴⁴分別獨立地表示氫原子、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ib中之二價基而成之基，於存在複數個R ⁴¹、R ⁴²、R ⁴³及R ⁴⁴之情形時，其等可相同，亦可不同， R ⁵³表示氫原子、鹵素原子、硝基、氰基、-OR ¹¹¹、-COR ¹¹¹、-OCOR ¹¹¹、-COOR ¹¹¹、-SR ¹¹¹、-SOR ¹¹¹、-SO ₂R ¹¹¹、-NR ¹¹²R ¹¹³、-NR ¹¹²COR ¹¹³、-CONR ¹¹²R ¹¹³、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ib中之二價基而成之基， R ¹¹¹、R ¹¹²及R ¹¹³分別獨立地表示氫原子、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ib中之二價基而成之基，於分別存在複數個R ¹¹¹、R ¹¹²及R ¹¹³之情形時，其等可相同，亦可不同， 取代上述具有取代基之烴基及上述具有取代基之含有雜環之基中之1個以上氫原子的取代基為選自下述群IIb中之原子或基) (群Ib：-O-、-COO-、-OCO-、-CO-、-CO-CO-、-CO-CO-O-、-CS-、-S-、-SO-、-SO ₂-、-NR'-、-NR'-CO-、-CO-NR'-、-NR'-COO-、-OCO-NR'-或-SiR'R''-。 群IIb：鹵素原子、氰基、硝基、-CO-H、-OH、-SH、-NH ₂、-COOH或-SO ₃H。 R'及R''分別獨立地表示氫原子或碳原子數1～20之未經取代之脂肪族烴基，於存在複數個R'或R''之情形時，其等可相同，亦可不同) [chemical 7]

(In the formula, X ¹ is a single bond, no bond, oxygen atom, sulfur atom, selenium atom, CR ⁴¹ R ⁴² , CO, NR ⁴³ or PR ⁴⁴ , X ² is an oxygen atom, sulfur atom, selenium atom, CR ⁴¹ R 44 ⁴² , CO, NR ⁴³ or PR ⁴⁴ , X ³ is NR ⁵³ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom, an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms , an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or one or more methylene groups in the above-mentioned hydrocarbon group or the above-mentioned heterocyclic ring-containing group are substituted to be selected from the following group Ib When there are a plurality of R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ , they may be the same or different. R ⁵³ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group -OR ¹¹¹ , -COR ¹¹¹ , -OCOR ¹¹¹ , -COOR ¹¹¹ , -SR ¹¹¹ , -SOR ¹¹¹ , -SO ₂ R ¹¹¹ , -NR ¹¹² R ¹¹³ , -NR ¹¹² COR ¹¹³ , -CONR ¹¹² R ¹¹³ , An unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group with 2 to 20 carbon atoms, or any of the above-mentioned hydrocarbon groups or the above-mentioned heterocyclic ring-containing groups One or more methylene groups are substituted with divalent groups selected from the following group Ib, R ¹¹¹ , R ¹¹² and R ¹¹³ each independently represent a hydrogen atom, an unsubstituted group having 1 to 20 carbon atoms Or a hydrocarbon group with a substituent, an unsubstituted or substituted heterocycle-containing group with 2 to 20 carbon atoms, or one or more methylene groups in the above-mentioned hydrocarbon group or the above-mentioned heterocycle-containing group are substituted as optional A group derived from a divalent group in the following group Ib, when there are a plurality of R ¹¹¹ , R ¹¹² and R ¹¹³ , which may be the same or different, replaces the above-mentioned hydrocarbon group having a substituent and the above-mentioned The substituent of one or more hydrogen atoms in the heterocyclic ring-containing group having a substituent is an atom or group selected from the following Group IIb) (Group Ib: -O-, -COO-, -OCO-, -CO -, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO ₂ -, -NR'-, -NR'-CO-, -CO-NR' -, -NR'-COO-, -OCO-NR'- or -SiR'R''-. Group IIb: Halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH ₂ , -COOH or -SO ₃ H. R' and R'' each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, when there are multiple R' or R'' , which can be the same or different)

Also, from the viewpoint of further improving the acid generation sensitivity of compound A, it is preferable that in the above-mentioned general formula (A), a is 1, b is 1, and the following partial structure (Aα ) is a group represented by the following general formula (Ara1) or (Arb1).

(式中，Ar、R ³³及c與式(A)相同。*1表示與R ³¹之鍵結部位，*2表示與R ³²之鍵結部位) [chemical 8]

(In the formula, Ar, ^R33 and c are the same as formula (A). *1 represents the bonding site with ^R31 , and *2 represents the bonding site with ^R32 )

(式中，X ¹、X ²、X ³分別與上述通式(Ara)、(Arb)中之內容相同， R ¹⁴¹、R ¹⁴²、R ¹⁵¹及R ¹⁵²分別獨立地表示鹵素原子、硝基、氰基、-OR ¹²¹、-COR ¹²¹、-OCOR ¹²¹、-COOR ¹²¹、-SR ¹²¹、-SOR ¹²¹、-SO ₂R ¹²¹、-NR ¹²²R ¹²³、-NR ¹²²COR ¹²³、-CONR ¹²²R ¹²³、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ic中之二價基而成之基， R ¹²¹、R ¹²²及R ¹²³分別獨立地表示氫原子、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ic中之二價基而成之基，於分別存在複數個R ¹²¹、R ¹²²及R ¹²³之情形時，其等可相同，亦可不同， 取代上述具有取代基之烴基及上述具有取代基之含有雜環之基中之1個以上氫原子的取代基為選自下述群IIc中之原子或基， a1為0～3， a2為0～3， c1為0～3， c2為0～1， *1表示與R ³¹之鍵結部位， *2表示與R ³²之鍵結部位) (群Ic：-O-、-COO-、-OCO-、-CO-、-CO-CO-、-CO-CO-O-、-CS-、-S-、-SO-、-SO ₂-、-NR'-、-NR'-CO-、-CO-NR'-、-NR'-COO-、-OCO-NR'-或-SiR'R''-。 群IIc：鹵素原子、氰基、硝基、-CO-H、-OH、-SH、-NH ₂、-COOH或-SO ₃H。 R'及R''分別獨立地表示氫原子或碳原子數1～20之未經取代之脂肪族烴基，於存在複數個R'或R''之情形時，其等可相同，亦可不同) [chemical 9]

(In the formula, X ¹ , X ² , and X ³ are the same as those in the above general formulas (Ara) and (Arb), respectively, and R ¹⁴¹ , R ¹⁴² , R ¹⁵¹ , and R ¹⁵² independently represent a halogen atom, a nitro group, Cyano, -OR ¹²¹ , -COR ¹²¹ , -OCOR ¹²¹ , -COOR ¹²¹ , -SR ¹²¹ , -SOR ¹²¹ , -SO ₂ R ¹²¹ , -NR ¹²² R ¹²³ , -NR ¹²² COR ¹²³ , -CONR ¹²² R ¹²³ , an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group with 2 to 20 carbon atoms, or the above hydrocarbon group or the above heterocyclic ring-containing group One or more of the methylene groups are substituted with divalent groups selected from the following group Ic, R ¹²¹ , R ¹²² and R ¹²³ independently represent a hydrogen atom, a hydrogen atom having 1 to 20 carbon atoms A substituted or substituted hydrocarbon group, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or one or more methylene groups in the above-mentioned hydrocarbon group or the above-mentioned heterocycle-containing group are substituted with A group selected from a divalent group in the following group Ic, when there are a plurality of R ¹²¹ , R ¹²² and R ¹²³ , they may be the same or different, substituting the above-mentioned hydrocarbon group having a substituent and The substituents for one or more hydrogen atoms in the heterocyclic ring-containing group having substituents are atoms or groups selected from the following group IIc, a1 is 0 to 3, a2 is 0 to 3, and c1 is 0 to 3 , c2 is 0～1, *1 represents the bonding site with ^R31 , *2 represents the bonding site with ^R32 ) (group Ic: -O-, -COO-, -OCO-, -CO-, - CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO ₂ -, -NR'-, -NR'-CO-, -CO-NR'-, - NR'-COO-, -OCO-NR'- or -SiR'R''-. Group IIc: Halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH ₂ , -COOH Or -SO ₃ H. R' and R'' each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group with 1 to 20 carbon atoms. When there are multiple R' or R'', the can be the same or different)

X ¹ of the above general formulas (Ara) and (Ara1) is preferably a single bond, no bond, CR ⁴¹ R ⁴² , CO or NR ⁴³ , among which, a single bond or no bond is preferred, and a single bond is most preferred. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity. The so-called "bondless" means that ^X1 does not have a direct chemical bond, for example, it refers to the state in which ^R11 and ^R20 are not bonded in the following general formula (A1).

X ² in the above general formulas (Ara) and (Ara1) is preferably a sulfur atom, CR ⁴¹ R ⁴² or NR ⁴³ , among which, CR ⁴¹ R ⁴² or NR ⁴³ is preferred. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

R ⁴¹ and R ⁴² used for X ² in the above general formulas (Ara) and (Ara1) are preferably hydrogen atoms, unsubstituted or substituted hydrocarbon groups with 1 to 20 carbon atoms, or one of the above hydrocarbon groups One or more methylene groups are substituted with divalent groups selected from the above group Ib, among which, hydrogen atoms or unsubstituted or substituted hydrocarbon groups with 1 to 20 carbon atoms are preferred, Particularly preferred is a hydrogen atom or an unsubstituted hydrocarbon group having 1 to 20 carbon atoms. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity. The number of carbon atoms of the hydrocarbon group represented by R ⁴¹ and R ⁴² used for X ² in the above general formulas (Ara) and (Ara1) is preferably 1-15, among them, 1-10 is more preferred, and 1 is particularly preferred. ~5. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

From the viewpoint of easy synthesis and excellent acid generation sensitivity, R ⁴³ in the above general formula (Ara) and (Ara1) is preferably an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, or the above-mentioned One or more methylene groups in the hydrocarbon group are substituted with divalent groups selected from the above-mentioned group Ib. Among them, unsubstituted or substituted hydrocarbon groups with 1 to 20 carbon atoms are preferred, especially It is preferably an unsubstituted hydrocarbon group having 1 to 20 carbon atoms. From the viewpoint of easy synthesis and excellent acid generation sensitivity, the number of carbon atoms in the hydrocarbon group represented by R ⁴³ in the above general formula (Ara) and (Ara1) is preferably 1 to 15, and preferably 2 to 15. 10, particularly good is 2-9. From the viewpoint of easy synthesis and excellent acid generation sensitivity, the aliphatic hydrocarbon group represented by ^R in the above general formula (Ara) and (Ara1) is preferably a straight chain or branched chain alkyl group, and among them, preferably branched chain alkyl. In the case of a branched chain, the number of carbon atoms is particularly preferably 3-9.

a1 in the above general formula (Ara1) is preferably 0-3, more preferably 0-1, particularly preferably 0. This is because compound A becomes a compound more excellent in acid generation sensitivity by setting a1 to the said number. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity. a2 in the general formula (Ara1) is preferably 0-3, more preferably 0-1, particularly preferably 0. This is because compound A becomes a compound more excellent in acid generation sensitivity by setting a2 to the said number. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity. c1 in the above general formula (Arb1) is preferably 0-3, more preferably 0-1, particularly preferably 0. This is because compound A becomes a compound more excellent in acid generation sensitivity by setting c1 to the said number. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity. c2 in the above general formula (Arb1) is preferably 0-1, particularly preferably 0. This is because compound A becomes a compound more excellent in acid generation sensitivity by setting c2 to the said number. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

In the present invention, X ² of the above general formula (Ara) or (Ara1) is preferably a sulfur atom, particularly preferably a compound in which X ² of (Ara1) is a sulfur atom, and a1=0, a2=0. When X ² in the above general formula (Ara) or (Ara1) is a sulfur atom, the compound A is particularly preferably a structure represented by the following general formula (A1). The reason is that compound A becomes a compound more excellent in acid generation sensitivity by having such a structure. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

(式中，R ¹¹及R ²⁰表示氫原子、鹵素原子、硝基、氰基、-OR ⁹⁰、-COR ⁹⁰、-OCOR ⁹⁰、-COOR ⁹⁰、-SR ⁹⁰、-SOR ⁹⁰、-SO ₂R ⁹⁰、-NR ⁹¹R ⁹²、-NR ⁹¹COR ⁹²、-CONR ⁹¹R ⁹²、下述通式(1)所表示之基、選自上述式(IVa)～(IVh)中之式所表示之基、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自上述群Ia中之二價基而成之基，或者表示R ¹¹及R ²⁰鍵結而形成之單鍵、-O-、-S-、-Se-、-CR ⁴¹R ⁴²-、-CO-、-NR ⁴³-或-PR ⁴⁴-， R ¹²、R ¹³、R ¹⁴、R ¹⁵、R ¹⁶、R ¹⁷、R ¹⁸及R ¹⁹表示氫原子、鹵素原子、硝基、氰基、-OR ⁹⁰、-COR ⁹⁰、-OCOR ⁹⁰、-COOR ⁹⁰、-SR ⁹⁰、-SOR ⁹⁰、-SO ₂R ⁹⁰、-NR ⁹¹R ⁹²、-NR ⁹¹COR ⁹²、-CONR ⁹¹R ⁹²、上述通式(1)所表示之基、選自上述式(IVa)～(IVh)中之式所表示之基、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自上述群Ia中之二價基而成之基， R ⁹⁰、R ⁹¹及R ⁹²分別獨立地表示氫原子、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自上述群Ia中之二價基而成之基，於分別存在複數個R ⁹⁰、R ⁹¹及R ⁹²之情形時，其等可相同，亦可不同， 取代上述具有取代基之烴基及上述具有取代基之含有雜環之基中之1個以上氫原子的取代基為選自上述群IIa中之原子或基。 其中，R ¹¹、R ¹²、R ¹³、R ¹⁴、R ¹⁵、R ¹⁶、R ¹⁷、R ¹⁸、R ¹⁹及R ²⁰之至少任一者為上述通式(1)所表示之基，剩餘中至少任一者為選自上述式(IVa)～(IVh)中之式所表示之基) [chemical 10]

(wherein, R ¹¹ and R ²⁰ represent hydrogen atom, halogen atom, nitro group, cyano group, -OR ⁹⁰ , -COR ⁹⁰ , -OCOR ⁹⁰ , -COOR ⁹⁰ , -SR ⁹⁰ , -SOR ⁹⁰ , -SO ₂ R ⁹⁰ , -NR ⁹¹ R ⁹² , -NR ⁹¹ COR ⁹² , -CONR ⁹¹ R ⁹² , a group represented by the following general formula (1), a group represented by a formula selected from the above-mentioned formulas (IVa) to (IVh) , an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group with 2 to 20 carbon atoms, or the above hydrocarbon group or the above heterocyclic ring-containing group One or more methylene groups are substituted with divalent groups selected from the group Ia above, or a single bond formed by bonding ^R11 and ^R20 , -O-, -S-, -Se -, -CR ⁴¹ R ⁴² -, -CO-, -NR ⁴³ -or -PR ⁴⁴ -, R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ represent a hydrogen atom, Halogen atom, nitro group, cyano group, -OR ⁹⁰ , -COR ⁹⁰ , -OCOR ⁹⁰ , -COOR ⁹⁰ , -SR ⁹⁰ , -SOR ⁹⁰ , -SO ₂ R ⁹⁰ , -NR ⁹¹ R ⁹² , -NR ⁹¹ COR ⁹² , -CONR ⁹¹ R ⁹² , the group represented by the above-mentioned general formula (1), the group represented by the formula selected from the above-mentioned formulas (IVa) to (IVh), unsubstituted or substituted Hydrocarbyl group, unsubstituted or substituted heterocyclic ring-containing group with 2 to 20 carbon atoms, or one or more methylene groups in the above-mentioned hydrocarbon group or the above-mentioned heterocyclic ring-containing group are substituted by a group selected from the above group In the group formed by the divalent group in Ia, R ⁹⁰ , R ⁹¹ and R ⁹² independently represent a hydrogen atom, an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, and a hydrocarbon group with 2 to 20 carbon atoms. An unsubstituted or substituted heterocycle-containing group, or a group in which one or more methylene groups in the above-mentioned hydrocarbon group or the above-mentioned heterocycle-containing group are substituted with divalent groups selected from the above-mentioned group Ia, When a plurality of R ⁹⁰ , R ⁹¹ , and R ⁹² exist, they may be the same or different, replacing one or more hydrogens in the above-mentioned hydrocarbon group having a substituent and the group containing a heterocyclic ring having a substituent The substituent of the atom is an atom or group selected from the above group IIa. Among them, at least any of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R 15 , R ¹⁶ , R ¹⁷ , ^{R 18 ,} R ¹⁹ and R ²⁰ One is the group represented by the above-mentioned general formula (1), and at least any one of the remaining is a group represented by a formula selected from the above-mentioned formulas (IVa) to (IVh))

R ¹¹ and R ²⁰ of the above general formula (A1) are preferably hydrogen atom, halogen atom, nitro group, cyano group, -OR ⁹⁰ , -COR ⁹⁰ , unsubstituted or substituted C1-20 A hydrocarbon group, a group in which one or more methylene groups in the above-mentioned hydrocarbon groups are substituted with a divalent group selected from the above-mentioned group Ia, or a single bond formed by bonding ^R11 and ^R20 , -O-, -S -, -Se-, -CR ⁴¹ R ⁴² -, -CO-, -NR ⁴³ - or -PR ⁴⁴ -, among them, hydrogen atom, halogen atom, nitro group, cyano group, or R ¹¹ and R ²⁰ The single bond formed by bonding, -O- or -NR ⁴³ - is particularly preferably a hydrogen atom, or the single bond formed by bonding R ¹¹ and R ²⁰ . The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

When R ¹¹ and R ²⁰ in the above general formula (A1) are bonded to each other to form -NR ⁴³ -, R ⁴³ is preferably an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or One or more methylene groups in the above-mentioned hydrocarbon groups are substituted with divalent groups selected from the above-mentioned group Ib, among them, unsubstituted or substituted hydrocarbon groups having 1 to 20 carbon atoms are preferred, Particularly preferred is an unsubstituted hydrocarbon group having 1 to 20 carbon atoms. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity. The number of carbon atoms in the hydrocarbon group represented by R ⁴³ in the general formula (A1) is preferably 1-15, among which, 1-10 is more preferred, and 1-5 is particularly preferred. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity. The hydrocarbon group represented by R ⁴³ in the above general formula (A1) is preferably a straight-chain or branched-chain alkyl group, among which, a straight-chain alkyl group is preferable. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁹ in the above general formula (A1) are preferably independently hydrogen atom, halogen atom, nitro group, cyano group, -OR ⁹⁰ , -COR ⁹⁰ , an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, or a group in which one or more methylene groups in the above hydrocarbon group are substituted with a divalent group selected from the above group Ic, wherein, A hydrogen atom, a nitro group, and a cyano group are preferable, and a hydrogen atom is particularly preferable. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

R ¹³ of the above general formula (A1) is preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR ⁹⁰ , -COR ⁹⁰ , an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, the above-mentioned A group in which one or more methylene groups in the hydrocarbon group is substituted with a divalent group selected from the above-mentioned group Ic, a group represented by the above-mentioned general formula (1), or a group represented by the above-mentioned formulas (IVa) to (IVh) Among them, preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, a group represented by the above-mentioned general formula (1) or a group represented by a group selected from the above-mentioned formulas (IVa) to (IVh), More preferably, it is a hydrogen atom, a group represented by the above-mentioned general formula (1), or a group represented by a formula selected from the above-mentioned formulas (IVa) to (IVh), particularly preferably a group represented by the above-mentioned general formula (1). The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

R ¹⁸ of the above general formula (A1) is preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR ⁹⁰ , -COR ⁹⁰ , an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, the above-mentioned One or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the above-mentioned group Ic, a group represented by the above-mentioned general formula (1), or a group selected from the above-mentioned formulas (IVa) to (IVh) Among the groups represented by the formula, among them, preferably hydrogen atom, halogen atom, nitro group, cyano group, the group represented by the above-mentioned general formula (1), or a group selected from the above-mentioned formulas (IVa) to (IVh) The group represented is more preferably a hydrogen atom, a group represented by the above-mentioned general formula (1) or a group represented by a formula selected from the above-mentioned formulas (IVa) to (IVh), especially preferably selected from the group of the above-mentioned formula (IVa )～(IVh) The group represented by the formula in (IVh).

In addition, in the above general formula (A1), one or more of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ is the above general formula ( 1) The group represented by R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ is one or more selected from the above formula (IVa )～(IVh) The base represented by the formula in (IVh) will suffice. Among them, it is preferable that one of R ¹³ and R ¹⁸ is a group represented by the above-mentioned general formula (1), and the other group is a group represented by a formula selected from the above-mentioned formulas (IVa) to (IVh). It is particularly preferred that R ¹³ of the above-mentioned general formula (A1) is a group represented by the above-mentioned general formula (1), and R ¹⁸ of the above-mentioned general formula (A1) is represented by a formula selected from the above-mentioned formulas (IVa) to (IVh) base of representation. The reason is that compound A becomes a compound more excellent in acid generation sensitivity by having such a structure. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

Among the groups represented by the formulas selected from the general formulas (IVa) to (IVh), preferably the groups represented by the formulas selected from the general formulas (IVa), (IVf) and (IVh), especially the general The group represented by formula (IVf). The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

R ⁶⁷ of the above general formula (IVf) is preferably a single bond. In addition, ^R68 is preferably an unsubstituted or substituted hydrocarbon group with 1 to 10 carbon atoms, among which, it is preferably an unsubstituted or substituted hydrocarbon group with 1 to 5 carbon atoms, especially preferably It is an unsubstituted or substituted hydrocarbon group having 1 to 3 carbon atoms, preferably an unsubstituted hydrocarbon group having 1 to 3 carbon atoms. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

Also, in the present invention, it is preferred that X ¹ of the above-mentioned general formula (Ara) or (Ara1) is a single bond, and X ² is NR ⁴³ , especially preferably in formula (Ara) or (Ara1), X ¹ is a single bond, and X ² is NR ⁴³ , a1=0, a2=0. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. In the case of a compound in which X ¹ is a single bond and X ² is NR ⁴³ in the above general formula (Ara) or (Ara1), compound A is particularly preferably a structure represented by the following general formula (A2). The reason is that compound A becomes a compound more excellent in acid generation sensitivity by having such a structure. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

(R ^12'、R ^13'、R ^14'、R ^15'、R ^16'、R ^17'、R ^18'及R ^19'分別獨立地表示氫原子、鹵素原子、硝基、氰基、-OR ⁹⁰、-COR ⁹⁰、-OCOR ⁹⁰、-COOR ⁹⁰、-SR ⁹⁰、-SOR ⁹⁰、-SO ₂R ⁹⁰、-NR ⁹¹R ⁹²、-NR ⁹¹COR ⁹²、-CONR ⁹¹R ⁹²、上述通式(1)所表示之基、選自上述式(IVa)～(IVh)中之式所表示之基、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自上述群Ia中之二價基而成之基， R ⁹⁰、R ⁹¹及R ⁹²分別獨立地表示氫原子、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自上述群Ia中之二價基而成之基，於分別存在複數個R ⁹⁰、R ⁹¹及R ⁹²之情形時，其等可相同，亦可不同， 取代上述具有取代基之烴基及上述具有取代基之含有雜環之基中之1個以上氫原子的取代基為選自上述群IIa中之原子或基。 其中，R ^12'、R ^13'、R ^14'、R ^15'、R ^16'、R ^17'、R ^18'及R ^19'之至少任一者為上述通式(1)所表示之基，剩餘中至少任一者為選自上述式(IVa)～(IVh)中之式所表示之基) [chemical 11]

(R ^12' , R ^13' , R ^14' , R ^15' , R ^{16' ,} R 17' , R ^18' and R ^19' each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR ⁹⁰ , -COR ⁹⁰ , -OCOR ⁹⁰ , -COOR ⁹⁰ , -SR ⁹⁰ , -SOR ⁹⁰ , -SO ₂ R ⁹⁰ , -NR ⁹¹ R ⁹² , -NR ⁹¹ COR ⁹² , -CONR ⁹¹ R ⁹² , the above general formula ( 1) The group represented by the group selected from the group represented by the formulas (IVa) to (IVh) above, an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, a hydrocarbon group with 2 to 20 carbon atoms An unsubstituted or substituted heterocycle-containing group, or a group in which one or more methylene groups in the above-mentioned hydrocarbon group or the above-mentioned heterocycle-containing group are substituted with divalent groups selected from the above-mentioned group Ia, R ⁹⁰ , R ⁹¹ and R ⁹² independently represent a hydrogen atom, an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring with 2 to 20 carbon atoms or one or more methylene groups in the above-mentioned hydrocarbon group or the above-mentioned group containing a heterocycle is substituted with a divalent group selected from the above-mentioned group Ia, when there are a plurality of R ⁹⁰ , R ⁹¹ and In the case of ^R92 , they may be the same or different, and the substituents substituting one or more hydrogen atoms in the above-mentioned hydrocarbon group with substituents and the above-mentioned heterocyclic ring-containing group with substituents are selected from the group IIa above. Among them, at least one of R ^12' , R ^13' , R ^14' , R ^15' , R ^16' , R ^17' , R ^18' and R ^19' is the above general formula (1) represented group, at least any one of the rest is a group represented by a formula selected from the above-mentioned formulas (IVa) to (IVh))

R ^12' , R ^14' , R ^15' , R ^16' , R ^17' and R ^19' in the above general formula (A2) are preferably independently hydrogen atom, halogen atom, nitro group, cyano group, - OR ⁹⁰ , -COR ⁹⁰ , an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, or one or more of the above hydrocarbon groups substituted with a divalent group selected from the above group Ic Among them, a hydrogen atom, a nitro group, and a cyano group are preferred, and a hydrogen atom is particularly preferred. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

R ^13' of the above general formula (A2) is preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR ⁹⁰ , -COR ⁹⁰ , an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, One or more methylene groups in the above-mentioned hydrocarbon groups are substituted with divalent groups selected from the above-mentioned group Ic, groups represented by the above-mentioned general formula (1), or groups represented by the above-mentioned formulas (IVa) to (IVh) The group represented by, among them, preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, a group represented by the above-mentioned general formula (1), or a group represented by a group selected from the above-mentioned formulas (IVa) to (IVh) , more preferably a hydrogen atom, a group represented by the above-mentioned general formula (1) or a group represented by a formula selected from the above-mentioned formulas (IVa) to (IVh), especially preferably a group represented by the above-mentioned general formula (1) . The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

R ^18' of the above general formula (A2) is preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR ⁹⁰ , -COR ⁹⁰ , an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, One or more methylene groups in the above-mentioned hydrocarbon groups are substituted with divalent groups selected from the above-mentioned group Ic, groups represented by the above-mentioned general formula (1), or groups selected from the above-mentioned formulas (IVa) to (IVh) ), among them, preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, a group represented by the above-mentioned general formula (1), or a group selected from the above-mentioned formulas (IVa) to (IVh) The group represented by the formula is more preferably a hydrogen atom, a group represented by the above-mentioned general formula (1) or a group selected from the group represented by the above-mentioned formula (IVa) to (IVh), especially preferably selected from the group of the above-mentioned formula ( The groups represented by the formulas in IVa) to (IVh).

In addition, in the above general formula (A2), one or more of R ^12' , R ^13' , R ^14' , R ^15' , R ^16' , R ^17' , R ^18' and R ^19' is the above general formula (A2). The group represented by formula (1) is sufficient, and one or more of R ^12' , R ^13' , R ^14' , R ^15' , R ^16' , R ^17' , R ^18' and R ^19' are selected from The groups represented by the formulas in the above formulas (IVa) to (IVh) are sufficient. Among them, it is preferred that one of R ^13' and R ^18' is a group represented by the above general formula (1), and the other group is a group represented by a formula selected from the above formulas (IVa) to (IVh) . It is particularly preferred that R ^13' of the above-mentioned general formula (A2) is a group represented by the above-mentioned general formula (1), and R ^18' of the above-mentioned general formula (A2) is selected from the above-mentioned formulas (IVa) to (IVh). The base represented by the formula. The reason is that compound A becomes a compound more excellent in acid generation sensitivity by having such a structure. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

Among the groups represented by the formulas selected from the general formulas (IVa) to (IVh), preferably the groups represented by the formulas selected from the general formulas (IVa), (IVf) and (IVh), especially the general The group represented by formula (IVf). The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

R ⁶⁷ of the above general formula (IVf) is preferably a single bond. In addition, ^R68 is preferably an unsubstituted or substituted hydrocarbon group with 1 to 10 carbon atoms, among which, it is preferably an unsubstituted or substituted hydrocarbon group with 1 to 5 carbon atoms, especially preferably It is an unsubstituted or substituted hydrocarbon group having 1 to 3 carbon atoms, preferably an unsubstituted hydrocarbon group having 1 to 3 carbon atoms. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

R ⁴³ in the above-mentioned general formula (A2) is preferably an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, or one or more methylene groups in the above-mentioned hydrocarbon group are substituted to be selected from the group Ib above Among them, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms is preferred, and an unsubstituted hydrocarbon group having 1 to 20 carbon atoms is particularly preferred. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity. The number of carbon atoms of the hydrocarbon group represented by R ⁴³ in the above general formula (A2) is preferably 1-15, among which, 2-10 is more preferred, and 2-9 is particularly preferred. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity. The hydrocarbon group represented by R ⁴³ in the above general formula (A2) is preferably a straight-chain or branched-chain alkyl group, among which a branched-chain alkyl group is preferred. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity. Furthermore, it is because the solubility to a solvent becomes favorable.

Also, in the present invention, it is preferred that X ¹ in the above general formula (Ara) or (Ara1) is a single bond, and X ² is CR ⁴¹ R ⁴² , especially preferably in the above general formula (Ara) or (Ara1) wherein X ¹ is a single bond, and X ² is CR ⁴¹ R ⁴² , a1=0, a2=0. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. In the case of the compound in which X ¹ is a single bond and X ² is CR ⁴¹ R ⁴² in the above general formula (Ara) or (Ara1), compound A is particularly preferably a structure represented by the following general formula (A3). The reason is that compound A becomes a compound more excellent in acid generation sensitivity by having such a structure. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity. In addition, the skeleton of formula (A3) also has the advantage of easily obtaining solvent solubility.

(R ^12''、R ^13''、R ^14''、R ^15''、R ^16''、R ^17''、R ^18''及R ^19''表示氫原子、鹵素原子、硝基、氰基、-OR ⁹⁰、-COR ⁹⁰、-OCOR ⁹⁰、-COOR ⁹⁰、-SR ⁹⁰、-SOR ⁹⁰、-SO ₂R ⁹⁰、-NR ⁹¹R ⁹²、-NR ⁹¹COR ⁹²、-CONR ⁹¹R ⁹²、上述通式(1)所表示之基、選自上述式(IVa)～(IVh)中之式所表示之基、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自上述群Ia中之二價基而成之基， R ⁹⁰、R ⁹¹及R ⁹²分別獨立地表示氫原子、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自上述群Ia中之二價基而成之基，於分別存在複數個R ⁹⁰、R ⁹¹及R ⁹²之情形時，其等可相同，亦可不同， 取代上述具有取代基之烴基及上述具有取代基之含有雜環之基中之1個以上氫原子的取代基為選自上述群IIa中之原子或基。 其中，R ^12''、R ^13''、R ^14''、R ^15''、R ^16''、R ^17''、R ^18''及R ^19''之至少任一者為上述通式(1)所表示之基，剩餘中至少任一者為選自上述式(IVa)～(IVh)中之式所表示之基) [chemical 12]

(R ^12'' , R ^13'' , R ^14'' , R ^15'' , R ^16'' , R ^17'' , R ^18'' and R ^19'' represent hydrogen atom, halogen atom, nitro group, Cyano, -OR ⁹⁰ , -COR ⁹⁰ , -OCOR ⁹⁰ , -COOR ⁹⁰ , -SR ⁹⁰ , -SOR ⁹⁰ , -SO ₂ R ⁹⁰ , -NR ⁹¹ R ⁹² , -NR ⁹¹ COR ⁹² , -CONR ⁹¹ R ⁹² , the group represented by the above-mentioned general formula (1), the group represented by the formulas selected from the above-mentioned formulas (IVa) to (IVh), unsubstituted or substituted hydrocarbon groups with 1 to 20 carbon atoms, carbon atoms The unsubstituted or substituted heterocyclic ring-containing group having a number of 2 to 20, or one or more methylene groups in the above-mentioned hydrocarbon group or the above-mentioned heterocyclic ring-containing group is substituted with a divalent group selected from the above-mentioned group Ia The resulting group, R ⁹⁰ , R ⁹¹ and R ⁹² independently represent a hydrogen atom, an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted hydrocarbon group with 2 to 20 carbon atoms A group containing a heterocycle, or one or more methylene groups in the above-mentioned hydrocarbon group or the above-mentioned group containing a heterocycle is substituted with a divalent group selected from the above-mentioned group Ia, where there are a plurality of R ^90. In the case of R ⁹¹ and R ⁹² , they may be the same or different, and the substituents substituting one or more hydrogen atoms in the above-mentioned hydrocarbon group with substituents and the above-mentioned heterocyclic ring-containing group with substituents are optional. Atoms or groups from the above group IIa. Among them, R ^12'' , R ^13'' , R ^14'' , R ^{15'', R 16' ', R 17' '} , R ^18'' and R ^19'' At least any one is the group represented by the above general formula (1), and at least any one of the remaining is a group represented by the formula selected from the above formulas (IVa) to (IVh))

R ⁴¹ and R ⁴² are preferably hydrogen atoms, unsubstituted or substituted hydrocarbon groups with 1 to 20 carbon atoms, or one or more methylene groups in the above hydrocarbon groups are substituted with two selected from the above group Ib. A group formed from valence groups, among them, preferably a hydrogen atom, or an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, particularly preferably a hydrogen atom or an unsubstituted hydrocarbon group with 1 to 20 carbon atoms Hydrocarbyl. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity. The number of carbon atoms in the hydrocarbon group represented by R ⁴¹ and R ⁴² in the above general formula (A3) is preferably 1-15, especially preferably 1-10, particularly preferably 1-5. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

R ^12'' , R ^15'' , R ^16'' and R ^19'' in the above general formula (A3) are preferably independently hydrogen atom, halogen atom, nitro group, cyano group, -OR ⁹⁰ , - COR ⁹⁰ , an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, or a group in which at least one methylene group in the above hydrocarbon group is substituted with a divalent group selected from the above group Ic, wherein , preferably a hydrogen atom, a nitro group, or a cyano group, particularly preferably a hydrogen atom. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

At least one of R ^13'' and R ^14'' in the above general formula (A3) is preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR ⁹⁰ , -COR ⁹⁰ , or a C1-20 An unsubstituted or substituted hydrocarbon group, a group in which one or more methylene groups in the above hydrocarbon group are substituted with a divalent group selected from the above group Ic, a group represented by the above general formula (1), or The group represented by the group selected from the above-mentioned formulas (IVa) to (IVh), among them, preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, a group represented by the above-mentioned general formula (1) or a group selected from the above-mentioned The group represented by the group in the formulas (IVa) to (IVh) is more preferably represented by a hydrogen atom, the group represented by the above general formula (1) or the group selected from the group in the above formulas (IVa) to (IVh) The group is particularly preferably a group represented by the above-mentioned general formula (1). In addition, R ^14'' is particularly preferred to satisfy these conditions. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

At least one of R ^17'' and R ^18'' in the above general formula (A3) is preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR ⁹⁰ , -COR ⁹⁰ , or a C1-20 An unsubstituted or substituted hydrocarbon group, a group in which one or more methylene groups in the above hydrocarbon group are substituted with a divalent group selected from the above group Ic, a group represented by the above general formula (1), or The group represented by the group selected from the above-mentioned formulas (IVa) to (IVh), among them, preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, a group represented by the above-mentioned general formula (1) or a group selected from the above-mentioned The group represented by the group in the formulas (IVa) to (IVh) is more preferably represented by a hydrogen atom, the group represented by the above general formula (1) or the group selected from the group in the above formulas (IVa) to (IVh) The group is particularly preferably a group represented by a group selected from the above-mentioned formulas (IVa) to (IVh). In addition, R ^17'' is especially preferable to satisfy these conditions. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

Also, in the general formula (A3), among R ^12'' , R ^13'' , R ^14'' , R ^15'' , R ^16'' , R ^17'' , R ^18'' and R ^19'' One or more of them may be represented by the above general formula (1), R ^12'' , R ^13'' , R ^14'' , R ^15'' , R ^16'' , R ^17'' , R ¹⁸ One or more of ^'' and R ^19'' may be represented by groups selected from the above formulas (IVa) to (IVh). Among them, it is preferred that one of R ^13'' and R ^18'' is represented by the above-mentioned general formula (1), and the other group is represented by a group selected from the above-mentioned formulas (IVa) to (IVh) or one of R ^14'' and R ^17'' is a group represented by the above general formula (1), and the other group is represented by a group selected from the above formulas (IVa) to (IVh) base. It is particularly preferred that R ^14'' of the above-mentioned general formula (A3) is a group represented by the above-mentioned general formula (1), and R ^17'' of the above-mentioned general formula (A3) is selected from the above-mentioned formulas (IVa) to (IVh) The base represented by the base in the middle. The reason is that compound A becomes a compound more excellent in acid generation sensitivity by having such a structure. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

In general formula (A3), the group represented by the group selected from general formula (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) and (IVh) Among them, groups represented by general formulas (IVa), (IVf) and (IVh) are preferred, and groups selected from groups represented by general formula (IVf) are particularly preferred. The reason for this is that compound A becomes a compound more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine, and it is easy to form an acid generator excellent in acid generation sensitivity.

As a specific example of the said compound A, the compound represented by following No.1-No.58 is mentioned.

[chemical 13]

[chemical 14]

[chemical 15]

[chemical 16]

[chemical 17]

[chemical 18]

[chemical 19]

[chemical 20]

[chem 21]

The production method of the above-mentioned compound A may be a method for obtaining a compound of a desired structure, and it can be synthesized using a known chemical reaction. For example, the method represented by the following flow chart can be mentioned. Specifically, the following method can be exemplified: an oxime compound is obtained by reacting a known ketone compound with hydroxylamine hydrochloride, then reacting a sulfonic anhydride with an oxime compound, and then reacting with a compound having a group represented by ^R , For example, chloroglyoxylic acid, which is a diketone body, is reacted to obtain compound A. The reaction conditions such as reaction temperature, reaction time, and the amount of raw materials used in the production method are not particularly limited, and known conditions can be used.

(式中之各符號與上述通式(1)、(IVf)、(Ara)同義) [chem 22]

(Each symbol in the formula is synonymous with the above-mentioned general formula (1), (IVf), (Ara))

The above compound A has the function of generating acid. As a method for generating an acid from the above-mentioned compound A, a method generally used for an acid generator can be used. Specifically, a method of irradiating energy rays, a method of performing heat treatment, and a method of performing these methods simultaneously or sequentially may, for example, be mentioned. Examples of the above-mentioned energy rays include g-rays (436 nm), h-rays (405 nm), i-rays (365 nm), visible rays, ultraviolet rays, extreme ultraviolet rays, X-rays, and charged particle beams. In addition, examples of light sources include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, metal halide lamps, electron beam irradiation devices, X-ray irradiation devices, lasers (argon lasers, dye lasers, etc.) , nitrogen laser, LED (Light Emitting Diode, light emitting diode), helium cadmium laser, etc.). The heating temperature in the above-mentioned heat treatment is, for example, preferably from 70°C to 450°C, preferably from 100°C to 300°C, and may be 150°C or higher. In addition, the heating time in the heat treatment is preferably, for example, from 1 minute to 100 minutes. This is because the effect of obtaining a composition with little color change can be effectively exhibited by setting it as said heat-processing conditions.

The use of the above-mentioned compound A may, for example, be an acid generator, and more specifically, a photoacid generator which generates an acid by irradiation with energy rays, or a thermal acid generator which generates an acid by heat treatment, etc. . Moreover, as a use of an acid generator, the use of adding to the composition containing a resin component is mentioned. Regarding the use of the above composition, for example, it can be used for optical filters, paints, coating agents, lining agents, adhesives, printing plates, insulating varnishes, insulating sheets, laminates, printed substrates, semiconductor devices/LED packages Sealant, molding material, putty, glass fiber impregnating agent, caulking for/for liquid crystal inlet/for organic EL (Electroluminescence)/for optical element/for electrical insulation/for electronic parts/for separation film Passivation films for semiconductors/solar cells, thin film transistors (TFT)/liquid crystal display devices/organic EL display devices/interlayer insulating films, surface protection films, printed circuit boards, or color TVs, PC (Personal Computer, personal computer) monitors, portable information terminals, color filters for CCD (Charge Coupled Device, Charge Coupled Device) image sensors, electrode materials for plasma display panels, printing inks, dental compositions , Resins for optical modeling, both liquid and dry films, micromachine parts, coatings for glass fiber cables, materials for holographic recording, magnetic recording materials, optical switches, masks for plating, etching masks, screen plates Printing stencils, touch panels such as transparent conductive films, MEMS (microelectromechanical system, micro-electromechanical systems) components, nanoimprint materials, optical processing such as two-dimensional and three-dimensional high-density packaging of semiconductor packaging, decorative sheets, artificial Microlens arrays used in fingernails, glass instead of optical films, electronic paper, optical discs, projectors, lasers for optical communications, etc., microlens arrays used in backlights of liquid crystal display devices, Fresnel used in screens such as projection TVs Lens parts of lens sheets such as lens sheets and lenticular lens sheets, or backlights using such sheets, optical lenses such as microlenses/camera lenses, optical elements, optical connectors, optical waveguides, insulating fillers, 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 sealing materials, components for solar cells/fuel cells/secondary batteries, batteries Solid electrolyte, insulating covering material, photosensitive drum for photocopier, gas separation membrane, concrete protection material/lining/soil injection agent/sealant/cooling and heat storage material/glass coating/foam, etc. civil engineering/construction materials, pipes/sealing Materials/coating materials/seal materials for sterilization treatment devices/medical materials such as contact lenses/oxygen-enriched membranes/biochips, automotive parts, various machine parts, etc., the use is not particularly limited. From the viewpoint of more effectively exhibiting the effect of excellent acid generation sensitivity of the present invention, the above-mentioned use is preferably used in a pattern-forming composition, for example, preferably used in a negative-type composition used together with an acid-hardening component , a positive-type composition for use with an acid-decomposable component (also referred to as an "acid-decomposable resin component"), and more specifically, preferably used for forming an optical lens, an optical element, an optical connector, Compositions such as interlayer insulating films used in optical waveguides, liquid crystal display devices/organic EL display devices/printed substrates that require high acid generation sensitivity.

B. Acid Generators One of the characteristics of the acid generator of the present invention is that it contains the above-mentioned compound A. When the acid generator contains Compound A, an acid generator excellent in acid generation sensitivity can be easily obtained.

1. Compound A As for the kind of the above-mentioned compound A used in the acid generator of the present invention, as long as it is easy to obtain an acid generator excellent in acid generation sensitivity, only one kind or two or more kinds may be used in the acid generator.

The content of the above-mentioned compound A in the acid generator of the present invention may be an amount that is easy to obtain an acid generator excellent in acid generation sensitivity, and can be appropriately set according to the type of acid generator and the like. The content of the above-mentioned compound A in the acid generator of the present invention may be, for example, 100 parts by mass in 100 parts by mass of the solid content of the above-mentioned acid generator, that is, the solid content of the above-mentioned acid generator is only the above-mentioned Compound A. The content of the above-mentioned compound A in the acid generator of the present invention may be less than 100 parts by mass in 100 parts by mass of the solid content of the acid generator, and the acid generator may be a composition comprising the above-mentioned compound A and other components, For example, it can be more than 20 mass parts and 99.99 mass parts or less. This is because it is easy to obtain an acid generator excellent in acid generation sensitivity by making content of compound A into the said range. When the acid generator of the present invention contains components other than the above-mentioned compound A, the content of the compound A in the acid generator of the present invention should be adjusted from the viewpoint of obtaining an acid generator with excellent acid generation sensitivity more easily. The lower limit is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and still more preferably 90 parts by mass or more, based on 100 parts by mass of the solid content of the acid generator. This is because it is easy to obtain an acid generator excellent in acid generation sensitivity by making the upper limit of the content of the said compound A into the said range. In addition, from the viewpoint of ease of particle size control of the acid generator, etc., the upper limit of the content of the compound A in the acid generator of the present invention is preferably 99 mass parts per 100 parts by mass of the solid content of the acid generator It is less than 95 parts by mass, more preferably less than 95 parts by mass, and still more preferably less than 90 parts by mass. This is because it is easy to obtain an acid generator excellent in acid generation sensitivity by making content of compound A into the said range. In addition, solid content includes all components except a solvent. Moreover, when containing 2 or more types of compound A, content of the said compound A shows the total amount of compound A.

The above-mentioned compound A may be the same as that described in the above-mentioned item "A. Compound", so the description here is omitted.

2. Other ingredients The above-mentioned acid generator may contain other components other than the above-mentioned compound A. As such another component, a solvent is mentioned, for example. The above-mentioned solvent is one capable of dispersing or dissolving each component in the acid generator. Therefore, even if it is a liquid at normal temperature (25 degreeC) and atmospheric pressure, the said compound A is not contained in a solvent. As for the above-mentioned solvents, both water and organic solvents can be used. In the present invention, the above-mentioned solvent is preferably an organic solvent. The reason for this is that the above compound A is easily dissolved or dispersed.

Examples of the above-mentioned organic solvent include carbonates such as propylene carbonate and diethyl carbonate; ketones such as acetone and 2-heptanone; ethylene glycol, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol. Polyols such as monomethyl ether or monophenyl ether of monoacetate and their derivatives; such as cyclic ethers of dioxane; esters such as ethyl formate and 3-methyl-3-methoxybutyl acetate Aromatic hydrocarbons such as toluene and xylene; lactones such as γ-caprolactone and δ-caprolactone, etc.

Content of the said solvent in the said acid generator can be 1 mass part or more and 99 mass parts or less with respect to 100 mass parts of acid generators.

Components other than the above compound A and solvent include those described in "2. Resin component" and "3. Other components" of "C. Composition" below. Moreover, as said other component, the well-known compound used as an acid generator, etc. are mentioned. The content of the above-mentioned other components can be appropriately set according to the use of the above-mentioned acid generator, for example, it can be set to be less than 50 parts by mass, more preferably 10 parts by mass or less, in 100 parts by mass of the solid content of the acid generator. The reason for this is that the above-mentioned acid generator can easily increase the content ratio of the compound A, and it is easier to obtain an acid generator excellent in acid generation sensitivity.

3. Other The method for producing the above-mentioned acid generator may be any method as long as it can contain the above-mentioned compound A in a required amount. When the above-mentioned acid generator contains Compound A and other components, a method using a known mixing method can be exemplified.

The use of the above-mentioned acid generator may, for example, be added to a composition containing a resin component. Specifically, it may be the same as that described in the above "A. Compound".

C. Composition One of the characteristics of the composition of the present invention is that it contains the above-mentioned compound A and a resin component. By containing the above-mentioned compound A, the acid generation sensitivity of the obtained composition etc. is excellent.

1. Compound A The type of the above-mentioned compound A used in the composition of the present invention may be only one type or two or more types in the composition as long as the effect of excellent acid generation sensitivity can be exerted.

The content of the compound A in the composition of the present invention can be appropriately set according to the type of resin component used, etc., as long as the effect of being excellent in acid generation sensitivity can be exhibited. The content of the compound A in the composition of the present invention is, for example, preferably from 0.05 to 100 parts by mass, more preferably from 0.05 to 20 parts by mass, relative to 100 parts by mass of the aforementioned resin component. The reason for this is that it is easy to obtain a composition capable of exhibiting an effect excellent in acid generation sensitivity. Also, the reason is that it is easy to form a composition in which coloring is suppressed, and the like. The content of the compound A in the composition of the present invention is preferably, for example, 0.001 to 20 parts by mass in 100 parts by mass of the solid content of the composition. The reason for this is that it is easy to obtain a composition capable of exhibiting an effect excellent in acid generation sensitivity. Also, the reason is that it is easy to form a composition in which coloring is suppressed, and the like. The content of the compound A in the composition of the present invention is preferably, for example, 0.001 to 20 parts by mass in 100 parts by mass of the composition. The reason for this is that it is easy to obtain a composition capable of exhibiting an effect excellent in acid generation sensitivity. Also, the reason is that it is easy to form a composition in which coloring is suppressed, and the like. When containing 2 or more types of compound A, content of the said compound A shows the total amount of compound A.

In addition, the above-mentioned compound A may be the same as that described in the above-mentioned item "A. Compound", so the description here is omitted.

2. Resin composition As the above-mentioned resin component, a polymer compound or a component capable of becoming a polymer compound can be used. In addition, the above-mentioned resin component may be an acid-reactive component having a structure capable of reacting with an acid generated from compound A, or may be a non-acid-reactive component that does not react with an acid generated from compound A, but The aforementioned resin component is preferably an acid-reactive component. The reason for this is that by making the resin component an acid-reactive component, the above-mentioned composition can easily obtain the effect of being excellent in the acid generation sensitivity which compound A has. Also, the reason is that it is easy to form a composition in which coloring is suppressed, and the like.

As for such an acid-reactive component, it is preferable to use an acid-hardening component that is hardened by polymerization or cross-linking with the acid generated from compound A, or to increase the resistance to the developer by the acid generated from compound A. Soluble acid-decomposing components. In the present invention, when the resin component is an acid-curable component, the effect of excellent acid generation sensitivity can be effectively exhibited, and the acid-curable component is easily cured. Also, when the resin component is an acid-decomposable component, the effect of excellent acid generation sensitivity can be effectively exhibited, and the acid-decomposable component is easily decomposed. Moreover, the composition which suppresses the coloring of the non-developed part which does not change the solubility in a developing solution can be obtained.

A cation polymerizable compound is mentioned as said acid-curable component. Examples of the cationically polymerizable compound include epoxy compounds, cyclic ether compounds such as oxetane compounds, vinyl ether compounds, vinyl compounds, styrenes, spiroorthoesters, and bicyclic orthoesters. , spirocarbonates, lactones, oxazolines, aziridines, cyclosiloxanes, ketals, cyclic anhydrides, lactams, aryl dialdehydes, etc., and the Equal to polymeric or cross-linked polymers and oligomers with polymeric groups in their side chains. These can be used individually or in mixture of 2 or more types. Specific examples of such cationic polymerizable compounds include acid-reactive organic substances described in International Publication No. 2017/130896, cationic polymerizable compounds described in International Publication No. 2014/084269, International Publication No. 2016/132413, etc. and other compounds.

A mixture of a cross-linkable resin and a cross-linking agent can also be used as the above-mentioned acid-curable component. Examples of the cross-linkable resin include: polyhydroxystyrene and its derivatives; polyacrylic acid and its derivatives; polymethacrylic acid and its derivatives; polyhydroxystyrene, acrylic acid, methacrylic acid and the like Copolymers of two or more selected from derivatives of hydroxystyrene, styrene and their derivatives; selected from cyclic olefins and their derivatives, maleic anhydride , and copolymers of three or more of acrylic acid and its derivatives; copolymers of three or more selected from cycloolefins and their derivatives, maleimide, and acrylic acid and its derivatives; polynorthene ; One or more high molecular polymers selected from the group consisting of metathesis ring-opening polymers; polymers with alkoxysilyl groups; High molecular polymers made by substituting the base part, etc. Examples of polymers containing structural units derived from hydroxystyrene, such as polyhydroxystyrene, include phenolic hydroxyl group-containing resins (QN) described in JP-A-2018-112670. The above-mentioned cross-linkable resin can also be used, for example, the resist base resin described in International Publication No. 2017/130896, and the action of the acid of the component (A) described in Japanese Patent Laid-Open No. 2003-192665. Resins whose solubility changes in a non-toxic developer, technical solution 3 of Japanese Patent Application Laid-Open No. 2004-323704, alkali-soluble resins described in Japanese Patent Application Laid-Open No. 10-10733, etc. As the above-mentioned polymer having an alkoxysilyl group, for example, a compound in which an alkoxysilyl group is not directly bonded to an aromatic ring can be used.

The said crosslinking agent should just be what can crosslink the said crosslinkable resin mutually in presence of an acid. This kind of crosslinking agent can use compounds containing epoxy groups, compounds containing hydroxyl groups, compounds containing alkoxy groups, compounds containing methylol groups, compounds containing carboxymethyl groups, etc., which can be mixed with the above resins in the presence of acid Compounds that react with acidic groups such as phenolic hydroxyl groups and carboxyl groups. As said crosslinking agent, more specifically, the crosslinking agent described in Unexamined-Japanese-Patent No. 2016-169173 and Unexamined-Japanese-Patent No. 2018-112670, etc. are mentioned.

The above-mentioned acid-decomposable components may be those whose solubility in the developer solution is increased by the acid generated by the compound A, for example, the compounds having phenolic hydroxyl groups, carboxyl groups, sulfonyl groups, and silanols are protected by protecting groups. Resins with some or all of the hydrogen atoms in the acidic groups in resins such as acidic groups. As a resin which has such an acidic group, the crosslinkable resin used as the said acid-curable component together with a crosslinking agent is mentioned, for example. Positive-type chemically amplified resins described in Japanese Patent Laid-Open No. 2018-112670 can also be used. The above-mentioned protecting group is sufficient as long as it can protect the above-mentioned acidic group, for example, the protecting group described in Japanese Patent Laid-Open No. 2016-169173, the acid-labile group described in International Publication No. 2017/130896, Japanese Patent Acid-dissociating groups described in JP-A-2018-112670, etc. Moreover, an alkoxysilyl group is mentioned as a group which protects the said silanol group with a protecting group. A polymer having an alkoxysilyl group used as an acid-decomposable component can be used, for example, as described in Japanese Patent Laid-Open No. 2019-66828 "having an alkoxy group containing an aromatic ring and directly bonded to the aromatic ring." The structural unit (I) of the silyl group, and the polymer component (A) containing the structural unit (II) of the acidic group" are exemplified. Moreover, as said developing solution, the developing solution described in the following "G. Manufacturing method of a pattern" is mentioned.

As the above-mentioned acid-reactive components, in addition to acid-hardening components and acid-decomposable components, components that react with acids may be used. For example, resins having alkali-soluble groups may also be resins that are insoluble by acids. Specifically, acid-insoluble resins in which intramolecular or intermolecular crosslinking reactions occur due to acid-catalyzed dehydration condensation of hydroxyl groups and carboxyl groups, such as those exemplified below, and carboxyl groups, can be mentioned. As an acid-insoluble resin which generates acid-catalyzed dehydration condensation of a carboxyl group and a carboxyl group, resin etc. which have a phthalic acid structure which dehydration-condenses carboxyl groups with an acid as mentioned below, etc. are mentioned, for example.

[chem 23]

The above-mentioned non-acid-reactive components can use those that do not react with the acid generated by compound A, more specifically, those that do not harden and decompose due to the acid generated by compound A, and that do not react with the acid generated by compound A can be used. Changes in solubility, etc., for example, thermoplastic resins such as polyolefin resins, polybutadiene resins, polystyrene resins, polystyrene-butadiene resins, polystyrene-olefin resins, etc. .

The content of the resin component in the composition of the present invention can be appropriately set according to the type of the resin component used, etc., as long as the effect of being excellent in acid generation sensitivity can be obtained. The content of the resin component in the composition of the present invention can be, for example, 10 parts by mass or more, preferably 30 parts by mass or more and 99.9 parts by mass or less, more preferably 50 parts by mass, based on 100 parts by mass of the solid content of the above composition. More than 99 parts by mass and less than or equal to 99 parts by mass. This is because the effect of being excellent in acid generation sensitivity can be effectively obtained. The content of the resin component in the composition of the present invention can be, for example, 10 parts by mass or more, more preferably 30 parts by mass or more and 99.9 parts by mass or less, particularly preferably 50 parts by mass or more 96 parts by mass, based on 100 parts by mass of the above-mentioned composition. Parts by mass or less. This is because the effect of being excellent in acid generation sensitivity can be effectively obtained.

3. Solvent The above composition may contain a solvent. The above-mentioned solvent is capable of dispersing or dissolving each component in the composition. Therefore, even if it is liquid at normal temperature (25 degreeC) and atmospheric pressure, the said compound A and a resin component are not contained in a solvent. As for the above-mentioned solvents, both water and organic solvents can be used. In the present invention, the above-mentioned solvent is preferably an organic solvent. The reason for this is that the above compound A is easily dissolved or dispersed. The above-mentioned organic solvent may be the same as that described in the item "B. Acid generator" above. Moreover, content of the said solvent in the composition of this invention can be set suitably according to the use etc. of the said composition, For example, it can set it as 1 mass part or more and 99 mass parts or less in 100 mass parts of the said composition.

4. Other ingredients The above-mentioned composition may contain other components as needed. Such other components can be selected according to the use of the composition, for example, benzotriazole-based, trioxane-based, benzoate-based ultraviolet absorbers; phenol-based, phosphorus-based, sulfur-based antioxidants; containing Antistatic agents for cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, etc.; halogen compounds, phosphate ester compounds, phosphoramide compounds, melamine compounds, fluororesins Or flame retardants such as metal oxides, (poly) melamine phosphate, (poly) piperamine phosphate, etc.; hydrocarbon-based, fatty acid-based, aliphatic alcohol-based, aliphatic ester-based, aliphatic amide-based or metal soap-based lubricants; Dyes, pigments, carbon black and other colorants; fumed silica, microparticle silica, silica, diatomaceous earth, clay, kaolin, diatomaceous earth, silica gel, calcium silicate, sericite, kaolin, flint, Silicic acid-based inorganic additives such as feldspar powder, vermiculite, ertesite, talc, mica, iron talc, pyrophyllite, and silicon dioxide; fillers such as glass fiber and calcium carbonate; crystallization such as nucleating agents and crystallization accelerators Rubber elasticity-imparting agents, silane coupling agents, flexible polymers, sensitizers, etc. In addition, the above-mentioned other components may contain acid diffusion control agents such as amine compounds, amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds. As said sensitizer, the compound disclosed as a spectral sensitizer in Japanese Patent Application Publication No. 2008-506749 is mentioned, for example. Examples of the acid diffusion controller include compounds disclosed in JP-A-2019-8300 as “[D] acid diffusion controller”. The content of these other components in the composition of this invention can be 50 mass parts or less in 100 mass parts of said compositions.

5. Other As for the method for producing the above-mentioned composition, any known method can be used as long as it can contain the above-mentioned components in a desired amount. For example, after dissolving or dispersing the said compound A in a solvent, the method etc. which add a resin component to the said solvent are mentioned.

D. hardening The cured product of the present invention is a cured product of the above composition. Moreover, the resin component contained in the said composition is an acid-curable component.

According to the present invention, by using the above-mentioned composition, a cured product in which the curing of the acid-curable component is sufficiently advanced can be obtained.

The cured product of the present invention uses the above composition. Also, the resin component is an acid-curable component. The above-mentioned cured product is obtained by hardening the acid-curable components, and includes a polymer formed by polymerizing the acid-curable components or a cross-linked product formed by cross-linking the acid-curable components. The content of such a composition can be the same as that described in the item "C. Composition" above, so the description here is omitted.

The plan view shape of the above-mentioned cured product can be appropriately set according to the application of the above-mentioned cured product, for example, it can be made into pattern shapes such as dots and lines.

The use of the above-mentioned cured product can be the same as that described in the item "A. Compound" above.

The method for producing the cured product is not particularly limited as long as the cured product of the above composition can be formed into a desired shape. For such a production method, for example, the production method described in the following "E. Production method of cured product" can be used.

E. Manufacturing method of hardened product Next, the manufacturing method of the cured product of this invention is demonstrated. One of the characteristics of the production method of the cured product of the present invention is to include a hardening step of hardening the composition. Moreover, the resin component contained in the said composition is an acid-curable component.

According to the present invention, by using the above-mentioned composition, the effect of being excellent in acid generation sensitivity can be effectively exhibited, and a cured product in which the acid-curable component can be sufficiently hardened can be easily formed.

1. Hardening step The hardening step in the present invention is a step of hardening the above composition. The method of curing the above-mentioned composition may be a method capable of curing the acid-curable component, and a method of generating an acid from compound A may be used. The method for generating acid from compound A may be any method that can generate a desired amount of acid from compound A, for example, a method of irradiating energy rays, a method of heat treatment, and a method of performing these simultaneously or sequentially . The method of irradiating such energy rays, the method of heat treatment, and the like may, for example, be the same as those described in the section "A. Compound". In this step, among others, the above-mentioned method of generating acid is preferably a method including irradiating energy rays. The reason for this is that the effect of being excellent in acid generation sensitivity can be effectively exerted, and the acid-curable component can be effectively hardened. In addition, the above-mentioned composition contains an acid-curable component as a resin component. The content of such a composition can be the same as that described in the item "C. Composition" above, so the description here is omitted.

2. Other steps The method for producing a hardened product of the present invention may optionally include other steps in addition to the above-mentioned hardening step. As the above-mentioned other steps, there may be mentioned: after the above-mentioned hardening step, a developing step of removing unpolymerized parts in the coating film of the composition to obtain a pattern-shaped hardened product; after the above-mentioned hardening step, heat-treating and then baking A baking step; a prebaking step of heat-treating the composition to remove the solvent in the composition before the hardening step; a step of forming a coating film of the composition before the hardening step. In the present invention, the above-mentioned other steps preferably have a post-baking step. The acid produced by Compound A can be efficiently diffused. The reason for this is that, as a result, a cured product in which the acid-curable component is sufficiently hardened is easily formed.

As a method of removing a non-polymerized part in the said image development process, the method of applying a developing solution, such as an alkaline developing solution, to a non-polymerized part is mentioned, for example. As the alkaline developing solution, those generally used as alkaline developing solutions such as tetramethylammonium hydroxide (TMAH) aqueous solution, potassium hydroxide aqueous solution, and potassium carbonate aqueous solution can be used. Moreover, as a developing solution, what is generally used as a solvent developing solution, such as propylene glycol monomethyl ether acetate (PEGMEA) and cyclohexanone, can be used. The developing method using the above-mentioned developing solution may be any method in which the portion to be developed is brought into contact with the developing solution, and known methods such as a shower method, a spray method, and a dipping method can be used. The implementation time of the above-mentioned developing step may be after the above-mentioned hardening step. As for the heating conditions in the above-mentioned post-baking step, as long as the strength of the cured product obtained in the curing step can be improved, for example, heating at a temperature of 200° C. to 250° C. for 20 minutes to 90 minutes can be used. As for the heating conditions in the above-mentioned prebaking step, as long as the solvent in the composition can be removed, for example, heating at a temperature of 70° C. to 150° C. for 30 seconds to 300 seconds can be used. In the above-mentioned step of forming the coating film, the method of coating the composition can use a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing, A known method such as dipping. The aforementioned coating film can be formed on a substrate. The base material can be appropriately set according to the application of the cured product, and examples include soda glass, quartz glass, semiconductor substrates, wiring substrates, metals, paper, plastics, and the like. Moreover, after forming the said hardened|cured material on a base material, it can peel from a base material, and can use it, and can also transfer from a base material to another to-be-adhered body and use.

F. Pattern The pattern of the present invention is produced using a positive photoresist comprising the above composition. Moreover, the resin component contained in the said composition is an acid-decomposable component.

According to the present invention, by using the above-mentioned composition, the effect of excellent acid generation sensitivity can be effectively exerted, and acid-decomposable components can be easily decomposed. As a result, it is easy to form a pattern excellent in dimensional accuracy and the like.

The pattern of the present invention uses the composition described above. Also, the resin component is an acid-decomposable component. The above-mentioned pattern is formed by forming a coating film using the above-mentioned composition and removing unnecessary parts. Specifically, it is formed in the following manner: after the coating film is formed, energy rays are irradiated through a specific mask, etc., acid is generated in the irradiated part to increase the solubility in the developer, and the irradiated part is removed by developing treatment. part. The content of such a composition can be the same as that described in the item "C. Composition" above, so the description here is omitted.

The top view shape of the above-mentioned pattern can be appropriately set according to the use of the above-mentioned pattern, for example, it can be made into pattern shapes such as dots and lines.

The use of the above-mentioned pattern can be the same as that described in the item "A. Compound" above.

The method for producing the above-mentioned pattern is not particularly limited as long as it can form the above-mentioned composition into a desired shape. For such a production method, for example, the production method described in the following "G. Production method of pattern" can be used.

G. Pattern manufacturing method Next, the manufacturing method of the pattern of this invention is demonstrated. The method for producing a pattern of the present invention has the steps of: forming a coating film using the above-mentioned composition, generating an acid from a compound contained in the formed coating film; and developing the coating film after the above-mentioned step of generating an acid from the compound, thereby A part of this coating film is removed to form a pattern. The resin component contained in the above composition is an acid-decomposable component.

According to the present invention, a pattern excellent in dimensional accuracy and the like can be obtained by using the composition described above.

1. The step of generating acid The step of generating an acid in the present invention is a step of generating an acid from the above-mentioned compound A contained in the coating film formed using the above-mentioned composition. In this step, the method for generating acid from the above-mentioned compound A may be a method that can generate a required amount of acid from compound A, for example, a method of irradiating energy rays, a method of heat treatment, and simultaneously or sequentially. The method of irradiating such energy rays, the method of heat treatment, and the like may, for example, be the same as those described in the section "A. Compound". In this step, among others, the above-mentioned method of generating acid is preferably a method including irradiating energy rays. The reason for this is that the effect of obtaining a pattern excellent in dimensional accuracy and the like can be effectively exhibited. In addition, in this step, the site where the acid is generated in the coating film is preferably a part of the coating film in plan view. The reason for this is that the step of forming the pattern described below is easy to carry out. The plan view shape and thickness of the said coating film can be suitably set according to the use etc. of a pattern coating film. In addition, the above-mentioned composition contains an acid-decomposable component as a resin component. The content of such a composition can be the same as that described in the item "C. Composition" above, so the description here is omitted.

2. Steps to form a pattern The step of forming a pattern in the present invention is a step of forming a pattern by developing the above-mentioned coating film to remove part of it after the step of generating an acid from the above-mentioned compound. As a method of performing image development in this step, the method of performing image development using a developing solution is mentioned. Such a developing solution and a developing method may be the same as those described in the item "E. Manufacturing method of cured product" above.

3. Other steps The method for producing a pattern of the present invention includes the above step of generating an acid and the step of forming a pattern, but may also include other steps as necessary. As such other steps, there may be mentioned: a step of forming a coating film of the above-mentioned composition before the above-mentioned step of generating an acid; Baking steps, etc. In the present invention, the above-mentioned other steps preferably have a post-exposure baking step. The acid produced by Compound A can be efficiently diffused. The reason for this is that, as a result, the decomposition of acid-decomposable components can be performed more efficiently. The above step of forming the coating film and the step of performing prebaking may be the same as those described in the item "E. Manufacturing method of cured product" above. Moreover, about the conditions of a post-exposure baking process, it can set it as 30 second - 300 second at 70 to 150 degreeC, for example.

4. Other The pattern produced by the above-mentioned production method and its use can be the same as those described in the above "A. Composition".

(式中，Ar為構成環之碳原子數為5～20之芳香族環基， R ³¹表示下述通式(1)所表示之基， R ³²為選自下述通式(IVa)、(IVb)、(IVc)、(IVd)、(IVe)、(IVf)、(IVg)及(IVh)中之式所表示之基， R ³³表示鹵素原子、硝基、氰基、-OR ³⁴、-COR ³⁴、-OCOR ³⁴、-COOR ³⁴、-SR ³⁴、-SOR ³⁴、-SO ₂R ³⁴、-NR ³⁵R ³⁶、-NR ³⁵COR ³⁶、-CONR ³⁵R ³⁶、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ia中之二價基而成之基， 於存在複數個R ³¹、R ³²或R ³³之情形時，其等可相同，亦可不同， R ³⁴、R ³⁵及R ³⁶分別獨立地表示氫原子、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ia中之二價基而成之基，於存在複數個R ³⁴、R ³⁵或R ³⁶之情形時，其等可相同，亦可不同， 取代上述具有取代基之烴基及上述具有取代基之含有雜環之基中之1個以上氫原子的取代基為選自下述群IIa中之原子或基， a表示1～20之整數， b表示1～20之整數， c表示0～18之整數， a、b及c之合計為21以下) [化25]

(式中，R ¹表示碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ia中之二價基而成之基， R ²表示氫原子、鹵素原子、硝基、氰基、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ia中之二價基而成之基， 取代上述具有取代基之烴基及上述具有取代基之含有雜環之基中之1個以上氫原子的取代基為選自下述群IIa中之原子或基， *表示鍵結部位) [化26]

(式中，R ⁵¹表示OR ⁸¹、NR ⁸²R ⁸³或碳原子數2～20之未經取代或具有取代基之含有雜環之基， R ⁵²及R ⁵³分別獨立地表示R ⁸¹或OR ⁸¹，R ⁵²與R ⁵³可鍵結而形成環， R ⁵⁵、R ⁵⁶、R ⁵⁸、R ⁵⁹、R ⁶¹、R ⁶²、R ⁶⁴、R ⁶⁵、R ⁷¹及R ⁷³分別獨立地表示碳原子數6～20之未經取代或具有取代基之芳基， R ⁵⁴、R ⁵⁷、R ⁶⁰、R ⁶³、R ⁶⁶、R ⁶⁷及R ⁷²分別獨立地表示碳原子數6～20之未經取代或具有取代基之伸芳基或單鍵， R ⁶⁸表示碳原子數1～20之未經取代或具有取代基之烴基， R ⁶⁹及R ⁷⁰分別獨立地表示R ⁸¹或OR ⁸¹， R ⁸¹、R ⁸²及R ⁸³分別獨立地表示氫原子或碳原子數1～20之未經取代或具有取代基之烴基， *表示鍵結部位) (群Ia：-O-、-COO-、-OCO-、-CO-、-CO-CO-、-CO-CO-O-、-CS-、-S-、-SO-、-SO ₂-、-NR'-、-NR'-CO-、-CO-NR'-、-NR'-COO-、-OCO-NR'-或-SiR'R''-。 群IIa：鹵素原子、氰基、硝基、-CO-H、-OH、-SH、-NH ₂、-COOH或-SO ₃H。 R'及R''分別獨立地表示氫原子或碳原子數1～20之未經取代之脂肪族烴基，於存在複數個R'或R''之情形時，其等可相同，亦可不同) [2] 如[1]中所記載之化合物，其中上述芳香族環基Ar為具有下述通式(Ara)或(Arb)所表示之結構之芳香族環基。 [化27]

(式中，X ¹為單鍵、無鍵、氧原子、硫原子、硒原子、CR ⁴¹R ⁴²、CO、NR ⁴³或PR ⁴⁴， X ²為氧原子、硫原子、硒原子、CR ⁴¹R ⁴²、CO、NR ⁴³或PR ⁴⁴， X ³為NR ⁵³， R ⁴¹、R ⁴²、R ⁴³及R ⁴⁴分別獨立地表示氫原子、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ib中之二價基而成之基，於存在複數個R ⁴¹、R ⁴²、R ⁴³及R ⁴⁴之情形時，其等可相同，亦可不同， R ⁵³表示氫原子、鹵素原子、硝基、氰基、-OR ¹¹¹、-COR ¹¹¹、-OCOR ¹¹¹、-COOR ¹¹¹、-SR ¹¹¹、-SOR ¹¹¹、-SO ₂R ¹¹¹、-NR ¹¹²R ¹¹³、-NR ¹¹²COR ¹¹³、-CONR ¹¹²R ¹¹³、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ib中之二價基而成之基， R ¹¹¹、R ¹¹²及R ¹¹³分別獨立地表示氫原子、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ib中之二價基而成之基，於分別存在複數個R ¹¹¹、R ¹¹²及R ¹¹³之情形時，其等可相同，亦可不同， 取代上述具有取代基之烴基及上述具有取代基之含有雜環之基中之1個以上氫原子的取代基為選自下述群IIb中之原子或基) (群Ib：-O-、-COO-、-OCO-、-CO-、-CO-CO-、-CO-CO-O-、-CS-、-S-、-SO-、-SO ₂-、-NR'-、-NR'-CO-、-CO-NR'-、-NR'-COO-、-OCO-NR'-或-SiR'R''-。 群IIb：鹵素原子、氰基、硝基、-CO-H、-OH、-SH、-NH ₂、-COOH或-SO ₃H。 R'及R''分別獨立地表示氫原子或碳原子數1～20之未經取代之脂肪族烴基，於存在複數個R'或R''之情形時，其等可相同，亦可不同) [3] 如[2]中所記載之化合物，其中上述a為1， 上述b為1，且 上述通式(A)中之下述部分結構(Aα)為下述通式(Ara1)或(Arb1)所表示之基。 [化28]

(式中，Ar、R ³³及c與式(A)相同。*1表示與R ³¹之鍵結部位，*2表示與R ³²之鍵結部位) [化29]

(式中，X ¹、X ²及X ³分別與上述通式(Ara)及(Arb)中之內容相同， R ¹⁴¹、R ¹⁴²、R ¹⁵¹及R ¹⁵²分別獨立地表示鹵素原子、硝基、氰基、-OR ¹²¹、-COR ¹²¹、-OCOR ¹²¹、-COOR ¹²¹、-SR ¹²¹、-SOR ¹²¹、-SO ₂R ¹²¹、-NR ¹²²R ¹²³、-NR ¹²²COR ¹²³、-CONR ¹²²R ¹²³、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ic中之二價基而成之基， R ¹²¹、R ¹²²及R ¹²³分別獨立地表示氫原子、碳原子數1～20之未經取代或具有取代基之烴基、碳原子數2～20之未經取代或具有取代基之含有雜環之基、或者上述烴基或上述含有雜環之基中之1個以上亞甲基被取代為選自下述群Ic中之二價基而成之基，於分別存在複數個R ¹²¹、R ¹²²及R ¹²³之情形時，其等可相同，亦可不同， 取代上述具有取代基之烴基及上述具有取代基之含有雜環之基中之1個以上氫原子的取代基為選自下述群IIc中之原子或基， a1為0～3， a2為0～3， c1為0～3， c2為0～1， *1表示與R ³¹之鍵結部位， *2表示與R ³²之鍵結部位) (群Ic：-O-、-COO-、-OCO-、-CO-、-CO-CO-、-CO-CO-O-、-CS-、-S-、-SO-、-SO ₂-、-NR'-、-NR'-CO-、-CO-NR'-、-NR'-COO-、-OCO-NR'-或-SiR'R''-。 群IIc：鹵素原子、氰基、硝基、-CO-H、-OH、-SH、-NH ₂、-COOH或-SO ₃H。 R'及R''分別獨立地表示氫原子或碳原子數1～20之未經取代之脂肪族烴基，於存在複數個R'或R''之情形時，其等可相同，亦可不同) [4] 如[1]至[3]中任一項所記載之化合物，其中上述R ³²為上述通式(IVa)、(IVf)及(IVh)之任一者所表示之基。 [5] 如[1]～[4]中任一項所記載之化合物，其中R ¹為碳原子數1～20之具有鹵素原子作為取代基之烴基，且 R ²為氰基、碳原子數1～20之具有鹵素原子作為取代基之烴基、或者碳原子數1～20之未經取代或具有鹵素原子作為取代基之烴基之1個以上亞甲基被取代為-COO-而成之基。 [6] 一種酸產生劑，其包含如[1]～[5]中任一項所記載之化合物。 [7] 一種組合物，其包含如[1]～[5]中任一項所記載之化合物、及 樹脂成分。 [8] 如[7]中所記載之組合物，其中上述樹脂成分為酸硬化性樹脂成分。 [9] 一種硬化物，其係如[8]中所記載之組合物之硬化物。 [10] 一種硬化物之製造方法，其具有使如[8]中所記載之組合物硬化之硬化步驟。 [11] 如[7]中所記載之組合物，其中上述樹脂成分為酸分解性樹脂成分。 [12] 一種圖案，其由如[11]中所記載之組合物製造。 [13] 一種圖案之製造方法，其具有如下步驟：使用如[11]中所記載之組合物形成塗膜，由所形成之塗膜中所包含之上述化合物產生酸；及 在由上述化合物產生酸之步驟後，使塗膜顯影而去除該塗膜之一部分，形成圖案。 [14] 一種圖案，其包含如[11]中所記載之組合物。 [15] 一種正型光阻，其包含如[11]中所記載之組合物。 In this invention, the following forms are mentioned. [1] A compound having a structure represented by the following general formula (A). [chem 24]

(In the formula, Ar is an aromatic ring group with 5 to 20 carbon atoms constituting the ring, R ³¹ represents a group represented by the following general formula (1), R ³² is selected from the following general formula (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) and (IVh) in the group represented by the formula, R ³³ represents a halogen atom, nitro, cyano, -OR ³⁴ , -COR ³⁴ , -OCOR ³⁴ , -COOR ³⁴ , -SR ³⁴ , -SOR ³⁴ , -SO ₂ R ³⁴ , -NR ³⁵ R ³⁶ , -NR ³⁵ COR 36 , -CONR 35 R ³⁶ , -CONR ³⁵ R ³⁶ , carbon number 1～ 20 unsubstituted or substituted hydrocarbon groups, unsubstituted or substituted heterocyclic ring-containing groups having 2 to 20 carbon atoms, or one or more methylene groups among the above-mentioned hydrocarbon groups or the above-mentioned heterocyclic ring-containing groups The group is substituted with a divalent group selected from the following group Ia. When there are a plurality of R ³¹ , R ³² or R ³³ , they may be the same or different, R ³⁴ , R ³⁵ and ^R36 independently represent a hydrogen atom, an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group with 2 to 20 carbon atoms, or the above-mentioned A hydrocarbon group or a group in which at least one methylene group is substituted with a divalent group selected from the group Ia below, when there are multiple R ³⁴ , R ³⁵ or R ³⁶ , which may be the same or different, and the substituents substituting one or more hydrogen atoms in the above-mentioned hydrocarbon group with substituents and the above-mentioned heterocyclic ring-containing group with substituents are atoms or groups selected from the following group IIa , a represents an integer of 1 to 20, b represents an integer of 1 to 20, c represents an integer of 0 to 18, and the total of a, b and c is 21 or less) [Chemical 25]

(wherein, R ¹ represents an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group with 2 to 20 carbon atoms, or the above hydrocarbon group or the above A group in which one or more methylene groups in a group containing a heterocycle is substituted with a divalent group selected from the following group Ia, ^R2 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, and the number of carbon atoms Unsubstituted or substituted hydrocarbon groups with 1 to 20 carbon atoms, unsubstituted or substituted heterocycle-containing groups with 2 to 20 carbon atoms, or one or more of the above-mentioned hydrocarbon groups or the above-mentioned heterocycle-containing groups A substituent in which a methylene group is substituted with a divalent group selected from the following group Ia, substituting one or more hydrogen atoms in the above-mentioned hydrocarbon group with a substituent and the above-mentioned heterocyclic ring-containing group with a substituent is an atom or group selected from the following group IIa, * represents a bonding site) [Chem. 26]

(In the formula, R ⁵¹ represents OR ⁸¹ , NR ⁸² R ⁸³ or an unsubstituted or substituted heterocyclic group with 2 to 20 carbon atoms, R ⁵² and R ⁵³ independently represent R ⁸¹ or OR ⁸¹ , R ⁵² and R ⁵³ can be bonded to form a ring, R ⁵⁵ , R ⁵⁶ , R ⁵⁸ , R ⁵⁹ , R ⁶¹ , R ⁶² , R ⁶⁴ , R ⁶⁵ , R ⁷¹ and R ⁷³ each independently represent 6 carbon atoms ~20 unsubstituted or substituted aryl groups, R ⁵⁴ , R ⁵⁷ , R ⁶⁰ , R ⁶³ , R ⁶⁶ , R ⁶⁷ and R ⁷² each independently represent an unsubstituted or substituted aryl group with 6 to 20 carbon atoms. The substituent is an aryl group or a single bond, R ⁶⁸ represents an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, R ⁶⁹ and R ⁷⁰ independently represent R ⁸¹ or OR ⁸¹ , R ⁸¹ , R ⁸² and R ⁸³ each independently represent a hydrogen atom or an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, and * represents a bonding site) (Group Ia: -O-, -COO-, -OCO-, - CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO ₂ -, -NR'-, -NR'-CO-, -CO-NR '-, -NR'-COO-, -OCO-NR'- or -SiR'R''-. Group IIa: Halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH _2. -COOH or -SO ₃ H. R' and R'' each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group with 1 to 20 carbon atoms. When there are multiple R' or R'' (they may be the same or different) [2] The compound as described in [1], wherein the aromatic ring group Ar is an aromatic ring having a structure represented by the following general formula (Ara) or (Arb) family ring group. [chem 27]

(In the formula, X ¹ is a single bond, no bond, oxygen atom, sulfur atom, selenium atom, CR ⁴¹ R ⁴² , CO, NR ⁴³ or PR ⁴⁴ , X ² is an oxygen atom, sulfur atom, selenium atom, CR ⁴¹ R 44 ⁴² , CO, NR ⁴³ or PR ⁴⁴ , X ³ is NR ⁵³ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom, an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms , an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or one or more methylene groups in the above-mentioned hydrocarbon group or the above-mentioned heterocyclic ring-containing group are substituted to be selected from the following group Ib When there are a plurality of R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ , they may be the same or different. R ⁵³ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group -OR ¹¹¹ , -COR ¹¹¹ , -OCOR ¹¹¹ , -COOR ¹¹¹ , -SR ¹¹¹ , -SOR ¹¹¹ , -SO ₂ R ¹¹¹ , -NR ¹¹² R ¹¹³ , -NR ¹¹² COR ¹¹³ , -CONR ¹¹² R ¹¹³ , An unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group with 2 to 20 carbon atoms, or any of the above-mentioned hydrocarbon groups or the above-mentioned heterocyclic ring-containing groups One or more methylene groups are substituted with divalent groups selected from the following group Ib, R ¹¹¹ , R ¹¹² and R ¹¹³ each independently represent a hydrogen atom, an unsubstituted group having 1 to 20 carbon atoms Or a hydrocarbon group with a substituent, an unsubstituted or substituted heterocycle-containing group with 2 to 20 carbon atoms, or one or more methylene groups in the above-mentioned hydrocarbon group or the above-mentioned heterocycle-containing group are substituted as optional A group derived from a divalent group in the following group Ib, when there are a plurality of R ¹¹¹ , R ¹¹² and R ¹¹³ , which may be the same or different, replaces the above-mentioned hydrocarbon group having a substituent and the above-mentioned The substituent of one or more hydrogen atoms in the heterocyclic ring-containing group having a substituent is an atom or group selected from the following Group IIb) (Group Ib: -O-, -COO-, -OCO-, -CO -, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO ₂ -, -NR'-, -NR'-CO-, -CO-NR' -, -NR'-COO-, -OCO-NR'- or -SiR'R''-. Group IIb: Halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH ₂ , -COOH or -SO ₃ H. R' and R'' each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, when there are multiple R' or R'' , etc. may be the same or different) [3] The compound as described in [2], wherein the above-mentioned a is 1, the above-mentioned b is 1, and the following partial structure (Aα) in the above-mentioned general formula (A) It is a group represented by the following general formula (Ara1) or (Arb1). [chem 28]

(In the formula, Ar, R ³³ and c are the same as formula (A). *1 represents the bonding site with R ³¹ , and *2 represents the bonding site with R ³² ) [Chemical 29]

(In the formula, X ¹ , X ² and X ³ are the same as those in the above general formulas (Ara) and (Arb) respectively, R ¹⁴¹ , R ¹⁴² , R ¹⁵¹ and R ¹⁵² independently represent a halogen atom, a nitro group, Cyano, -OR ¹²¹ , -COR ¹²¹ , -OCOR ¹²¹ , -COOR ¹²¹ , -SR ¹²¹ , -SOR ¹²¹ , -SO ₂ R ¹²¹ , -NR ¹²² R ¹²³ , -NR ¹²² COR ¹²³ , -CONR ¹²² R ¹²³ , an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group with 2 to 20 carbon atoms, or the above hydrocarbon group or the above heterocyclic ring-containing group One or more of the methylene groups are substituted with divalent groups selected from the following group Ic, R ¹²¹ , R ¹²² and R ¹²³ independently represent a hydrogen atom, a hydrogen atom having 1 to 20 carbon atoms A substituted or substituted hydrocarbon group, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or one or more methylene groups in the above-mentioned hydrocarbon group or the above-mentioned heterocycle-containing group are substituted with A group selected from a divalent group in the following group Ic, when there are a plurality of R ¹²¹ , R ¹²² and R ¹²³ , they may be the same or different, substituting the above-mentioned hydrocarbon group having a substituent and The substituents for one or more hydrogen atoms in the heterocyclic ring-containing group having substituents are atoms or groups selected from the following group IIc, a1 is 0 to 3, a2 is 0 to 3, and c1 is 0 to 3 , c2 is 0～1, *1 represents the bonding site with ^R31 , *2 represents the bonding site with ^R32 ) (group Ic: -O-, -COO-, -OCO-, -CO-, - CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO ₂ -, -NR'-, -NR'-CO-, -CO-NR'-, - NR'-COO-, -OCO-NR'- or -SiR'R''-. Group IIc: Halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH ₂ , -COOH Or -SO ₃ H. R' and R'' each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group with 1 to 20 carbon atoms. When there are multiple R' or R'', the may be the same or different) [4] The compound as described in any one of [1] to [3], wherein the above-mentioned R ³² is any one of the above-mentioned general formulas (IVa), (IVf) and (IVh) The basis of the representation. [5] The compound as described in any one of [1] to [4], wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms with a halogen atom as a substituent, and R ² is a cyano group, a carbon number A hydrocarbon group with 1 to 20 halogen atoms as a substituent, or a hydrocarbon group with 1 to 20 carbon atoms that is unsubstituted or has a halogen atom as a substituent, in which one or more methylene groups are substituted with -COO- . [6] An acid generator comprising the compound according to any one of [1] to [5]. [7] A composition comprising the compound according to any one of [1] to [5], and a resin component. [8] The composition as described in [7], wherein the resin component is an acid-curable resin component. [9] A hardened product of the composition described in [8]. [10] A method for producing a hardened product, comprising a hardening step of hardening the composition described in [8]. [11] The composition as described in [7], wherein the resin component is an acid-decomposable resin component. [12] A pattern produced from the composition as described in [11]. [13] A method for producing a pattern, comprising the steps of: forming a coating film using the composition described in [11], generating an acid from the above-mentioned compound contained in the formed coating film; After the acid step, the coating film is developed to remove a part of the coating film to form a pattern. [14] A pattern comprising the composition as described in [11]. [15] A positive photoresist comprising the composition described in [11].

The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are examples, and those having substantially the same configuration as the technical idea described in the claims of the present invention and having the same function and effect are included in the technical scope of the present invention. [Example]

Hereinafter, although an Example etc. are given and this invention is demonstrated in more detail, this invention is not limited to these Examples.

[Example 1] (Synthesis of Compound No.1) ・N-Alkylation Add 33.4 g (200 mmol) of carbazole, 3.9 g (12 mmol) of tetrabutylammonium bromide, and 167.7 g (180 mmol) of o-xylene into a 1 L four-neck flask, and stir at room temperature. 93.5 g (800 mmol) of 48% by mass potassium hydroxide aqueous solution was added dropwise thereto. The mixture was heated and stirred at 40° C. on an oil bath, and 40.6 g (210 mmol) of 1-bromo-2-ethylhexane was added dropwise. Heat and stir at 120° C. on an oil bath for 3 hours. After cooling to room temperature, ion-exchanged water was added to carry out oil-water separation. After washing once with 3% by mass hydrochloric acid and three times with ion-exchanged water, the organic layer was concentrated to obtain 52.3 g of the target intermediate 1-A of a light red oily substance at a yield of 94%.

[chem 30]

・Acylation Add 25.2 g (90 mmol) of intermediate 1-A, 13.2 g (110 mmol) of DMAP (N,N-dimethyl-4-aminopyridine) and 337.9 g (theoretical yield 10 times of EDC (1,2-dichloroethane), stirred at 5°C on an ice bath. 19.9 g (95 mmol) of trifluoroacetic anhydride was added dropwise thereto. Furthermore, 36 g (270 mmol) of aluminum chloride was divided into 6 parts and added while paying attention to heat generation. After warming up to room temperature, it was stirred for 3 hours. The reaction solution was poured into ion-exchanged water, chloroform was added, and oil-water separation was performed. After washing with ion-exchanged water three times, 50 g of silica gel was added to the organic layer and filtered. The filtrate was concentrated to obtain a crude product of the target intermediate 1-B as a yellow oil. It was used for the next reaction without purification.

[chem 31]

・Oximation reaction Add 18.8 g (50 mmol) of intermediate 1-B, 3.8 g (55 mmol) of hydroxylamine hydrochloride and 97.6 g (5 times the theoretical yield) of ethanol to a 500 mL four-necked flask, and place on an oil bath Heat to reflux at 90°C for 7 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure, chloroform was added to the residue, and the residue was washed three times with ion-exchanged water. After concentration, Intermediate 1-C was used for the next reaction without purification.

[chem 32]

・Sulfonate Add 13.5 g (40 mmol) of intermediate 1-C, 104.5 g (5 times the theoretical yield) of chloroform and 8.1 g (80 mmol) of triethylamine to a 300 mL four-neck flask, and place in an ice bath at 5 Stirring is carried out at ℃. 16.9 g (60 mmol) of trifluoromethanesulfonic anhydride was added dropwise thereto so as not to exceed 10°C, and after the dropwise addition was completed, it was stirred at room temperature for 2 hours. The reaction solution was poured into ice water, and after the oil and water were separated, it was washed 3 times with ion-exchanged water. After concentration, the ketone body of the raw material remained in HPLC (high performance liquid chromatograph) measurement, but the intermediate 1-D was used for the next reaction without purification.

[chem 33]

・Diketone introduction Add 10.5 g (20 mmol) of intermediate 1-D and 62.3 g (6 times the theoretical yield) of EDC to a 300 mL four-necked flask, and stir in an ice bath. 3.6 g (24 mmol) of chloroglyoxylate was added dropwise thereto. Furthermore, 3.5 g (26 mmol) of aluminum chloride was divided into 4 parts and added while paying attention to heat generation. After confirming that the raw materials disappeared by HPLC, the reaction solution was poured into ion-exchanged water. After oil and water were separated, the organic layer was washed with water three times and then concentrated. The residue was purified by silica gel column chromatography (developing solvent: ethyl acetate:hexane = volume ratio 1:10 to 1:5). Methanol was added to the residue for dispersion washing, and after filtration, hexane was further added for dispersion washing. 2.06 g of the target compound No. 1 was obtained in a yield of 16%. The measurement results of ¹ H-NMR and ¹⁹ F-NMR are shown in Table 1 and Table 2.

[chem 34]

[Example 2] (Synthesis of Compound No. 2) Instead of 1-bromo-2-ethylhexane, methyl chloroglyoxylate was used instead of chloroglyoxylate. Compound No.2 was synthesized by the same method as Compound No.1. It was confirmed by ¹ H-NMR and ¹⁹ F-NMR that the obtained solid was the target object. The measurement results are shown in Table 1 and Table 2.

[chem 35]

[Example 3] (Synthesis of Compound No. 3) Compound No. 3 was synthesized in the same manner as the step after the acylation reaction of Compound No. 1, except that fennel was used as the main raw material instead of carbazole. It was confirmed by ¹ H-NMR and ¹⁹ F-NMR that the obtained solid was the target object. The measurement results are shown in Table 1 and Table 2.

[chem 36]

[Example 4] (Synthesis of Compound No.4) Add 2.0 g (32 mmol) of Compound No.1 and 21.5 g (10 times the theoretical yield) of EDC into a 100 mL four-neck flask, and stir on an ice bath. Add 1.5 g (110 mmol) of aluminum chloride in 4 parts and pay attention to heat generation. After confirming that the raw materials disappeared by HPLC, the reaction solution was poured into ion-exchanged water. After oil and water were separated, the organic layer was washed with water three times and then concentrated. The residue was purified by silica gel column chromatography (developing solvent: ethyl acetate:hexane = volume ratio 1:10 to 1:5). 1.27 g of the target compound No. 4 was obtained in a yield of 59%.

[chem 37]

[Table 1] ¹ H-NMR (solvent: CDCl ₃ ) Chemical shift ppm (number of protons, multiplicity) Compound No.1 8.85(s, 1H), 8.59(s, 1H), 8.27(d, 1H), 8.26(d, 1H), 7.67(t, 1H), 7.55(m, 1H), 4.58(t, 2H), 4.53 (d, 2H), 2.18(m, 1H), 1.50-1.28(m, 11H), 0.98(d, 3H), 0.88(d, 3H) Compound No.2 8.85(s, 1H), 8.32(s, 1H), 8.20(d, 1H), 8.09(d, 1H), 7.66(t, 1H), 7.55(m, 1H), 4.53(t, 2H), 3.61 (s, 3H), 0.98(d, 3H) Compound No.3 8.26(s, 1H), 8.13(d, 1H), 8.11(d, 1H), 8.02(d, 1H), 7.96(d, 1H), 7.69(s, 1H), 7.53(d, 1H), 4.50 (t, 2H), 4.11(s, 1H), 1.44(d, 3H) Compound No.4 8.86(s, 1H), 8.71(s, 1H), 8.67(d, 1H), 8.26(d, 1H), 7.65(t, 1H), 7.53(m, 1H), 4.57(t, 2H), 4.52 (d, 2H), 2.18(m, 1H), 1.51 - 1.24(m, 11H), 0.93(d, 3H), 0.84(d, 3H)

[Table 2] ¹⁹ F-NMR (solvent: CDCl ₃ ) chemical shift ppm Compound No.1 -65.58, -70.84 Compound No.2 -65.58, -70.82 Compound No.3 -66.26, -70.87 Compound No.4 -70.27

[Examples 5-7 and Comparative Examples 1-2] According to the composition described in the following Table 3, a resin component, an acid generator, and a surfactant were added to propylene glycol monomethyl ether acetate (PGMEA), and stirred at 25° C. for 1 hour to obtain a composition (solid content) 25% by mass of PGMEA solution). The following materials were used for each component. In addition, the compounding quantity in Table 3 represents a mass part.

Resin component: MARUKA LYNKER TST (manufactured by Maruzen Petrochemical Co., Ltd., p-hydroxystyrene-styrene-tert-butyl acrylate copolymer, acid-decomposable component) Surfactant: FZ2122 (manufactured by Toray Dow Corning) Acid generators: compounds produced in Examples 1 to 3 (including acid generators of Compound Nos. 1 to 3) Acid generator: the following comparative compounds No. 1, 2

[chem 38]

1. Sensitivity evaluation The above-prepared composition was filtered through a 5 μm microfilter, and spin-coated (1300 rpm, 7 s) on a glass substrate so that the film thickness after prebaking became 3 μm. Then, prebaking was performed at 110° C. for 120 seconds using a heating plate to obtain a positive photoresist film. After exposure using a high-pressure mercury lamp, PEB (Post Exposure Bake) was performed at 120° C. for 120 seconds, and developed with 2.38 mass % tetramethylammonium hydroxide aqueous solution for 10 seconds to obtain a positive pattern. The line width (width of the part removed by development) of the pattern obtained with a mask opening of 20 μm and exposure amounts of 20 mJ/cm ² and 40 mJ/cm ² was measured using a microscope. The wider the development width, the higher the sensitivity was evaluated. The results are shown in Table 3.

2. Solubility For each acid generator, the solubility in PGMEA at 25°C was evaluated. The results are shown in Table 3. The values shown in Table 3 are soluble concentrations (% by mass).

3. Mole absorptivity (ε) and transmittance The absorption spectrum of the positive-type photoresist film obtained in the same manner as described in "1. Sensitivity evaluation" was measured using a UV-visible spectrophotometer (U-3010 manufactured by Hitachi High-Tech Science), and 365 nm was calculated. Mole absorptivity and transmittance at 400 nm. The results are shown in Table 3.

[table 3] Example 5 Example 6 Example 7 Comparative example 1 Comparative example 2 combination resin 24.70 24.70 24.70 24.70 24.70 acid generator Compound No.1 0.25 Compound No.2 0.25 Compound No.3 0.25 Comparative Compound No.1 0.25 Comparative Compound No.2 0.25 Surfactant 0.05 0.05 0.05 0.05 0.05 PGMEA 75.00 75.00 75.00 75.00 75.00 evaluate Developing width (μm) Exposure (20 mJ/cm ² ) 32 28 20 19 15 Exposure (40 mJ/cm ² ) 37 33 26 twenty four 17 Solubility (wt%) 25 5 20 20 1.5 ε(365nm) 1.18 E+04 1.16 E+04 9.84 E+03 1.21 E+04 6.50 E+02 Transmittance@400 nm(%) 98.1 98.9 99.2 97.7 96.3

The absorption coefficients of the compounds No.1-3 used in Examples 5-7 under the i-line (365 nm) maintained relatively high values. It was confirmed that the line width of the pattern obtained by the composition of the example using the compound No. 1 to 3 of the present invention is thicker than the developed width of the pattern obtained by the composition of the comparative example using other compounds, and the acid generation Excellent sensitivity. In addition, the positive photoresist film of each example had the highest transmittance at 400 nm, and a highly transparent photoresist film with suppressed coloration was obtained. Furthermore, Compound Nos. 1 to 3 of the present invention have relatively high solubility in solvents. As described above, the compound of the present invention is excellent in high sensitivity and high transparency, and has sufficient solvent solubility, and is suitable as a photoacid generator used in a photoresist.

Claims (13)

A compound having a structure represented by the following general formula (A), [Chemical 1]

(In the formula, Ar is an aromatic ring group with 5 to 20 carbon atoms constituting the ring, R ³¹ represents a group represented by the following general formula (1), R ³² is selected from the following general formula (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) and (IVh) in the group represented by the formula, R ³³ represents a halogen atom, nitro, cyano, -OR ³⁴ , -COR ³⁴ , -OCOR ³⁴ , -COOR ³⁴ , -SR ³⁴ , -SOR ³⁴ , -SO ₂ R ³⁴ , -NR ³⁵ R ³⁶ , -NR ³⁵ COR 36 , -CONR 35 R ³⁶ , -CONR ³⁵ R ³⁶ , carbon number 1～ 20 unsubstituted or substituted hydrocarbon groups, unsubstituted or substituted heterocyclic ring-containing groups having 2 to 20 carbon atoms, or one or more methylene groups among the above-mentioned hydrocarbon groups or the above-mentioned heterocyclic ring-containing groups The group is substituted with a divalent group selected from the following group Ia. When there are a plurality of R ³¹ , R ³² or R ³³ , they may be the same or different, R ³⁴ , R ³⁵ and ^R36 independently represent a hydrogen atom, an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group with 2 to 20 carbon atoms, or the above-mentioned A hydrocarbon group or a group in which at least one methylene group is substituted with a divalent group selected from the group Ia below, when there are multiple R ³⁴ , R ³⁵ or R ³⁶ , which may be the same or different, and the substituents substituting one or more hydrogen atoms in the above-mentioned hydrocarbon group with substituents and the above-mentioned heterocyclic ring-containing group with substituents are atoms or groups selected from the following group IIa , a represents an integer of 1 to 20, b represents an integer of 1 to 20, c represents an integer of 0 to 18, and the total of a, b and c is 21 or less) [Chemical 2]

(wherein, R ¹ represents an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group with 2 to 20 carbon atoms, or the above hydrocarbon group or the above A group in which one or more methylene groups in a group containing a heterocycle is substituted with a divalent group selected from the following group Ia, ^R2 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, and the number of carbon atoms Unsubstituted or substituted hydrocarbon groups with 1 to 20 carbon atoms, unsubstituted or substituted heterocycle-containing groups with 2 to 20 carbon atoms, or one or more of the above-mentioned hydrocarbon groups or the above-mentioned heterocycle-containing groups A substituent in which a methylene group is substituted with a divalent group selected from the following group Ia, substituting one or more hydrogen atoms in the above-mentioned hydrocarbon group with a substituent and the above-mentioned heterocyclic ring-containing group with a substituent is an atom or group selected from the following group IIa, * represents a bonding site) [Chem. 3]

(In the formula, R ⁵¹ represents OR ⁸¹ , NR ⁸² R ⁸³ or an unsubstituted or substituted heterocyclic group with 2 to 20 carbon atoms, R ⁵² and R ⁵³ independently represent R ⁸¹ or OR ⁸¹ , R ⁵² and R ⁵³ can be bonded to form a ring, R ⁵⁵ , R ⁵⁶ , R ⁵⁸ , R ⁵⁹ , R ⁶¹ , R ⁶² , R ⁶⁴ , R ⁶⁵ , R ⁷¹ and R ⁷³ each independently represent 6 carbon atoms ~20 unsubstituted or substituted aryl groups, R ⁵⁴ , R ⁵⁷ , R ⁶⁰ , R ⁶³ , R ⁶⁶ , R ⁶⁷ and R ⁷² each independently represent an unsubstituted or substituted aryl group with 6 to 20 carbon atoms. The substituent is an aryl group or a single bond, R ⁶⁸ represents an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, R ⁶⁹ and R ⁷⁰ independently represent R ⁸¹ or OR ⁸¹ , R ⁸¹ , R ⁸² and R ⁸³ each independently represent a hydrogen atom or an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, and * represents a bonding site) (Group Ia: -O-, -COO-, -OCO-, - CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO ₂ -, -NR'-, -NR'-CO-, -CO-NR '-, -NR'-COO-, -OCO-NR'- or -SiR'R''-; Group IIa: Halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH _2. -COOH or -SO ₃ H; R' and R'' each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, when there are multiple R' or R'' , they may be the same or different). The compound as claimed in item 1, wherein the above-mentioned aromatic ring group Ar is an aromatic ring group having a structure represented by the following general formula (Ara) or (Arb), [Chemical 4]

(In the formula, X ¹ is a single bond, no bond, oxygen atom, sulfur atom, selenium atom, CR ⁴¹ R ⁴² , CO, NR ⁴³ or PR ⁴⁴ , X ² is an oxygen atom, sulfur atom, selenium atom, CR ⁴¹ R 44 ⁴² , CO, NR ⁴³ or PR ⁴⁴ , X ³ is NR ⁵³ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom, an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms , an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or one or more methylene groups in the above-mentioned hydrocarbon group or the above-mentioned heterocyclic ring-containing group are substituted to be selected from the following group Ib When there are a plurality of R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ , they may be the same or different. R ⁵³ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group -OR ¹¹¹ , -COR ¹¹¹ , -OCOR ¹¹¹ , -COOR ¹¹¹ , -SR ¹¹¹ , -SOR ¹¹¹ , -SO ₂ R ¹¹¹ , -NR ¹¹² R ¹¹³ , -NR ¹¹² COR ¹¹³ , -CONR ¹¹² R ¹¹³ , An unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group with 2 to 20 carbon atoms, or any of the above-mentioned hydrocarbon groups or the above-mentioned heterocyclic ring-containing groups One or more methylene groups are substituted with divalent groups selected from the following group Ib, R ¹¹¹ , R ¹¹² and R ¹¹³ each independently represent a hydrogen atom, an unsubstituted group having 1 to 20 carbon atoms Or a hydrocarbon group with a substituent, an unsubstituted or substituted heterocycle-containing group with 2 to 20 carbon atoms, or one or more methylene groups in the above-mentioned hydrocarbon group or the above-mentioned heterocycle-containing group are substituted as optional A group derived from a divalent group in the following group Ib, when there are a plurality of R ¹¹¹ , R ¹¹² and R ¹¹³ , which may be the same or different, replaces the above-mentioned hydrocarbon group having a substituent and the above-mentioned The substituent of one or more hydrogen atoms in the heterocyclic ring-containing group having a substituent is an atom or group selected from the following Group IIb) (Group Ib: -O-, -COO-, -OCO-, -CO -, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO ₂ -, -NR'-, -NR'-CO-, -CO-NR' -, -NR'-COO-, -OCO-NR'- or -SiR'R''-; Group IIb: Halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH ₂ , -COOH or -SO ₃ H; R' and R'' each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, when there are multiple R' or R'' , which may be the same or different). Such as the compound of claim 2, wherein the above-mentioned a is 1, the above-mentioned b is 1, and the following partial structure (Aα) in the above-mentioned general formula (A) is a group represented by the following general formula (Ara1) or (Arb1) , [Chem.5]

(In the formula, Ar, ^R33 and c are the same as formula (A); *1 represents the bonding site with ^R31 , and *2 represents the bonding site with ^R32 ) [Chemical 6]

(In the formula, X ¹ , X ² and X ³ are the same as those in the above general formulas (Ara) and (Arb) respectively, R ¹⁴¹ , R ¹⁴² , R ¹⁵¹ and R ¹⁵² independently represent a halogen atom, a nitro group, Cyano, -OR ¹²¹ , -COR ¹²¹ , -OCOR ¹²¹ , -COOR ¹²¹ , -SR ¹²¹ , -SOR ¹²¹ , -SO ₂ R ¹²¹ , -NR ¹²² R ¹²³ , -NR ¹²² COR ¹²³ , -CONR ¹²² R ¹²³ , an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group with 2 to 20 carbon atoms, or the above hydrocarbon group or the above heterocyclic ring-containing group One or more of the methylene groups are substituted with divalent groups selected from the following group Ic, R ¹²¹ , R ¹²² and R ¹²³ independently represent a hydrogen atom, a hydrogen atom having 1 to 20 carbon atoms A substituted or substituted hydrocarbon group, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or one or more methylene groups in the above-mentioned hydrocarbon group or the above-mentioned heterocycle-containing group are substituted with A group selected from a divalent group in the following group Ic, when there are a plurality of R ¹²¹ , R ¹²² and R ¹²³ , they may be the same or different, substituting the above-mentioned hydrocarbon group having a substituent and The substituents for one or more hydrogen atoms in the heterocyclic ring-containing group having substituents are atoms or groups selected from the following group IIc, a1 is 0 to 3, a2 is 0 to 3, and c1 is 0 to 3 , c2 is 0～1, *1 represents the bonding site with ^R31 , *2 represents the bonding site with ^R32 ) (group Ic: -O-, -COO-, -OCO-, -CO-, - CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO ₂ -, -NR'-, -NR'-CO-, -CO-NR'-, - NR'-COO-, -OCO-NR'- or -SiR'R''-; Group IIc: halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH ₂ , -COOH or -SO ₃ H; R' and R'' each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, and when there are multiple R' or R'', the same may be the same or different). The compound according to any one of claims 1 to 3, wherein said R ³² is a group represented by any one of the above general formulas (IVa), (IVf) and (IVh). The compound according to any one of claims 1 to 3, wherein ^R1 is a hydrocarbon group with 1 to 20 carbon atoms having a halogen atom as a substituent, and ^R2 is a cyano group, and a hydrocarbon group with 1 to 20 carbon atoms having a halogen atom A group in which one or more methylene groups of a hydrocarbon group as a substituent or an unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a halogen atom as a substituent are substituted with -COO-. An acid generator comprising the compound according to any one of claims 1 to 5. A composition comprising a compound as claimed in any one of claims 1 to 3, and Resin composition. The composition according to claim 7, wherein the above-mentioned resin component is an acid-curable resin component. A cured product, which is the cured product of the composition according to claim 8. A method for producing a hardened product, comprising a hardening step of hardening the composition according to claim 8. The composition according to claim 7, wherein the resin component is an acid-decomposable resin component. A pattern made of the composition according to claim 11. A pattern manufacturing method, which has the following steps: Forming a coating film using the composition according to claim 11, generating an acid from the above-mentioned compound contained in the formed coating film; and After the step of generating an acid from the above compound, the coating film is developed to remove a part of the coating film to form a pattern.