Onium salt compounds

Abstract

To provide an onium salt compound having excellent solvent compatibility and excellent storage stability. 【Solution means】General formula (1): JPEG2026049542000097.jpg49119 (In the formula, R A represents a C1-15 alkyl group which may have a substituent, etc. R 4 represents a hydrogen atom, etc. R 5 and R 6 are the same or different and represent a hydrogen atom, etc.; alternatively, the said R 5 and R 6 may be bonded to each other together with the two adjacent carbon atoms to form a saturated or unsaturated carbon ring. The said saturated or unsaturated carbon ring may further have a substituent. The dotted line represents a single bond or a double bond. X - represents a boron anion containing a fluorine-containing aromatic ring, etc.). An onium salt compound represented by the formula.

Description

[Technical Field]

[0001] This disclosure relates to onium salt compounds, etc. [Background technology]

[0002] In recent years, energy conservation has been demanded in various fields in response to social issues such as those represented by the SDGs. In response to this demand, light is widely used as an environmentally friendly energy source. For example, in industry, photosensitive materials that utilize light, such as adhesives, sealants, and photoresists, have been industrialized (see, for example, Patent Documents 1-3). As the aforementioned photosensitive material, for example, a reactive composition obtained by mixing an acid generator with a reactive compound such as an epoxy compound, or a cured product thereof, is known.

[0003] To date, there have been two types of acid generators: thermal acid generators and photoacid generators. For example, as a thermal acid generator, Patent Document 4 reports a sulfonium salt (onium salt compound) that generates acid when heated. The reactive composition obtained by mixing the acid generator described in Patent Document 4 with a reactive compound had the characteristic of being able to react at low temperatures.

[0004] Furthermore, dual-type acid generators that generate acid not only with heat but also with light have been reported (for example, Patent Documents 5 and 6). Patent Documents 5 and 6 disclose onium salt compounds as acid generators, in which the countercation is benzothiazolium and the counteranion is antimony.

[0005] However, the acid generators described in Patent Documents 5 and 6 above use highly toxic antimony and also have the problem of being soluble only in specific solvents. Furthermore, reactive compositions, which are mixtures of acid generators with reactive compounds such as epoxy, may experience increased viscosity due to reactions during long-term storage. Therefore, higher storage stability is required for these reactive compositions. Therefore, there is a strong demand for novel acid-generating compounds that exhibit excellent solubility in various solvents (hereinafter referred to as "solvent compatibility") and superior storage stability. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2009-013315 [Patent Document 2] Japanese Patent Publication No. 2010-235862 [Patent Document 3] Japanese Patent Publication No. 2022-190822 [Patent Document 4] Japanese Patent Publication No. 2019-189698 [Patent Document 5] Japanese Patent Application Publication No. 02-268173 [Patent Document 6] Japanese Patent Application Publication No. 07-025863 [Overview of the project] [Problems that the invention aims to solve]

[0007] This disclosure aims to provide a novel onium salt compound that exhibits excellent solvent compatibility and storage stability. [Means for solving the problem]

[0008] The inventors of this invention conducted extensive research to achieve the above objectives and, as a result, discovered that the above problems could be solved by introducing a special structure to the counteranion of the onium salt, thus completing the invention.

[0009] In other words, this disclosure is as follows: Section 1. General formula (1):

[0010] [ka]

[0011] (In the formula, R A This represents a optionally substituted C1-15 alkyl group, an optionally substituted C2-15 alkenyl group, an optionally substituted C2-15 alkynyl group, an optionally substituted 3-15 member saturated or unsaturated carbocyclic group, or an optionally substituted heterocyclic group. R 4 This represents a hydrogen atom, an optionally substituted C1-15 alkyl group, an optionally substituted C2-15 alkenyl group, an optionally substituted C2-15 alkynyl group, an optionally substituted 3-15 member saturated or unsaturated carbocyclic group, an optionally substituted C1-15 alkylcarbonyl group, an optionally substituted 3-15 member saturated or unsaturated carbocyclic carbonyl group, an optionally substituted C1-15 alkoxycarbonyl group, an optionally substituted 3-15 member saturated or unsaturated carbocyclic oxycarbonyl group, an optionally substituted aminocarbonyl group, or a carboxyl group. R 5 and R 6is, independently of each other, a hydrogen atom, a halogen atom, a nitro group, a cyano group, a C1-C15 alkyl group which may have a substituent, a C2-C15 alkenyl group which may have a substituent, a C2-C15 alkynyl group which may have a substituent, a 3-15 membered saturated or unsaturated carbocyclic group which may have a substituent, a C1-C15 alkoxy group which may have a substituent, an oxy group having a 3-15 membered saturated or unsaturated carbocyclic group which may have a substituent, a C1-C15 alkylcarbonyl group which may have a substituent, a carbonyl group having a 3-15 membered saturated or unsaturated carbocyclic group which may have a substituent, a C(-1)-C15 alkoxycarbonyl group which may have a substituent, an oxycarbonyl group having a 3-15 membered saturated or unsaturated carbocyclic group which may have a substituent, an aminocarbonyl group which may have a substituent, a carboxyl group, an amino group which may have a substituent, a C1-C15 alkylthio group which may have a substituent, a thio group having a 3-15 membered saturated or unsaturated carbocyclic group which may have a substituent, a C1-C15 alkylsulfinyl group which may have a substituent, a sulfinyl group having a 3-15 membered saturated or unsaturated carbocyclic group which may have a substituent, a C1-C15 alkylsulfonyl group which may have a substituent, a sulfonyl group having a 3-15 membered saturated or unsaturated carbocyclic group which may have a substituent, or a heterocyclic group which may have a substituent; or, the above R 5 and R 6 may be bonded to each other together with the carbon atoms to which these two groups are respectively adjacent to form a saturated or unsaturated carbocyclic ring. The saturated or unsaturated carbocyclic ring may further have a substituent. The dotted line represents a single bond or a double bond. X - represents a boron anion containing a fluorine-containing aromatic ring, a gallium anion containing a fluorine-containing aromatic ring, a carbon anion containing a fluorine-containing sulfonyl group, a cyclic sulfonimide anion having a fluorine atom, or a phosphorus anion containing a fluorine-containing alkyl group. The onium salt compound represented by Item 2. The above R A is represented by the following general formula (1-R A):

[0012] [ka]

[0013] (In the formula, R 1 This includes hydrogen atoms, halogen atoms, nitro groups, cyano groups, optionally substituted C1-15 alkyl groups, optionally substituted C2-15 alkenyl groups, optionally substituted C2-15 alkynyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring groups, optionally substituted C1-15 alkoxy groups, optionally substituted C1-15 alkylcarbonyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring carbonyl groups, optionally substituted C1-15 alkoxycarbonyl groups, and optionally substituted 3-15 member saturated or unsaturated carbon ring oxycarbonyl groups. This represents a group, an optionally substituted aminocarbonyl group, a carboxyl group, an optionally substituted amino group, an optionally substituted C1-15 alkylthio group, an optionally substituted thio group having an optionally substituted 3-15 member saturated or unsaturated carbon ring, an optionally substituted C1-15 alkylsulfinyl group, an optionally substituted 3-15 member saturated or unsaturated carbon ring, an optionally substituted C1-15 alkylsulfonyl group, an optionally substituted 3-15 member saturated or unsaturated carbon ring, an optionally substituted heterocyclic group, or an optionally substituted silyl group. R 2 This represents a hydrogen atom, a halogen atom, an optionally substituted C1-15 alkyl group, an optionally substituted C2-15 alkenyl group, an optionally substituted 3-15 member saturated or unsaturated carbocyclic group, or an optionally substituted heterocyclic group. R 3 This represents a hydrogen atom, a halogen atom, a C1-15 alkyl group which may have substituents, or a saturated or unsaturated carbon ring group which may have substituents; Alternatively, the aforementioned R1 , R 2 and R 3 Of these, two or three adjacent groups may bond to each other to form a saturated or unsaturated carbon ring or a heterocycle. The saturated or unsaturated carbon ring or heterocycle may further have substituents. * indicates the bonding position with the sulfur atom in the general formula (1) above. The onium salt compound described in item 1, which is a group represented by the group. Section 3. The aforementioned R 1 This includes hydrogen atoms, optionally substituted C1-15 alkyl groups, optionally substituted C2-15 alkenyl groups, optionally substituted C2-15 alkynyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring groups, optionally substituted C1-15 alkylcarbonyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring carbonyl groups, optionally substituted C1-15 alkoxycarbonyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring oxycarbonyl groups, and even if substituted... A good aminocarbonyl group, a carboxyl group, a optionally substituted C1-15 alkylthio group, a optionally substituted thio group having a 3-15 member saturated or unsaturated carbon ring, a optionally substituted C1-15 alkylsulfinyl group, a optionally substituted sulfinyl group having a 3-15 member saturated or unsaturated carbon ring, a optionally substituted C1-15 alkylsulfonyl group, a optionally substituted sulfonyl group having a 3-15 member saturated or unsaturated carbon ring, a optionally substituted heterocyclic group, or an optionally substituted silyl group; The aforementioned R 2 This is a hydrogen atom, a C1-15 alkyl group which may have substituents, or a saturated or unsaturated carbon ring group which may have substituents; The aforementioned R 3 This is a hydrogen atom, a C1-15 alkyl group which may have substituents, or a saturated or unsaturated carbon ring group which may have substituents; Alternatively, the aforementioned R 1 , R2 and R 3 The onium salt compound according to claim 2, wherein two or three adjacent groups may bond to each other to form a saturated or unsaturated carbon ring or heterocycle, and the saturated or unsaturated carbon ring or heterocycle may further have substituents. Section 4. The aforementioned X - The general formula is (XA1): - B(R X1 )a(R X2 )b represents the boron anion (In the formula, R X1 is a fluorine atom or C n F 2n+1 It indicates the base. X2 This is an unsubstituted phenyl group, or a fluorine atom and C n F 2n+1 This represents a phenyl group having at least one substituent selected from the group consisting of groups. n is an integer from 1 to 15. a is an integer from 0 to 3. b is an integer from 1 to 4. a+b is 4. (However, the above R X2 If the group is an unsubstituted phenyl group, then a represents an integer between 1 and 3. General formula (XC1): - C(R X5 )(R X6 )(R X7 ) Carbon anion represented by (In the formula, R X5 , R X6 and R X7 C is the same or different. t F 2t+1 A sulfonyl group having a group; or at least one C t F 2t+1 This indicates a phenylsulfonyl group containing a group. t represents an integer from 1 to 15. ); or, General formula (XD1):

[0014] [ka]

[0015] An onium salt compound according to any one of items 1 to 3, which is a cyclic sulfonimide anion having a fluorine atom, represented by the formula (wherein r is an integer from 1 to 6). Section 5. The aforementioned X - teeth, The following general formula (XA2):

[0016] [ka]

[0017] (In the formula, R 30 , R 31 , R 32 , R 33 and R 34 These are the same or different hydrogen atoms, fluorine atoms, or C n F 2n+1 The base is shown. However, the R 30 , R 31 , R 32 , R 33 and R 34 One of them is a fluorine atom or C n F 2n+1 It is a boron anion represented by (where n is an integer from 1 to 15). The following general formula (XC2):

[0018] [ka]

[0019] (In the formula, R 40 , R 41 and R 42 C is the same or different. t F 2t+1 The base is shown. t is an integer from 1 to 15.) A carbon anion represented by ); or, General formula (XD1):

[0020] [ka]

[0021] The onium salt compound according to any one of items 1 to 4, which is a cyclic sulfonimide anion having a fluorine atom and is represented by (where r represents an integer of 1 to 6). Item 6. Said R 5 and R 6 are bonded to each other together with the carbon atoms to which these two groups are adjacent respectively to form a saturated or unsaturated carbocyclic ring, and the saturated or unsaturated carbocyclic ring may further have a substituent. The onium salt compound according to any one of items 1 to 5. Item 7. Said R 4 is an unsubstituted C1-15 alkyl group. The onium salt compound according to any one of items 1 to 6. Item 8. An acid generator containing the onium salt compound according to any one of items 1 to 7. Item 9. A polymerization initiator containing the onium salt compound according to any one of items 1 to 7. Item 10. A reactive composition containing the onium salt compound according to any one of items 1 to 7 and a reactive compound. Item 11. A polymer obtained from the reactive composition according to item 10. Item 12. An adhesive, a sealing material or a resist containing the reactive composition according to item 10. Item 13. The reactive composition according to item 10, which is for an adhesive, a sealing material or a resist. Item 14. Use of the onium salt compound according to any one of items 1 to 7 as an acid generator. Item 15. Use of the onium salt compound according to any one of items 1 to 7 as a polymerization initiator. Item 16. Use of the polymer of the reactive composition according to item 10 or 13. Item 17. Use of the reactive composition according to item 10 or 13 as an adhesive. Item 18. Use of the reactive composition described in item 10 or 13 for use as a encapsulant. Section 19. Use of the reactive composition described in item 10 or 13 for resists.

[0022] Furthermore, in the case of product inventions defined by a manufacturing method within this disclosure, it is currently impossible or impractical to specify all the components included or the structure thereof; therefore, these are described using product-by-process claims. [Effects of the Invention]

[0023] According to this disclosure, it is possible to provide novel onium salt compounds that have excellent solvent compatibility and excellent storage stability. Furthermore, the onium salt compounds of this disclosure can function not only as acid generators but also as radical generators. [Modes for carrying out the invention]

[0024] The forms for implementing this disclosure will be described in detail below. Unless otherwise specified, all terms used in the claims and specification shall have the definitions commonly used in the art.

[0025] Onium salt compounds The onium salt compounds disclosed herein are compounds represented by the following general formula (1). Hereinafter, the onium salt compounds disclosed herein may also be simply referred to as "onium salts," etc.

[0026] [ka]

[0027] Here, R in the general formula (1) 4This represents a hydrogen atom, an optionally substituted C1-15 alkyl group, an optionally substituted C2-15 alkenyl group, an optionally substituted C2-15 alkynyl group, an optionally substituted 3-15 member saturated or unsaturated carbocyclic group, an optionally substituted C1-15 alkylcarbonyl group, an optionally substituted 3-15 member saturated or unsaturated carbocyclic carbonyl group, an optionally substituted C1-15 alkoxycarbonyl group, an optionally substituted 3-15 member saturated or unsaturated carbocyclic oxycarbonyl group, an optionally substituted aminocarbonyl group, or a carboxyl group. Among them, the preferred R 4 These include C1-15 alkyl groups which may have substituents, and saturated or unsaturated carbon ring groups which may have substituents. A more preferred R 4 These are unsubstituted C1-15 alkyl groups. A more preferable R 4 These are unsubstituted C1-6 alkyl groups.

[0028] R 5 and R 6These are identical or different hydrogen atoms, halogen atoms, nitro groups, cyano groups, optionally substituted C1-15 alkyl groups, optionally substituted C2-15 alkenyl groups, optionally substituted C2-15 alkynyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring groups, optionally substituted C1-15 alkoxy groups, optionally substituted 3-15 member saturated or unsaturated carbon ring oxy groups, optionally substituted C1-15 alkylcarbonyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring carbonyl groups, optionally substituted C1-15 alkoxycarbonyl groups, and substituted This represents an oxycarbonyl group having a 3-15 member saturated or unsaturated carbon ring, an optionally substituted aminocarbonyl group, a carboxyl group, an optionally substituted amino group, an optionally substituted C1-15 alkylthio group, an optionally substituted thio group having a 3-15 member saturated or unsaturated carbon ring, an optionally substituted C1-15 alkylsulfinyl group, an optionally substituted sulfinyl group having a 3-15 member saturated or unsaturated carbon ring, an optionally substituted C1-15 alkylsulfonyl group, an optionally substituted sulfonyl group having a 3-15 member saturated or unsaturated carbon ring, or an optionally substituted heterocyclic group; Alternatively, the aforementioned R 5 and R 6 These two groups may bond to each other with adjacent carbon atoms to form a saturated or unsaturated carbon ring. The saturated or unsaturated carbon ring may further have substituents.

[0029] Among them, the preferred R 5 These include hydrogen atoms, halogen atoms, nitro groups, cyano groups, and C1-15 alkyl groups which may have substituents. A more preferred R 5 These include a hydrogen atom and a C1-15 alkyl group which may have substituents. A more preferable R 5 These include hydrogen atoms and unsubstituted C1-6 alkyl groups. Among them, preferable R 6 is a hydrogen atom, a halogen atom, a nitro group, a cyano group, and a C1-15 alkyl group which may have a substituent. More preferable R 6 is a hydrogen atom and a C1-15 alkyl group which may have a substituent. Even more preferable R 6 is a hydrogen atom and an unsubstituted C1-6 alkyl group.

[0030] Alternatively, the said R 5 and R 6 may be bonded to each other together with the adjacent carbon atoms to form a saturated or unsaturated carbocyclic ring. The said saturated or unsaturated carbocyclic ring may further have a substituent.

[0031] When the said R 5 and R[[ID=2­5]] 6 are bonded to each other together with the adjacent carbon atoms to form a saturated or unsaturated carbocyclic ring, the saturated or unsaturated carbocyclic ring is preferably a benzene ring (also referred to as a phenyl ring) and a naphthalene ring. Here, the compound represented by the general formula (1) when the saturated or unsaturated carbocyclic ring is a benzene ring means a compound having a benzothiazole ring. The compound represented by the general formula (1) when the saturated or unsaturated carbocyclic ring is a naphthalene ring means a compound having a naphthothiazole ring. Examples of the naphthalene ring include 1,2-naphthalene, 2,3-naphthalene, and 3,4-naphthalene. More preferably, the saturated or unsaturated carbocyclic ring is a benzene ring.

[0032] The dotted line indicates a single bond or a double bond.

[0033] X -represents a boron anion containing a fluorine-containing aromatic ring, a gallium anion containing a fluorine-containing aromatic ring, a carbon anion containing a fluorine-containing sulfonyl group, a cyclic sulfonimide anion having a fluorine atom, or a phosphorus anion containing a fluorine-containing alkyl group.

[0034] R A represents an optionally substituted C1-C15 alkyl group, an optionally substituted C2-C15 alkenyl group, an optionally substituted C2-C15 alkynyl group, an optionally substituted 3- to 15-membered saturated or unsaturated carbocyclic group, or an optionally substituted heterocyclic group.

[0035] Said R A is preferably a group represented by the following general formula (1-R A ):

[0036]

Chemical formula

[0037] wherein, in the general formula (1-R

[0038] ), R A in 1This includes hydrogen atoms, halogen atoms, nitro groups, cyano groups, optionally substituted C1-15 alkyl groups, optionally substituted C2-15 alkenyl groups, optionally substituted C2-15 alkynyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring groups, optionally substituted C1-15 alkoxy groups, optionally substituted C1-15 alkylcarbonyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring carbonyl groups, optionally substituted C1-15 alkoxycarbonyl groups, and optionally substituted 3-15 member saturated or unsaturated carbon ring oxycarbonyl groups. This represents a group, an optionally substituted aminocarbonyl group, a carboxyl group, an optionally substituted amino group, an optionally substituted C1-15 alkylthio group, an optionally substituted thio group having an optionally substituted 3-15 member saturated or unsaturated carbon ring, an optionally substituted C1-15 alkylsulfinyl group, an optionally substituted 3-15 member saturated or unsaturated carbon ring, an optionally substituted C1-15 alkylsulfonyl group, an optionally substituted 3-15 member saturated or unsaturated carbon ring, an optionally substituted heterocyclic group, or an optionally substituted silyl group.

[0039] Among them, the preferred R 1Examples include hydrogen atoms, optionally substituted C1-15 alkyl groups, optionally substituted C2-15 alkenyl groups, optionally substituted C2-15 alkynyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring groups, optionally substituted C1-15 alkylcarbonyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring carbonyl groups, optionally substituted C1-15 alkoxycarbonyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring oxycarbonyl groups, and substituted The group may be an aminocarbonyl group, a carboxyl group, a C1-15 alkylthio group which may have a substituent, a thio group having a 3-15 member saturated or unsaturated carbon ring which may have a substituent, a C1-15 alkylsulfinyl group which may have a substituent, a sulfinyl group having a 3-15 member saturated or unsaturated carbon ring which may have a substituent, a C1-15 alkylsulfonyl group which may have a substituent, a sulfonyl group having a 3-15 member saturated or unsaturated carbon ring which may have a substituent, a heterocyclic group which may have a substituent, or a silyl group which may have a substituent.

[0040] A more preferred R 1These include a hydrogen atom, a C1-15 alkyl group which may have one or more substituents selected from Group 1 below, a C2-15 alkenyl group which may have one or more substituents selected from Group 1 below, a C2-15 alkynyl group which may have one or more substituents selected from Group 1 below, a 3-15 member saturated or unsaturated carbon ring group which may have one or more substituents selected from Group 3 below, a C1-15 alkylcarbonyl group which may have one or more substituents selected from Group 1 below, a carbonyl group having a 3-15 member saturated or unsaturated carbon ring which may have one or more substituents selected from Group 3 below, a C1-15 alkoxycarbonyl group which may have one or more substituents selected from Group 1 below, an oxycarbonyl group having a 3-15 member saturated or unsaturated carbon ring which may have one or more substituents selected from Group 3 below, and one or more selected from Group 5 below. These are optionally substituted aminocarbonyl groups, carboxyl groups, optionally substituted C1-15 alkylthio groups selected from Group 1 below, optionally substituted thio groups having a 3-15 member saturated or unsaturated carbon ring, optionally substituted from Group 3 below, optionally substituted C1-15 alkylsulfinyl groups selected from Group 1 below, optionally substituted 3-15 member saturated or unsaturated carbon rings, optionally substituted from Group 3 below, optionally substituted C1-15 alkylsulfonyl groups selected from Group 1 below, optionally substituted 3-15 member saturated or unsaturated carbon rings, optionally substituted from Group 3 below, optionally substituted heterocyclic groups selected from Group 3 below, and optionally substituted silyl groups selected from Group 6 below.

[0041] A more preferable R 1These include a hydrogen atom, a C1-15 alkyl group which may have one or more substituents selected from Group 2 below, a C2-15 alkenyl group which may have one or more substituents selected from Group 2 below, a C2-15 alkynyl group which may have one or more substituents selected from Group 2 below, a 3-15 member saturated or unsaturated carbon ring group which may have one or more substituents selected from Group 4 below, a C1-15 alkylcarbonyl group which may have one or more substituents selected from Group 2 below, a carbonyl group having a 3-15 member saturated or unsaturated carbon ring which may have one or more substituents selected from Group 4 below, a C1-15 alkoxycarbonyl group which may have one or more substituents selected from Group 2 below, an oxycarbonyl group having a 3-15 member saturated or unsaturated carbon ring which may have one or more substituents selected from Group 4 below, and one or more selected from Group 5 below. These are optionally substituted aminocarbonyl groups, carboxyl groups, optionally substituted C1-15 alkylthio groups selected from Group 2 below, optionally substituted thio groups having a 3-15 member saturated or unsaturated carbon ring, optionally substituted from Group 4 below, optionally substituted C1-15 alkylsulfinyl groups selected from Group 2 below, optionally substituted 3-15 member saturated or unsaturated carbon rings, optionally substituted from Group 4 below, optionally substituted C1-15 alkylsulfonyl groups selected from Group 2 below, optionally substituted 3-15 member saturated or unsaturated carbon rings, optionally substituted from Group 4 below, optionally substituted heterocyclic groups selected from Group 4 below, and optionally substituted silyl groups selected from Group 6 below.

[0042] R 2 This represents a hydrogen atom, a halogen atom, an optionally substituted C1-15 alkyl group, an optionally substituted C2-15 alkenyl group, an optionally substituted 3-15 member saturated or unsaturated carbocyclic group, or an optionally substituted heterocyclic group. Among them, the preferred R2 is a hydrogen atom, a C1-C15 alkyl group which may have one or more substituents selected from the following <Group 1>, or a 3- to 15-member saturated or unsaturated carbocyclic group which may have one or more substituents selected from the following <Group 3>. More preferred R 2 is a hydrogen atom, a C1-C15 alkyl group which may have one or more substituents selected from the following <Group 2>, and a 3- to 15-member saturated or unsaturated carbocyclic group which may have one or more substituents selected from the following <Group 4>.

[0043] R 3 represents a hydrogen atom, a halogen atom, a C1-C15 alkyl group which may have a substituent, or a 3- to 15-member saturated or unsaturated carbocyclic group which may have a substituent. Among them, preferred R 3 is a hydrogen atom, a C1-C15 alkyl group which may have one or more substituents selected from the following <Group 1>, and a C1-C15 alkyl group which may have one or more substituents selected from the following <Group 3>. More preferred R 3 is a hydrogen atom, a C1-C15 alkyl group which may have one or more substituents selected from the following <Group 2>, and a 3- to 15-member saturated or unsaturated carbocyclic group which may have one or more substituents selected from the following <Group 4>.

[0044] Alternatively, among the above R 1 R 2 and R 3 two or three adjacent groups may be bonded to each other to form a saturated or unsaturated carbocyclic or heterocyclic ring. The saturated or unsaturated carbocyclic or heterocyclic ring may further have a substituent.

[0045] Preferred saturated or unsaturated carbocyclic rings are C3-C15 carbocyclic rings which may have at least one or more substitutions selected from the following <Group 3>. A more preferred saturated or unsaturated carbon ring is a C3-15 carbon ring that may have at least one substitution selected from the following group 4. Further preferred saturated or unsaturated carbon rings include indene which may have one or more substituents selected from the group consisting of substituted or unsubstituted phenyl groups and oxo groups; fluorene which may have one or more substituents selected from the group consisting of substituted or unsubstituted phenyl groups and oxo groups; adamantane which may have one or more substituents selected from the group consisting of substituted or unsubstituted phenyl groups and oxo groups; cyclopentane which may have one or more substituents selected from the group consisting of substituted or unsubstituted phenyl groups and oxo groups; and cyclopentene which may have one or more substituents selected from the group consisting of substituted or unsubstituted phenyl groups and oxo groups.

[0046] A preferred heterocycle is one which may have at least one substituent selected from the following group 3. A more preferred heterocycle is one which may have at least one substituent selected from the following group 4. A more preferred heterocycle is succinimide (maleimide), which may have one or more substituents selected from the group consisting of substituted or unsubstituted phenyl groups and oxo groups.

[0047] * indicates the bond position with the sulfur atom in the general formula (1) above.

[0048] X - This is a boron anion (XA) containing a fluorine-containing aromatic ring. - This is also the case.), gallium anion containing a fluorine-containing aromatic ring (XB - This can also be the case. ), a carbon anion containing a fluorine-containing sulfonyl group (XC - This is also the case. ), cyclic sulfonimide anions having a fluorine atom (XD - This can also be the case. ), or a phosphate anion containing a fluorine-containing alkyl group (XE - This also indicates that...

[0049] Here, the preferred X - For example, the general formula (XA1): - B(R X1 )a(R X2 )b represents the boron anion (In the formula, R X1 is a fluorine atom or C n F 2n+1 It indicates the base. X2 This is an unsubstituted phenyl group, or a fluorine atom and C n F 2n+1 This represents a phenyl group having at least one substituent selected from the group consisting of groups. n is an integer from 1 to 15. a is an integer from 0 to 3. b is an integer from 1 to 4. a+b is 4. (However, the above R X2 If the group is an unsubstituted phenyl group, then a represents an integer between 1 and 3.

[0050] General formula (XB1): - Ga(R X3 )a(R X4 )b represents a gallium anion (In the formula, R X3 is a fluorine atom or C n F 2n+1 It indicates the base. X4 This is an unsubstituted phenyl group, or a fluorine atom and C n F 2n+1 This represents a phenyl group having at least one substituent selected from the group consisting of such substituents. n is an integer from 1 to 15. a is an integer from 0 to 3. b is an integer from 1 to 4. a+b is 4.

[0051] General formula (XC1): - C(R X5 )(R X6 )(R X7 ) Carbon anion represented by (In the formula, R X5 , R X6 and R X7 C is the same or different. t F 2t+1 A sulfonyl group having a group; or at least one C tF 2t+1 This indicates a phenylsulfonyl group containing a group. t represents an integer between 1 and 15.

[0052] General formula (XD1):

[0053] [ka]

[0054] A cyclic sulfonimide anion having a fluorine atom, represented by (wherein r is an integer from 1 to 6); or,

[0055] General formula (XE1):P(R X8 )c(R X9 Phosphate anion containing a fluorine-containing alkyl group represented by )d (In the formula, R X8 C u F 2u+1 It indicates the base. X9 represents a fluorine atom. u represents an integer from 1 to 15. c represents an integer from 1 to 6. d represents an integer from 0 to 5. c+d represents 6.

[0056] A more preferred boron anion represented by XA1 is: The following general formula (XA2):

[0057] [ka]

[0058] (In the formula, R 30 , R 31 , R 32 , R 33 and R 34 These are the same or different hydrogen atoms, fluorine atoms, or C n F 2n+1 The base is shown. However, the R 30 , R 31 , R 32 , R 33 and R 34 One of them is a fluorine atom or C nF 2n+1 It is a boron anion represented by (where n is an integer from 1 to 15).

[0059] Here, the substituent R in general formula (XA2) 30 , R 31 , R 32 , R 33 and R 34 Regarding this, a preferred group is shown. Preferred R 30 These include hydrogen atoms, fluorine atoms, and trifluoromethyl groups. Preferred R 31 These include hydrogen atoms, fluorine atoms, and trifluoromethyl groups. Preferred R 32 These include hydrogen atoms, fluorine atoms, and trifluoromethyl groups. Preferred R 33 These include hydrogen atoms, fluorine atoms, and trifluoromethyl groups. Preferred R 34 These include hydrogen atoms, fluorine atoms, and trifluoromethyl groups.

[0060] Among the boron anions represented by the above general formula (XA2), a more preferred combination of substituents is R 30 is a fluorine atom, R 31 is a fluorine atom, R 32 is a fluorine atom, R 33 is a fluorine atom, and R 34 is a fluorine atom; R 30 is a hydrogen atom, R 31 is a hydrogen atom, R 32 is a fluorine atom, R 33 is a hydrogen atom, and R 34 is a hydrogen atom; R 30 is a trifluoromethyl group, R 31 is a trifluoromethyl group, R 32 is a trifluoromethyl group, R 33 is a trifluoromethyl group, and R 34 is a trifluoromethyl group; R 30is a hydrogen atom, R 31 is a trifluoromethyl group, R 32 is a hydrogen atom, R 33 is a trifluoromethyl group, and R 34 is a hydrogen atom; R 30 is a hydrogen atom, R 31 is a hydrogen atom, R 32 is a trifluoromethyl group, R 33 is a hydrogen atom, and R 34 That is a hydrogen atom.

[0061] More preferable boron anions represented by the general formula (XA2) are the boron anion represented by the general formula (XA2-1), the boron anion represented by the general formula (XA2-2), and the boron anion represented by the general formula (XA2-3).

[0062] [ka]

[0063] A more preferred gallium anion represented by XB1 is: The following general formula (XB2):

[0064] [ka]

[0065] (In the formula, R 35 , R 36 , R 37 , R 38 and R 39 These are the same or different hydrogen atoms, fluorine atoms, or C n F 2n+1 The base is shown. However, the R 35 , R 36 , R 37 , R 38 and R 39 One of them is a fluorine atom or C n F 2n+1 It is a gallium anion represented by (where n is an integer from 1 to 15).

[0066] Here, the substituent R in general formula (XB2) 35 , R 36 , R 37 , R 38 and R 39 Regarding this, a preferred group is shown. Preferred R 35 These include hydrogen atoms, fluorine atoms, and trifluoromethyl groups. Preferred R 36 These include hydrogen atoms, fluorine atoms, and trifluoromethyl groups. Preferred R 37 These include hydrogen atoms, fluorine atoms, and trifluoromethyl groups. Preferred R 38 These include hydrogen atoms, fluorine atoms, and trifluoromethyl groups. Preferred R 39 These include hydrogen atoms, fluorine atoms, and trifluoromethyl groups.

[0067] Among the boron anions represented by the above general formula (XB2), a more preferred combination of substituents is R 35 is a fluorine atom, R 36 is a fluorine atom, R 37 is a fluorine atom, R 38 is a fluorine atom, and R 39 is a fluorine atom; R 35 is a hydrogen atom, R 36 is a hydrogen atom, R 37 is a fluorine atom, R 38 is a hydrogen atom, and R 39 is a hydrogen atom; R 35 is a trifluoromethyl group, R 36 is a trifluoromethyl group, R 37 is a trifluoromethyl group, R 38 is a trifluoromethyl group, and R 39 is a trifluoromethyl group; R 35 is a hydrogen atom, R 36 is a trifluoromethyl group, R 37 is a hydrogen atom, R38 is a trifluoromethyl group, and R 39 is a hydrogen atom; R 35 is a hydrogen atom, R 36 is a hydrogen atom, R 37 is a trifluoromethyl group, R 38 is a hydrogen atom, and R 39 That is a hydrogen atom.

[0068] A more preferred carbon anion represented by XC1 (also called a methide anion) is: The following general formula (XC2):

[0069] [ka]

[0070] (In the formula, R 40 , R 41 and R 42 C is the same or different. t F 2t+1 This indicates the group. t is an integer from 1 to 15. It is a carbon anion represented by ( ).

[0071] Here, substituent R in general formula (XC2) 40 , R 41 and R 42 Regarding this, a preferred group is shown. Preferred R 40 These include difluoromethyl groups, trifluoromethyl groups, or pentafluoroethyl groups. Preferred R 41 These include difluoromethyl groups, trifluoromethyl groups, or pentafluoroethyl groups. Preferred R 42 These include difluoromethyl groups, trifluoromethyl groups, or pentafluoroethyl groups. Particularly preferred carbon anion combinations include R 40 is a trifluoromethyl group, R 41 is a trifluoromethyl group, and R 42 This is a trifluoromethyl group.

[0072] A more preferred carbon anion represented by the general formula (XC2) is: The following general formula (XC2-1):

[0073] [ka]

[0074] This is a carbon anion represented by [formula].

[0075] A more preferred cyclic sulfonimide anion represented by the general formula (XD1) is a cyclic sulfonimide anion in which r is an integer between 2 and 5.

[0076] More preferable cyclic sulfonimide anions represented by the general formula (XD1) are the cyclic sulfonimide anions represented by the following general formula (XD1-1) and the cyclic sulfonimide anions represented by the general formula (XD1-2).

[0077] [ka]

[0078] General formula (XE1):P(R X8 )c(R X9 Phosphorus anions containing a fluorine-containing alkyl group represented by )d include (CF3CF2)2PF4 - (CF3CF2)3PF3 - , ((CF3)2CF)2PF4 - , ((CF3)2CF)3PF3 - (CF3CF2CF2)2PF4 - (CF3CF2CF2)3PF3 - , ((CF3)2CFCF2)2PF4 - , ((CF3)2CFCF2)3PF3 - (CF3CF2CF2CF2)2PF4 - , and (CF3CF2CF2CF2)3PF3 -Examples include anions represented by [the formula shown]. Among these, a preferred phosphorus anion containing a fluorine-containing alkyl group is (CF3CF2)3PF3 - (CF3CF2CF2)3PF3 - , ((CF3)2CF)3PF3 - , ((CF3)2CF)2PF4 - , ((CF3)2CFCF2)3PF3 - , and ((CF3)2CFCF2)2PF4 - This is an anion represented by [formula].

[0079] Furthermore, Japanese Patent Publication No. 2007-224183 (Patent Document 7) describes an energy-sensitive ray acid generator (Claim 1). In addition, paragraph

[0192] of the same document lists 2-methylthio-3-benzylbenzothiazolium tetrakis(pentafluorophenyl)borate (1Z-1) and 2-methylthio-3-benzylbenzothiazolium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (1Z-2) on a single line, but they are not listed in the examples section of the same document. Since the document does not specify how the above-mentioned compounds (1Z-1) and (1Z-2) were produced or what effects were obtained, it cannot be said that the above-mentioned invention is disclosed in the document. Furthermore, it is preferable that the onium salt compounds of this disclosure exclude the compounds represented by the following formula (1Z-1) and the compounds represented by the formula (1Z-2).

[0080] [ka]

[0081] Furthermore, preferred onium salt compounds include the compound represented by the following general formula (1A-1), the compound represented by the general formula (1A-2), the compound represented by the general formula (1A-3), and the compound represented by the general formula (1A-4).

[0082] Among the onium salt compounds represented by the general formula (1), R5 and R 6 However, if a saturated or unsaturated carbon ring is not formed, the compound is represented by the following general formula (1A-1) or the general formula (1A-2).

[0083] [ka]

[0084] Here, in general formula (1A-1) and general formula (1A-2), R A , R 4 and X - This is the same as described above. R 5 and R 6 These are identical or different hydrogen atoms, halogen atoms, nitro groups, cyano groups, optionally substituted C1-15 alkyl groups, optionally substituted C2-15 alkenyl groups, optionally substituted C2-15 alkynyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring groups, optionally substituted C1-15 alkoxy groups, optionally substituted 3-15 member saturated or unsaturated carbon ring oxy groups, optionally substituted C1-15 alkylcarbonyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring carbonyl groups, optionally substituted C1-15 alkoxycarbonyl groups, and substituted This represents an oxycarbonyl group having a 3-15 member saturated or unsaturated carbon ring, an optionally substituted aminocarbonyl group, a carboxyl group, an optionally substituted amino group, an optionally substituted C1-15 alkylthio group, an optionally substituted thio group having a 3-15 member saturated or unsaturated carbon ring, an optionally substituted C1-15 alkylsulfinyl group, an optionally substituted sulfinyl group having a 3-15 member saturated or unsaturated carbon ring, an optionally substituted C1-15 alkylsulfonyl group, an optionally substituted sulfonyl group having a 3-15 member saturated or unsaturated carbon ring, or an optionally substituted heterocyclic group.

[0085] Furthermore, among the onium salt compounds represented by general formula (1), the R 5 and R 6 However, when each atom bonds with an adjacent carbon atom to form a saturated or unsaturated carbon ring, it is an onium salt compound represented by the following general formula (1A-3) (hereinafter, this may be referred to as "benzothiazolium salt") or an onium salt compound represented by the general formula (1A-4).

[0086] [ka]

[0087] (In the formula, R A , R 4 and X - This is the same as described above. R 7 , R 8 , R 9 and R 10These are identical or different hydrogen atoms, halogen atoms, nitro groups, cyano groups, optionally substituted C1-15 alkyl groups, optionally substituted C2-15 alkenyl groups, optionally substituted C2-15 alkynyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring groups, optionally substituted C1-15 alkoxy groups, optionally substituted 3-15 member saturated or unsaturated carbon ring oxy groups, optionally substituted C1-15 alkylcarbonyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring carbonyl groups, optionally substituted C1-15 alkoxycarbonyl groups, and substituted This represents an oxycarbonyl group having a 3-15 member saturated or unsaturated carbon ring, an optionally substituted aminocarbonyl group, a carboxyl group, an optionally substituted amino group, an optionally substituted C1-15 alkylthio group, an optionally substituted thio group having a 3-15 member saturated or unsaturated carbon ring, an optionally substituted C1-15 alkylsulfinyl group, an optionally substituted sulfinyl group having a 3-15 member saturated or unsaturated carbon ring, an optionally substituted C1-15 alkylsulfonyl group, an optionally substituted sulfonyl group having a 3-15 member saturated or unsaturated carbon ring, or an optionally substituted heterocyclic group. Alternatively, the aforementioned R 7 , R 8 , R 9 and R 10 Of these, at least two groups may bond to each other with adjacent carbon atoms to form a saturated or unsaturated carbon ring. The saturated or unsaturated carbon ring may further have substituents.

[0088] Preferred R 7 R is one or more substituents selected from <Group 3>. A more preferred R 7 is one or more substituents selected from <Group 4>. Preferred R 8 However, one or more substituents selected from <Group 3> are preferred. 8 is one or more substituents selected from <Group 4>. Preferred R 9 However, one or more substituents selected from <Group 3> are preferred. 9 is one or more substituents selected from <Group 4>. Preferred R 10 However, one or more substituents selected from <Group 3> are preferred. 10 is one or more substituents selected from <Group 4>.

[0089] [ka]

[0090] (In the formula, R A , R 4 and X - This is the same as above. R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20These are identical or different hydrogen atoms, halogen atoms, nitro groups, cyano groups, optionally substituted C1-15 alkyl groups, optionally substituted C2-15 alkenyl groups, optionally substituted C2-15 alkynyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring groups, optionally substituted C1-15 alkoxy groups, optionally substituted 3-15 member saturated or unsaturated carbon ring oxy groups, optionally substituted C1-15 alkylcarbonyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring carbonyl groups, optionally substituted C1-15 alkoxycarbonyl groups, and substituted This represents an oxycarbonyl group having a 3-15 member saturated or unsaturated carbon ring, an optionally substituted aminocarbonyl group, a carboxyl group, an optionally substituted amino group, an optionally substituted C1-15 alkylthio group, an optionally substituted thio group having a 3-15 member saturated or unsaturated carbon ring, an optionally substituted C1-15 alkylsulfinyl group, an optionally substituted sulfinyl group having a 3-15 member saturated or unsaturated carbon ring, an optionally substituted C1-15 alkylsulfonyl group, an optionally substituted sulfonyl group having a 3-15 member saturated or unsaturated carbon ring, or an optionally substituted heterocyclic group. Alternatively, the aforementioned R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 Of these, at least two groups may bond to each other with adjacent carbon atoms to form a saturated or unsaturated carbon ring. The saturated or unsaturated carbon ring may further have substituents.

[0091] Among the onium salts disclosed herein, preferred are compounds represented by the following general formula (1B).

[0092] [ka]

[0093] Here, R in the formula 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X - The dotted lines are the same as described above.

[0094] Examples of compounds represented by the general formula (1B) include the compounds represented by the general formula (1B-1), the compounds represented by the general formula (1B-2), the compounds represented by the general formula (1B-3), the compounds represented by the general formula (1B-4), and so on.

[0095] [ka]

[0096] Here, R in the formula 1 , R 2 , R 3 , R 4 , R 5 , R 6 and X - This is the same as described above.

[0097] [ka]

[0098] Here, R in the formula 1 , R 2 , R 3 , R 4 , R 5 , R 6 and X - This is the same as described above.

[0099] [ka]

[0100] Here, in the formula, R1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 , R 10 and X - This is the same as described above.

[0101] [ka]

[0102] Here, in the formula, R 1 , R 2 , R 3 , R 4 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 and X - This is the same as described above.

[0103] Among the compounds represented by the general formula (1B), more preferred onium salt compounds include, for example, the compounds represented by the following general formula (1C). [ka]

[0104] Here, in the general formula (1C) R 4 , R 5 , R 6 , dotted line and X - This is the same as described above. Furthermore, the R 21 , R 22 , R 23 , R 24 and R 25These are the same or different hydrogen atoms, halogen atoms, hydroxyl groups, nitro groups, cyano groups, optionally substituted C1-15 alkyl groups, optionally substituted C2-15 alkenyl groups, optionally substituted C2-15 alkynyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring groups, optionally substituted C1-15 alkoxy groups, optionally substituted 3-15 member saturated or unsaturated carbon ring oxy groups, optionally substituted C1-15 alkylcarbonyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring carbonyl groups, optionally substituted C1-15 alkoxycarbonyl groups, and substituted This represents an oxycarbonyl group having an optionally substituted 3-15 member saturated or unsaturated carbon ring, an optionally substituted aminocarbonyl group, a carboxyl group, an optionally substituted amino group, an optionally substituted C1-15 alkylthio group, an optionally substituted 3-15 member saturated or unsaturated carbon ring thio group, an optionally substituted C1-15 alkylsulfinyl group, an optionally substituted 3-15 member saturated or unsaturated carbon ring sulfinyl group, an optionally substituted C1-15 alkylsulfonyl group, an optionally substituted 3-15 member saturated or unsaturated carbon ring sulfonyl group, or an optionally substituted heterocyclic group. The aforementioned R 26 This represents a hydrogen atom, a halogen atom, a hydroxyl group, an optionally substituted C1-15 alkyl group, an optionally substituted C2-15 alkenyl group, an optionally substituted 3-15 member saturated or unsaturated carbocyclic group, or an optionally substituted heterocyclic group. The aforementioned R 27 This represents a hydrogen atom, a halogen atom, a hydroxyl group, a C1-15 alkyl group which may have substituents, or a saturated or unsaturated carbon ring group which may have substituents. q represents an integer between 1 and 6. Note that if q is an integer between 2 and 6, then there are two or more R 26 These may be the same or different, and there may be two or more R 27These may be the same or different. Furthermore, the onium salt compounds included in this disclosure may be optical isomers.

[0105] Examples of compounds represented by the general formula (1C) include the compound represented by the general formula (1C-1), the compound represented by the general formula (1C-2), the compound represented by the general formula (1C-3), the compound represented by the general formula (1C-4), and so on.

[0106] [ka]

[0107] Here, R in the formula 4 , R 5 , R 6 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 q and X - This is the same as described above.

[0108] [ka]

[0109] Here, R in the formula 4 , R 5 , R 6 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 q and X - This is the same as described above.

[0110] [ka]

[0111] Here, R in the formula 4 , R7 , R 8 , R 9 , R 10 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 q and X - This is the same as described above.

[0112] [ka]

[0113] Here, R in the formula 4 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 q and X - This is the same as described above.

[0114] Preferred R 21 , R 22 , R 23 , R 24 and R 25 These may be the same or different hydrogen atoms, halogen atoms, hydroxyl groups, optionally substituted C1-15 alkyl groups, optionally substituted C2-15 alkenyl groups, optionally substituted C2-15 alkynyl groups, optionally substituted 3-15 member saturated or unsaturated carbocyclic groups, optionally substituted C1-15 alkoxy groups, optionally substituted C1-15 alkylcarbonyl groups, and optionally substituted C1-15 alkoxycarbonyl groups. A more preferred R 21 , R22 , R 23 , R 24 and R 25 These include, identically or differently, a hydrogen atom, a hydroxyl group, a C1-15 alkyl group which may have one or more substituents selected from Group 2 below, a C2-15 alkenyl group which may have one or more substituents selected from Group 2 below, a C2-15 alkynyl group which may have one or more substituents selected from Group 2 below, a 3-15 member saturated or unsaturated carbocyclic group which may have one or more substituents selected from Group 4 below, a C1-15 alkoxy group which may have one or more substituents selected from Group 2 below, a C1-15 alkylcarbonyl group which may have one or more substituents selected from Group 2 below, and a C1-15 alkoxycarbonyl group which may have one or more substituents selected from Group 2 below.

[0115] Preferred R 26 These include a hydrogen atom, a hydroxyl group, a C1-15 alkyl group which may have substituents, and a saturated or unsaturated carbon ring group which may have substituents. A more preferred R 26 These include a hydrogen atom, a hydroxyl group, a C1-15 alkyl group which may have one or more substituents selected from Group 2 below, and a 3-15 member saturated or unsaturated carbon ring group which may have one or more substituents selected from Group 4 below.

[0116] Preferred R 27 These include a hydrogen atom, a hydroxyl group, a C1-15 alkyl group which may have substituents, and a saturated or unsaturated carbon ring group which may have substituents. A more preferred R 27 These include a hydrogen atom, a hydroxyl group, a C1-15 alkyl group which may have one or more substituents selected from Group 2 below, and a 3-15 member saturated or unsaturated carbon ring group which may have one or more substituents selected from Group 4 below.

[0117] q is an integer between 1 and 6, preferably between 1 and 4, and more preferably between 1 and 3.

[0118] Furthermore, among the compounds represented by the general formula (1B), more preferred onium salt compounds include, for example, the compounds represented by the following general formula (1D). [ka]

[0119] Here, in the general formula (1D) R 4 , R 5 , R 6 , dotted line and X - This is the same as described above. Furthermore, the R 50 , R 51 and R 52These are identical or different hydrogen atoms, halogen atoms, nitro groups, cyano groups, optionally substituted C1-15 alkyl groups, optionally substituted C2-15 alkenyl groups, optionally substituted C2-15 alkynyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring groups, optionally substituted C1-15 alkoxy groups, optionally substituted 3-15 member saturated or unsaturated carbon ring oxy groups, optionally substituted C1-15 alkylcarbonyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring carbonyl groups, optionally substituted C1-15 alkoxycarbonyl groups, and substituted This represents an oxycarbonyl group having a 3-15 member saturated or unsaturated carbon ring, an optionally substituted aminocarbonyl group, a carboxyl group, an optionally substituted amino group, an optionally substituted C1-15 alkylthio group, an optionally substituted thio group having a 3-15 member saturated or unsaturated carbon ring, an optionally substituted C1-15 alkylsulfinyl group, an optionally substituted sulfinyl group having a 3-15 member saturated or unsaturated carbon ring, an optionally substituted C1-15 alkylsulfonyl group, an optionally substituted sulfonyl group having a 3-15 member saturated or unsaturated carbon ring, or an optionally substituted heterocyclic group. The aforementioned R 53 This represents a hydrogen atom, a halogen atom, a hydroxyl group, an optionally substituted C1-15 alkyl group, an optionally substituted C2-15 alkenyl group, an optionally substituted 3-15 member saturated or unsaturated carbocyclic group, or an optionally substituted heterocyclic group. The aforementioned R 54 This represents a hydrogen atom, a halogen atom, a hydroxyl group, a C1-15 alkyl group which may have substituents, or a saturated or unsaturated carbon ring group which may have substituents. q represents an integer between 1 and 6. Note that if q is an integer of 1, then the above R 53 or R 54 And, the aforementioned R 50These atoms may bond to each other with adjacent carbon atoms to form an unsaturated carbon ring. The unsaturated carbon ring may further have substituents. If q is an integer between 2 and 6, then two or more R 53 These may be the same or different, and there may be two or more R 54 These may be the same or different.

[0120] Examples of compounds represented by the general formula (1D) include the compound represented by the general formula (1D-1), the compound represented by the general formula (1D-2), the compound represented by the general formula (1D-3), the compound represented by the general formula (1D-4), and so on.

[0121] [ka]

[0122] Here, R in the formula 4 , R 5 , R 6 , R 50 , R 51 , R 52 , R 53 , R 54 q and X - This is the same as described above.

[0123] [ka]

[0124] Here, R in the formula 4 , R 5 , R 6 , R 50 , R 51 , R 52 , R 53 , R 54 q and X - This is the same as described above.

[0125] [ka]

[0126] Here, R in the formula 4 , R 7 , R 8 , R 9 , R 10 , R 50 , R 51 , R 52 , R 53 , R 54 q and X - This is the same as described above.

[0127] [ka]

[0128] Here, R in the formula 4 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 50 , R 51 , R 52 , R 53 , R 54 q and X - This is the same as described above.

[0129] Preferred R 50 , R 51 , R 52 , R 53 and R 54 These may be the same or different hydrogen atoms, halogen atoms, optionally substituted C1-15 alkyl groups, optionally substituted C2-15 alkenyl groups, optionally substituted C2-15 alkynyl groups, optionally substituted 3-15 member saturated or unsaturated carbocyclic groups, optionally substituted C1-15 alkoxy groups, optionally substituted C1-15 alkylcarbonyl groups, and optionally substituted C1-15 alkoxycarbonyl groups. A more preferred R 50 , R51 , R 52 , R 53 and R 54 These include, identically or differently, a hydrogen atom, a C1-15 alkyl group which may have one or more substituents selected from Group 2 below, a C2-15 alkenyl group which may have one or more substituents selected from Group 2 below, a C2-15 alkynyl group which may have one or more substituents selected from Group 2 below, a 3-15 member saturated or unsaturated carbocyclic group which may have one or more substituents selected from Group 4 below, a C1-15 alkoxy group which may have one or more substituents selected from Group 2 below, a C1-15 alkylcarbonyl group which may have one or more substituents selected from Group 2 below, and a C1-15 alkoxycarbonyl group which may have one or more substituents selected from Group 2 below.

[0130] Preferred R 53 These include a hydrogen atom, a C1-15 alkyl group which may have substituents, and a saturated or unsaturated carbon ring group which may have substituents. A more preferred R 53 These include a hydrogen atom, a C1-15 alkyl group which may have one or more substituents selected from Group 2 below, and a 3-15 member saturated or unsaturated carbon ring group which may have one or more substituents selected from Group 4 below.

[0131] Preferred R 54 These are a hydrogen atom, a C1-15 alkyl group which may have substituents, and a saturated or unsaturated carbon ring group which may have substituents. A more preferred R 54 These include a hydrogen atom, a C1-15 alkyl group which may have one or more substituents selected from Group 2 below, and a 3-15 member saturated or unsaturated carbon ring group which may have one or more substituents selected from Group 4 below.

[0132] q is an integer between 1 and 6, preferably between 1 and 4, and more preferably between 1 and 3.

[0133] Furthermore, among the compounds represented by the general formula (1B), more preferred onium salt compounds include, for example, the compounds represented by the following general formula (1E).

[0134] [ka]

[0135] Here, in the general formula (1D) R 4 , R 5 , R 6 , dotted line, and X - This is the same as described above. Furthermore, the R 60 This represents a hydrogen atom, a optionally substituted C1-15 alkyl group, an optionally substituted C2-15 alkenyl group, an optionally substituted C2-15 alkynyl group, an optionally substituted C1-15 alkoxy group, an optionally substituted 3-15 member saturated or unsaturated carbon ring oxy group, an optionally substituted aryl group, or an optionally substituted heterocyclic group. The aforementioned R 61 , R 62 and R 63 This represents, either identically or differently, a hydrogen atom, a halogen atom, a nitro group, a cyano group, an optionally substituted C1-15 alkyl group, an optionally substituted C2-15 alkenyl group, an optionally substituted C2-15 alkynyl group, an optionally substituted C1-15 alkoxy group, an optionally substituted 3-15 member saturated or unsaturated carbon ring oxy group, an optionally substituted aryl group, or an optionally substituted heterocyclic group.

[0136] Examples of compounds represented by the general formula (1E) include the compounds represented by the general formula (1E-1), the compounds represented by the general formula (1E-2), the compounds represented by the general formula (1E-3), the compounds represented by the general formula (1E-4), and so on.

[0137] [ka]

[0138] Here, R in the formula 4 , R 5 , R 6 , R 60 , R 61 , R 62 , R 63 and X - This is the same as described above.

[0139] [ka]

[0140] Here, R in the formula 4 , R 5 , R 6 , R 60 , R 61 , R 62 , R 63 and X - This is the same as described above.

[0141] [ka]

[0142] Here, R in the formula 4 , R 7 , R 8 , R 9 , R 10 , R 60 , R 61 , R 62 , R 63 and X - This is the same as described above.

[0143] [ka]

[0144] Here, R in the formula 4 , R 11 , R 12 , R 13, R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 60 , R 61 , R 62 , R 63 and X - This is the same as described above.

[0145] Preferred R 60 These include a hydrogen atom, a C1-15 alkyl group which may have substituents, and a saturated or unsaturated carbon ring group which may have substituents. A more preferred R 60 These include a hydrogen atom, a C1-15 alkyl group which may have one or more substituents selected from Group 2 below, and a 3-15 member saturated or unsaturated carbon ring group which may have one or more substituents selected from Group 4 below.

[0146] Preferred R 61 These include a hydrogen atom and a C1-15 alkyl group which may have substituents. A more preferred R 61 These are a hydrogen atom and a C1-15 alkyl group which may have one or more substituents selected from the following group 2.

[0147] Preferred R 62 These include a hydrogen atom and a C1-15 alkyl group which may have substituents. A more preferred R 62 These are a hydrogen atom and a C1-15 alkyl group which may have one or more substituents selected from the following group 2.

[0148] Preferred R 63 These include a hydrogen atom and a C1-15 alkyl group which may have substituents. A more preferred R 63These are a hydrogen atom and a C1-15 alkyl group which may have one or more substituents selected from the following group 2.

[0149] Among the onium salt compounds represented by the above general formula (1), preferred compounds are: R A However, it may be a substituted C1-15 alkyl group, a substituted C2-15 alkenyl group, a substituted C2-15 alkynyl group, a substituted 3-15 member saturated or unsaturated carbocyclic group, or a substituted heterocyclic group; R 4 However, it may be a substituted C1-15 alkyl group, a substituted C2-15 alkenyl group, a substituted 3-15 member saturated or unsaturated carbocyclic group, or a substituted C1-15 alkylcarbonyl. R 5 and R 6 However, they are the same or different hydrogen atoms, or C1-15 alkyl groups which may have substituents; Alternatively, the aforementioned R 5 and R 6 These two groups may each bond with adjacent carbon atoms to form an unsaturated carbon ring, and the unsaturated carbon ring may further have substituents; The dotted lines represent single or double bonds; X - However, the onium salt compound is a boron anion containing a fluorine-containing aromatic ring, a gallium anion containing a fluorine-containing aromatic ring, a carbon anion containing a fluorine-containing sulfonyl group, a cyclic sulfonimide anion having a fluorine atom, or a phosphorus anion containing a fluorine-containing alkyl group.

[0150] Among the onium salt compounds represented by the above general formula (1), a more preferred compound is the onium salt compound represented by the general formula (1A-3), specifically the R in the above general formula (1). 5 and R 6However, these two groups are bonded to each other with adjacent carbon atoms to form an unsaturated carbon ring, and the unsaturated carbon ring may further have substituents.

[0151] Among the onium salt compounds represented by the above general formula (1), a more preferred compound is among the onium salt compounds represented by the above general formula (1A-3), R A However, it is a C1-15 alkyl group having one or more substituents selected from <Group 1>, a C2-15 alkenyl group having one or more substituents selected from <Group 1>, a C2-15 alkynyl group having one or more substituents selected from <Group 1>, a 3-15 member saturated or unsaturated carbon ring group having one or more substituents selected from <Group 3>, or a heterocyclic group having one or more substituents selected from <Group 3>; R 4 However, it is a C1-15 alkyl group which may have one or more substituents selected from <Group 1>, or a 3-15 member saturated or unsaturated carbon ring group which may have one or more substituents selected from <Group 3>; R 7 However, it is one or more substituents selected from <group 3>; R 8 However, it is one or more substituents selected from <group 3>; R 9 However, it is one or more substituents selected from <group 3>; R 10 However, it is one or more substituents selected from <group 3>; Alternatively, the aforementioned R 7 , R 8 , R 9 and R 10 Of these, at least two groups may bond to each other with adjacent carbon atoms to form a phenyl ring, and the phenyl ring may further have one or more substituents selected from group 3; X -However, the compound is an onium salt which is a boron anion represented by the above general formula (XA2), a gallium anion represented by the above general formula (XB2), a carbon anion represented by the above general formula (XC2), or a cyclic sulfonimide anion represented by the above general formula (XD1).

[0152] Among the onium salt compounds represented by the above general formula (1A-3), particularly preferred onium salts are: R A However, it is a C1-15 alkyl group which may have one or more substituents selected from Group 2, a C2-15 alkenyl group which may have one or more substituents selected from Group 2, a C2-15 alkynyl group which may have one or more substituents selected from Group 2, a 3-15 member saturated or unsaturated carbon ring group which may have one or more substituents selected from Group 4, or a heterocyclic group which may have one or more substituents selected from Group 4; R 4 However, it is a C1-15 alkyl group which may have one or more substituents selected from <Group 2>, or a 3-15 member saturated or unsaturated carbon ring group which may have one or more substituents selected from <Group 4>; R 7 However, one or more substituents selected from <Group 4>; R 8 However, one or more substituents selected from <Group 4>; R 9 However, it is one or more substituents selected from <group 4>; R 10 However, one or more substituents selected from <Group 4>; Alternatively, the aforementioned R 7 , R 8 , R 9 and R 10 Of these, at least two groups may bond to each other with adjacent carbon atoms to form a phenyl ring, and the phenyl ring may further have one or more substituents selected from group 4; X -However, the compound is an onium salt which is a boron anion represented by the above general formula (XA2), a gallium anion represented by the above general formula (XB2), a carbon anion represented by the above general formula (XC2), or a cyclic sulfonimide anion represented by the above general formula (XD1).

[0153] The following are definitions of terms used in this specification.

[0154] The notation Cx~y can be rephrased as Cx~Cy, or simply as having x~y carbon atoms. The notation Cx~Cy indicates that a molecule has x to y carbon atoms. Here, x and y represent integers, and it is understood that all integers between x and y are also disclosed individually. For example, C1-15 has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 carbon atoms; C1-6 has 1, 2, 3, 4, 5, or 6 carbon atoms; C1-3 has 1, 2, or 3 carbon atoms; C2-15 has 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 carbon atoms C1-6 refers to a ring with 1, 2, 3, 4, 5, or 6 carbon atoms, C2-3 refers to a ring with 2 or 3 carbon atoms, 3-15 membered (C3-15 ring) refers to a cyclic compound with 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 members, and 3-7 membered (C3-7 ring) refers to a cyclic compound with 3, 4, 5, 6, or 7 members.

[0155] "May have substituents" means that the substituent is either substituted or unsubstituted. Furthermore, when this term is used and the number of substituents is not explicitly stated, it indicates that there is one or more substituents, i.e., one or two or more.

[0156] There are no particular limitations on the halogen atoms; for example, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0157] The carbon chains such as "alkyl," "alkenyl," "alkynyl," and "alkoxy" may be straight or branched.

[0158] There are no particular limitations on the C1-15 alkyl groups. Specifically, examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, isopentyl group, 1-methylbutyl group, 2-methylbutyl group, neopentyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 1-isopropylpropyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, etc. In this specification, n- means normal, sec- means secondary, t- means tertiary, and i- means iso.

[0159] A C2-15 alkenyl group refers to an unsaturated hydrocarbon group having one or more double bonds and being linear or branched. Furthermore, if geometric isomers exist, it may be either the E or Z isomer, or a mixture of the E and Z isomers in any proportion; there are no particular limitations as long as it falls within the specified C range. There are no particular limitations on the C2-15 alkenyl group. Specifically, examples include vinyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 3-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 4-methyl-3-pentenyl group, 3-methyl-2-pentenyl group, 1-methylvinyl group, 2-methylvinyl group, 1,2-dimethylvinyl group, 2,2-dimethylvinyl group, 1,2,2-trimethylvinyl group, etc. Examples of substituted C2-15 alkenyl groups include 1-phenylvinyl group and 2-phenylvinyl group.

[0160] A C2-15 alkynyl group refers to an unsaturated hydrocarbon group that has one or more triple bonds and is linear or branched. There are no particular limitations on the C2-15 alkynyl group. Specifically, examples include ethynyl group, 1-propynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1,1-dimethyl-2-propynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, etc.

[0161] A C1-15 alkoxy group refers to a group in which the aforementioned C1-15 alkyl groups are bonded via an oxygen atom. There are no particular limitations on the C1-15 alkoxy groups. Specifically, examples include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentyloxy group, isopentyloxy group, 1-methylbutoxy group, 2-methylbutoxy group, neopentyloxy group, 1-ethylpropyloxy group, 1,2-dimethylpropyloxy group, hexyloxy group, and 1-methylpentyloxy group. Examples include the groups 2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy, 1,1-dimethylbutoxy, 2,2-dimethylbutoxy, 3,3-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,3-dimethylbutoxy, 2-ethylbutoxy, 1-isopropylpropyloxy, 1,1,2-trimethylpropyloxy, and 1,2,2-trimethylpropyloxy.

[0162] An oxy group having a 3-15 member saturated or unsaturated carbon ring refers to a group in which the aforementioned 3-15 member saturated or unsaturated carbon rings are bonded via an oxycarbonyl group. There are no particular limitations on the oxycarbonyl group having a saturated or unsaturated carbon ring with 3 to 15 members. Specifically, examples include oxy groups having a saturated carbon ring such as cyclopropyloxy and cyclohexyloxy groups; and oxy groups having an unsaturated carbon ring such as cyclopropenyloxy, cyclohexenyloxy, and phenoxy groups.

[0163] There are no particular limitations on the 3- to 15-membered saturated or unsaturated carbocyclic group, and examples include 3- to 15-membered cycloalkyl groups, 3- to 15-membered cycloalkenyl groups, C6-14 aryl groups, etc.

[0164] There are no particular limitations on the C3-15 cycloalkyl group, and examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group. The C3-15 cycloalkyl group may be substituted with an oxo group. Examples of C3-15 cycloalkyl groups substituted with an oxo group include cyclopentan-3-one and cyclohexane-3-one.

[0165] There are no particular limitations on the C3-C15 cycloalkenyl group; examples include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, and cyclooctenyl groups. There are no particular limitations on the position of the double bond in the C3-C8 cycloalkenyl group.

[0166] There are no particular limitations on the C6-14 aryl group; examples include phenyl, naphthyl, anthracenyl, indenyl, acenaphthinyl, acenaphthenyl, fluorenyl, phenantrenyl, and azlenyl groups. The aryl group can be rephrased as an aromatic hydrocarbon group. Examples of substituted C6-14 aryl groups include tolyl, xylyl, mesityl, and biphenyl groups.

[0167] There are no particular limitations on the heterocyclic group; for example, saturated or unsaturated heterocyclic groups can be used. Examples of saturated or unsaturated heterocyclic groups include 5-7 member saturated or unsaturated heterocyclic groups having 1-6 atoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms.

[0168] There are no particular limitations on saturated heterocyclic groups; they include not only saturated heterocyclic groups but also non-aromatic heterocyclic groups. Examples of saturated heterocyclic groups include 4-6 membered monocyclic saturated heterocyclic groups, or fused saturated heterocyclic groups formed by the fusion of such monocyclic saturated heterocyclic groups with a benzene ring or a monocyclic aromatic ring. The ring constituent atoms of the saturated heterocyclic group may be substituted with oxo groups.

[0169] There are no particular limitations on monocyclic saturated heterocyclic groups or monocyclic non-aromatic heterocyclic groups, and specifically, for example, oxetanyl group, chetanyl group, azetidinyl group, pyrrolidinyl group, pyrrolidinyl-2-one group, piperidinyl group, morpholinyl group, thiomorpholinyl group, piperazinyl group, hexamethyleneiminyl group, oxazolidinyl group, thiazolidinyl group, imidazolidinyl group, oxazolinyl group, thiazolinyl group, isoxazolinyl group, imidazolinyl group, dioxolyl group, dioxolanyl group, dihydrooxadiazolyl group, 2-oxopyrrolidine-1-yl group, 2,4-dioxopyrimidine-5-yl group, 2-oxo-1, Examples include 3-oxazolidine-5-yl group, 5-oxo-1,2,4-oxadiazolin-3-yl group, 1,3-dioxolan-2-yl group, 1,3-dioxan-2-yl group, 1,3-dioxepane-2-yl group, pyranyl group, tetrahydropyranyl group, thiopyranyl group, tetrahydrothiopyranyl group, 1-oxidetetrahydrothiopyranyl group, 1,1-dioxidetetrahydrothiopyranyl group, tetrahydrofuranyl group, dioxanyl group, pyrazolidinyl group, pyrazolinyl group, tetrahydropyrimidinyl group, dihydrotriazolyl group, tetrahydrotriazolyl group, succinimidyl group, pyrrolidonyl group, etc.

[0170] There are no particular limitations on the condensed saturated heterocyclic group or the monocyclic non-aromatic saturated heterocyclic group. Specifically, examples include dihydroindolyl group, dihydroisoindolyl group, dihydrobenzofuranyl group, dihydrobenzodioxynyl group, dihydrobenzodioxepinyl group, tetrahydrobenzofuranyl group, chromenyl group, dihydroquinolinyl group, tetrahydroquinolinyl group, dihydroisoquinolinyl group, tetrahydroisoquinolinyl group, dihydrophthalazinyl group, 1,3-benzooxol group, and the like.

[0171] There are no particular limitations on the unsaturated heterocyclic group, and examples include a 5- or 6-membered monocyclic aromatic heterocyclic group containing 1 to 6 heteroatoms selected from oxygen, sulfur, and nitrogen atoms in addition to carbon atoms as ring constituent atoms; and an aromatic fused heterocyclic group obtained by condensing the monocyclic aromatic heterocyclic group with a benzene ring or a monocyclic aromatic ring. The ring constituent atoms of the saturated or unsaturated heterocyclic group may be substituted with oxo groups.

[0172] There are no particular limitations on the aromatic monocyclic heterocyclic groups. Specifically, examples include furyl groups, chenyl groups, pyridyl groups, 2-oxopyridyl groups, pyrimidinyl groups, pyridadinyl groups, pyrazinyl groups, pyrrolyl groups, imidazolyl groups, pyrazolyl groups, thiazolyl groups, isothiazolyl groups, oxazolyl groups, isoxazolyl groups, oxadiazolyl groups (e.g., 1,3,4-oxadiazolyl groups, 1,2,4-oxadiazolyl groups), thiadiazolyl groups (e.g., 1,3,4-thiadiazolyl groups, 1,2,4-thiadiazolyl groups), triazolyl groups (e.g., 1,2,4-triazolyl groups), tetrazolyl groups, and triazinyl groups (e.g., 1,3,5-triazinyl groups, 1,2,4-triazinyl groups). There are no particular limitations on the aromatic condensed heterocyclic groups, and specifically, for example, quinolinyl group, isoquinolinyl group, quinazolinyl group, quinoxalinyl group, synnolinyl group, phthalazinyl group, naphthylidinyl group, benzofuranyl group, benzochenyl group, benzoxazolyl group, benzoisoxazolyl group, benzothiazolyl group, benzoisothiazolyl group, benzimidazolyl group, benzotriazolyl group, indolyl group, isoindolyl group, indazolyl group, fluorophosphate group Lysyl group, chenopyridyl group, pyrrolopyridyl group (e.g., pyrrolopyridyl[1,2-a]pyridyl group, pyrrolopyridyl[2,3-b]pyridyl group), oxazolopyridyl group (e.g., oxazolo[3,2-a]pyridyl group, oxazolo[5,4-b]pyridyl group, oxazolo[4,5-b]pyridyl group), isoxazolopyridyl group (e.g., isoxazolo[2,3-a]pyridyl group, isoxazolo[4,5-b]pyridyl group, isoxazolo[5,4-b]pyridyl group) Pyrazolopyridyl groups (e.g., thiazolo[3,2-a]pyridyl group, thiazolo[5,4-b]pyridyl group, thiazolo[4,5-b]pyridyl group), isothiazolopyridyl groups (e.g., isothiazolo[2,3-a]pyridyl group, isothiazolo[4,5-b]pyridyl group, isothiazolo[5,4-b]pyridyl group), imidazopyridyl groups (e.g., imidazo[1,2-a]pyridyl group, imidazo[4,5-b]pyridyl group), pyrazolopyridyl groups (e.g., pyrazolopyridyl group, e.g., thiazolo[3,2-a]pyridyl group, thiazolo[5,4-b]pyridyl group), isothiazolopyridyl groups (e.g., isothiazolo[2,3-a]pyridyl group, isothiazolo[4,51,2-a]pyridyl group, Examples include pyrazolo[1,4-a]pyridyl group, pyrazolo[3,4-a]pyridyl group, pyrazolo[4,3-a]pyridyl group), indolidinyl group, triazolopyridyl group (for example, [1,2,4-]triazolo[1,5-a]pyridyl group), triazolopyrimidinyl group, pyrrolopyrimidinyl group, pyrrolopyrazinyl group, imidazopyrimidinyl group, imidazopyrazinyl group, pyrazolopyrimidinyl group, pyrazolotenyl group, pyrazolotriazinyl group, etc.

[0173] An oxy group having a saturated or unsaturated heterocyclic ring refers to a saturated or unsaturated heterocyclic ring bonded via an oxygen atom. There are no particular limitations on the oxy group having an unsaturated heterocycle. Specifically, examples include pyridyloxy group, pyridadinyloxy group, pyrimidinyloxy group, pyrazinyloxy group, triazinyloxy group, tetradinyloxy group, thienyloxy group, thiazolyloxy group, isothiazolyloxy group, thiadiazolyloxy group, furyloxy group, pyrrolyloxy group, imidazolyloxy group, pyrazolyloxy group, oxazolyloxy group, isoxazolyloxy group, triazolyloxy group, oxadiazolyloxy group, thiadiazolyloxy group, tetrazolyloxy group, and the like.

[0174] The term C1-15 alkylcarbonyl group refers to a group in which the aforementioned C1-15 alkyl group is bonded via a carbonyl group. There are no particular limitations on the C1-15 alkylcarbonyl group, but specifically, examples include methylcarbonyl group, ethylcarbonyl group, propylcarbonyl group, isopropylcarbonyl group, butylcarbonyl group, isobutylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, pentylcarbonyl group, isopentylcarbonyl group, etc.

[0175] A carbonyl group having a 3- to 15-membered saturated or unsaturated carbon ring refers to a group in which the aforementioned 3- to 15-membered saturated or unsaturated carbon rings are bonded via a carbonyl group. The carbonyl group having a saturated or unsaturated carbon ring with 3 to 15 members is not particularly limited, and specific examples include the cyclopropyl carbonyl group, cyclohexyl carbonyl group, cyclopropenyl carbonyl group, cyclohexenyl carbonyl group, and phenyl carbonyl group (benzoyl group).

[0176] The term C1-15 alkoxycarbonyl group refers to a group in which the aforementioned C1-15 alkoxy group is bonded via a carbonyl group. There are no particular limitations on the C1-15 alkoxycarbonyl group. Specifically, examples include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, isopentyloxycarbonyl group, and so on.

[0177] An oxycarbonyl group having a 3-15 member saturated or unsaturated carbon ring refers to a group in which the aforementioned 3-15 member saturated or unsaturated carbon rings are bonded via an oxycarbonyl group. There are no particular limitations on the oxycarbonyl group having a saturated or unsaturated carbon ring with 3 to 15 members. Specifically, examples include oxycarbonyl groups having a saturated carbon ring, such as cyclopropyloxycarbonyl group and cyclohexyloxycarbonyl group; and oxycarbonyl groups having an unsaturated carbon ring, such as cyclopropenyloxycarbonyl group, cyclohexenyloxycarbonyl group, and phenoxycarbonyl group.

[0178] Examples of an aminocarbonyl group which may have substituents include R 70 R 71 Examples include NCO groups. Here, in the formula, R 70 and R 71 This represents, either identically or differently, a hydrogen atom, an optionally substituted C1-15 alkyl group, an optionally substituted C2-15 alkenyl group, or an optionally substituted C2-15 alkynyl group.

[0179] Examples of amino groups that may have substituents include R 72 R 73 Examples include N groups. Here, in the formula, R 72 and R 73 This represents, either identically or differently, a hydrogen atom, an optionally substituted C1-15 alkyl group, an optionally substituted C2-15 alkenyl group, or an optionally substituted C2-15 alkynyl group.

[0180] A C1-C15 alkylthio group refers to a group in which the aforementioned C1-C15 alkyl groups are bonded via a thio group (sulfide). There are no particular limitations on the C1-15 alkylthio group, and examples include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, t-butylthio group, pentylthio group, isopentylthio group, etc.

[0181] A thio group having a 3- to 15-membered saturated or unsaturated carbon ring refers to a 3- to 15-membered saturated or unsaturated carbon ring bonded via a thio group. There are no particular limitations on the thio group having a saturated or unsaturated carbon ring with 3 to 15 members. Specifically, examples include cyclopropylthio group, cyclohexyloxythio group, cyclopropenylthio group, phenylthio group, and the like.

[0182] A C1-C15 alkylsulfinyl group refers to a group in which the aforementioned C1-C15 alkyl groups are bonded via a sulfinyl (sulfoxide) group. The C1-15 alkylsulfinyl group is not particularly limited, and examples include methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, isobutylsulfinyl group, sec-butylsulfinyl group, t-butylsulfinyl group, pentylsulfinyl group, isopentylsulfinyl group, and so on.

[0183] A sulfinyl group having a 3- to 15-membered saturated or unsaturated carbon ring refers to a group in which the aforementioned 3- to 15-membered saturated or unsaturated carbon rings are bonded via a sulfinyl group. The sulfinyl group having a saturated or unsaturated carbon ring with 3 to 15 members is not particularly limited, and specific examples include the cyclopropyl sulfinyl group, cyclohexyloxysulfinyl group, cyclopropenylsulfinyl group, and phenylsulfinyl group.

[0184] A C1-C15 alkylsulfonyl group refers to a group in which the aforementioned C1-C15 alkyl groups are bonded via a sulfonyl group. The C1-15 alkylsulfonyl group is not particularly limited, and examples include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, t-butylsulfonyl group, pentylsulfonyl group, isopentylsulfonyl group, etc.

[0185] A sulfonyl group having a 3- to 15-membered saturated or unsaturated carbon ring refers to a group in which the aforementioned 3- to 15-membered saturated or unsaturated carbon rings are bonded via a sulfonyl group. There are no particular limitations on the sulfonyl group having a saturated or unsaturated carbon ring with 3 to 15 members. Specifically, examples include the cyclopropylsulfonyl group, cyclohexyloxysulfonyl group, cyclopropenylsulfonyl group, and phenylsulfonyl group.

[0186] Examples of silyl groups that may have substituents include R 80 R 81 R 82 Examples include Si groups. R 80 R 81 R 82 There are no particular limitations on the Si group, and examples include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group (TIPS), t-butyldimethylsilyl group (TBS), t-butyldiphenylsilyl group (TBDPS), triphenylsilyl group, dimethylphenylsilyl group, diethylphenylsilyl group, methyldiphenylsilyl group, and ethyldiphenylsilyl group.

[0187] The substituents in this disclosure are not particularly limited and include, for example, one or more substituents selected from Group 1, one or more substituents selected from Group 2, one or more substituents selected from Group 3, one or more substituents selected from Group 4, one or more substituents selected from Group 5, one or more substituents selected from Group 6, and so on.

[0188] Specifically, the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, or alkoxy group may have one or more substituents selected from the following <Group 1>, and if it has two or more substituents, the substituents may be the same or different.

[0189] <Group 1>: Halogen atom; hydroxyl group; optionally substituted C3-6 cycloalkyl group; optionally substituted C1-6 alkoxy group; optionally substituted (C1-6 alkyl) carbonyl group; carboxyl group; optionally substituted (C1-6 alkoxy) carbonyl group; optionally substituted phenyl group, optionally substituted naphthyl group, optionally substituted phenylcarbonyl group; optionally substituted C1-6 alkylthio group; optionally substituted phenylthio group; optionally substituted C1-6 alkylsulfonyl group; optionally substituted phenylsulfonyl group; R 80 R 81 R 82 Si group, cyano group; nitro group; formyl group; oxy group having a saturated or unsaturated carbon ring with 3 to 15 members, which may be substituted; C1 to 6 alkylsulfinyl group, which may be substituted; phenylsulfinyl group, which may be substituted; R 70 R 71 NCO group; and; R 72 R 73 N group. Furthermore, the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, or alkoxy group of Group 1 may be substituted with one or more halogens, and if substituted with two or more halogens, the halogens may be the same or different. Alkyl groups substituted with halogen atoms are called haloalkyl groups. Alkenyl groups substituted with halogen atoms are called haloalkenyl groups. Alkoxy groups substituted with halogen atoms are called haloalkoxy groups. Cycloalkyl groups substituted with halogen atoms are called halocycloalkyl groups. Cycloalkenyl groups substituted with halogen atoms are called halocycloalkenyl groups. Alkoxy groups substituted with halogen atoms are called haloalkoxy groups.

[0190] Furthermore, as the one or more substituents selected from the above-mentioned <Group 1>, one or more substituents selected from the following <Group 2> are preferred.

[0191] <Group 2>: Halogen atom; hydroxyl group; C3-6 cycloalkyl group which may have at least one substituent selected from the group consisting of halogen atom, C1-6 alkyl group, C2-6 alkenyl group and C1-6 alkoxy group and (C1-6 alkoxy)carbonyl group; C1-6 alkoxy group which may have at least one substituent selected from the group consisting of halogen atom, C1-6 alkyl group, C2-6 alkenyl group and C1-6 alkoxy group and (C1-6 alkoxy)carbonyl group; halogen atom, C1-6 alkyl group, (C1-6 alkyl)carbonyl group having at least one substituent selected from the group consisting of C2-6 alkenyl groups, C1-6 alkoxy groups, and (C1-6 alkoxy)carbonyl groups; carboxyl group; (C1-6 alkoxy)carbonyl group having at least one substituent selected from the group consisting of halogen atom, C1-6 alkyl group, C2-6 alkenyl group, C1-6 alkoxy group, and (C1-6 alkoxy)carbonyl group; halogen atom, C1-6 alkyl group, C2-6 alkenyl group Phenyl groups which may have at least one substituent selected from the group consisting of C1-6 alkoxy groups and (C1-6 alkoxy)carbonyl groups; naphthyl groups which may have at least one substituent selected from the group consisting of halogen atoms, C1-6 alkyl groups, C2-6 alkenyl groups and C1-6 alkoxy groups and (C1-6 alkoxy)carbonyl groups; phenylcarbonyl groups which may have at least one substituent selected from the group consisting of halogen atoms, C1-6 alkyl groups, C2-6 alkenyl groups and C1-6 alkoxy groups and (C1-6 alkoxy)carbonyl groups; C1-6 alkylthio groups which may have at least one substituent selected from the group consisting of halogen atoms, C1-6 alkyl groups, C2-6 alkenyl groups and C1-6 alkoxy groups and (C1-6 alkoxy)carbonyl groups; phenylthio groups which may have at least one substituent selected from the group consisting of halogen atoms, C1-6 alkyl groups, C2-6 alkenyl groups and C1-6 alkoxy groups and (C1-6 alkoxy)carbonyl groups;C1-6 alkylsulfonyl groups which may have at least one substituent selected from the group consisting of halogen atoms, C1-6 alkyl groups, C2-6 alkenyl groups, C1-6 alkoxy groups and (C1-6 alkoxy)carbonyl groups; phenylsulfonyl groups which may have at least one substituent selected from the group consisting of halogen atoms, C1-6 alkyl groups, C2-6 alkenyl groups and C1-6 alkoxy groups and (C1-6 alkoxy)carbonyl groups; and tri(C1-6 alkyl)silyl groups.

[0192] The above saturated or unsaturated carbocyclic groups (sometimes referred to as carbocyclic groups) and heterocyclic groups may have one or more substituents selected from the following group 3, and if they have two or more substituents, the substituents may be the same or different.

[0193] <Group 3>: Halogen atom; hydroxyl group; cyano group; nitro group; formyl group; oxo group; carboxyl group; C1-6 alkyl group; C1-6 alkoxy group; phenoxy group; C1-6 alkoxy group with C3-6 unsaturated carbon ring; (C1-6 alkoxy)C1-6 alkyl group; C2-6 alkenyl group; C2-6 alkynyl group; C3-6 cycloalkyl group; C1-6 alkylthio group; C3-6 alkylthio group with C3-6 unsaturated carbon ring; C1-6 alkylsulfinyl group; C1-6 alkylsulfonyl group; C1-6 alkylamino group; di(C1-6 alkyl )amino group; (C1-6 alkyl)carbonyl group; carbonyl group having a C3-6 unsaturated carbon ring; (C1-6 alkoxy)carbonyl group; oxycarbonyl group having a C3-6 unsaturated carbon ring; (C1-6 alkyl)aminocarbonyl group; di(C1-6 alkyl)aminocarbonyl group; phenyl group which may have at least one substituent selected from the group consisting of a halogen atom, a C1-6 alkyl group, a C2-6 alkenyl group and a C1-6 alkoxy group and a (C1-6 alkoxy)carbonyl group; and tri(C1-6 alkyl)silyl group.

[0194] Furthermore, the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, or alkoxy group of Group 3 may be substituted with one or more halogens, and if substituted with two or more halogens, the halogens may be the same or different.

[0195] Furthermore, as the one or more substituents selected from the above-mentioned <Group 3>, one or more substituents selected from the following <Group 4> are preferred.

[0196] <Group 4>: Halogen atom; nitro group; oxo group; carboxyl group; C1-6 alkyl group; C1-6 alkoxy group; phenoxy group; (C1-6 alkoxy)C1-6 alkyl group; di(C1-6 alkyl)amino group; (C1-6 alkyl)carbonyl group; carbonyl group having a C3-6 unsaturated carbon ring; (C1-6 alkoxy)carbonyl group; oxycarbonyl group having a C3-6 unsaturated carbon ring; and a phenyl group which may have at least one substituent selected from the group consisting of halogen atom, C1-6 alkyl group, C2-6 alkenyl group, C1-6 alkoxy group and (C1-6 alkoxy)carbonyl group.

[0197] The above amino group may have one or more substituents selected from the following group 5, and if it has two or more substituents, the substituents may be the same or different.

[0198] <Group 5>: C1-6 alkyl groups; (C1-6 alkoxy)C1-6 alkyl groups; C2-6 alkenyl groups; C2-6 alkynyl groups; C3-6 cycloalkyl groups; (C1-6 alkyl)carbonyl groups; (C3-6 cycloalkyl)carbonyl groups; and (C1-6 alkoxy)carbonyl groups.

[0199] Furthermore, the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, or alkoxy group of Group 5 may be substituted with one or more halogen atoms, and if substituted with two or more halogen atoms, the halogen atoms may be the same or different.

[0200] The above silyl group may have one or more substituents selected from the following group 6, and if it has two or more substituents, the substituents may be the same or different.

[0201] <Group 6>: C1-6 alkyl groups; C2-6 alkenyl groups; C2-6 alkynyl groups; C3-6 cycloalkyl groups; and; phenyl groups which may have one or more C1-6 alkyl groups.

[0202] Furthermore, the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, or alkynyl group of Group 6 may be substituted with one or more halogen atoms, and if substituted with two or more halogen atoms, the halogen atoms may be the same or different.

[0203] A C1-6 haloalkyl group refers to a C1-6 alkyl group in which one or more hydrogen atoms are arbitrarily substituted with halogen atoms. When a molecule is substituted with two or more halogen atoms, these halogen atoms may be identical or different, and there are no particular restrictions on the number of substitutions, as long as they can exist as substituents. There are no particular limitations on the C1-6 haloalkyl groups, and examples include monofluoromethyl group, difluoromethyl group, trifluoromethyl group, monochloromethyl group, monobromomethyl group, monoiodomethyl group, chlorodifluoromethyl group, bromodifluoromethyl group, 1-fluoroethyl group, 2-fluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, pentafluoroethyl group, 2,2,2-trichloroethyl group, 3,3-difluoropropyl group, 3,3,3-trifluoropropyl group, heptafluoropropyl group, heptafluoroisopropyl group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, nonafluorobutyl group, nonafluoro-sec-butyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, undecafluoropentyl group, tridecafluorohexyl group, etc.

[0204] A haloalkenyl group refers to a C2-C6 alkenyl group in which one or more hydrogen atoms are arbitrarily substituted with halogen atoms. When substituted with two or more halogen atoms, these halogen atoms may be the same or different, and there is no particular limit to the number of substitutions as long as they can exist as substituents. There are no particular limitations on the C2-C6 haloalkenyl group, but specific examples include 2-fluorovinyl group, 2,2-difluorovinyl group, 2,2-dichlorovinyl group, 3-fluoroallyl group, 3,3-difluoroallyl group, 3,3-dichloroallyl group, 4,4-difluoro-3-butenyl group, 5,5-difluoro-4-pentenyl group, 6,6-difluoro-5-hexenyl group, etc.

[0205] A C2-6 haloalkynyl group refers to a C2-6 alkynyl group in which one or more hydrogen atoms are arbitrarily substituted with halogen atoms. When a molecule is substituted with two or more halogen atoms, these halogen atoms may be identical or different, and there are no particular restrictions on the number of substitutions, as long as they can exist as substituents. There are no particular limitations on the C2-6 haloalkynyl group; for example, 2-fluoroethynyl group, 2-chloroethynyl group, 2-bromoethynyl group, 2-iodoethynyl group, 3,3-difluoro-1-propynyl group, 3-chloro-3,3-difluoro-1-propynyl group, 3-bromo-3,3-difluoro-1-propynyl group, 3,3,3-trifluoro-1-propynyl group, 4,4-difluoro-1-butynyl group, 4,4-difluoro-2-butynyl group, 4-chloro-4,4-difluoro-1-butynyl group, 4-chloro-4,4-difluoro-2-butynyl group, 4-bromo-4,4-difluoro Examples include -1-butynyl group, 4-bromo-4,4-difluoro-2-butynyl group, 4,4,4-trifluoro-1-butynyl group, 4,4,4-trifluoro-2-butynyl group, 5,5-difluoro-3-pentynyl group, 5-chloro-5,5-difluoro-3-pentynyl group, 5-bromo-5,5-difluoro-3-pentynyl group, 5,5,5-trifluoro-3-pentynyl group, 6,6-difluoro-4-hexynyl group, 6-chloro-6,6-difluoro-4-hexynyl group, 6-bromo-6,6-difluoro-4-hexynyl group, and 6,6,6-trifluoro-4-hexynyl group.

[0206] A C1-C6 haloalkoxy group refers to a C1-C6 alkoxy group in which one or more hydrogen atoms are arbitrarily substituted with halogen atoms. When a molecule is substituted with two or more halogen atoms, these halogen atoms may be identical or different, and there are no particular restrictions on the number of substitutions, as long as they can exist as substituents. There are no particular limitations on the C1-6 haloalkoxy group. Specifically, examples include difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, pentafluoroethoxy, 2,2,2-trichloroethoxy, 3,3-difluoropropyloxy, 3,3,3-trifluoropropyloxy, heptafluoropropyloxy, heptafluoroisopropyloxy, 2,2,2-trifluoro-1-(trifluoromethyl)-ethoxy, nonafluorobutoxy, nonafluoro-sec-butoxy, 3,3,4,4,5,5,5-heptafluoropentyloxy, undecafluoropentyloxy, tridecafluorohexyloxy, and the like.

[0207] A halocycloalkyl group refers to a C3-15 cycloalkyl group in which one or more hydrogen atoms are arbitrarily substituted with halogen atoms. A halocycloalkenyl group refers to a C3-15 cycloalkenyl group in which one or more hydrogen atoms are arbitrarily substituted with halogen atoms.

[0208] Method for producing onium salt compounds There are no particular limitations on the method for producing the onium salt compound represented by general formula (1). For example, the onium salt compound represented by general formula (1) can be produced from the compound represented by general formula (2) below by the production route shown in scheme 1 below.

[0209] (Scheme 1) [ka]

[0210] In the formula, R A , R 4 , R 5 , R 6 , X -The dotted lines are the same as described above. L is a leaving group. There are no particular limitations on the leaving group, and examples include halogen atoms such as fluoro, chloro, bromo, and iodo groups; mesylate, tosyl, nosyl, cyano, alkyl sulfate, and triflat groups. Y is a counter anion. Examples of counter anions include fluoro groups, chloro groups, bromo groups, iodo groups, mesylate groups, tosyl groups, nosyl groups, cyano groups, alkyl sulfate groups, and triflate groups. M is a cation. Examples of cations include hydrogen ions; alkali metal ions such as sodium ions, lithium ions, potassium ions, rubidium ions, cesium ions, and beryllium ions; alkaline earth metal ions such as magnesium ions, calcium ions, strontium ions, and barium ions; metal ions such as scandium ions, titanium ions, zirconium ions, vanadium ions, niobium ions, chromium ions, molybdenum ions, manganese ions, iron ions, ruthenium ions, cobalt ions, rhodium ions, nickel ions, palladium ions, copper ions, silver ions, zinc ions, cadmium ions, aluminum ions, gallium ions, tin ions, and antimony ions; and ammonium ions such as tetramethylammonium and tetrabutylammonium.

[0211] (Process I) Process I is the process shown in Scheme I below.

[0212] [ka]

[0213] In the formula, R A , R 5 , R 6 L and the dotted line are the same as described above.

[0214] Specifically, step I is a step in which a compound represented by general formula (2) and a compound represented by general formula (3) are reacted to produce a compound represented by general formula (4). Step I can be carried out, for example, in the presence of an acid or base, or in a solvent.

[0215] The compound represented by general formula (2) used in this reaction can be obtained commercially or manufactured by known methods. For example, 4-mercaptobenzothiazole, 4-methyl-2-mercaptobenzothiazole, 2-mercaptothiazoline, etc., can be purchased from Tokyo Chemical Industry Co., Ltd.

[0216] In step I, the amount of the compound represented by general formula (3) is not particularly limited as long as it is at least 1 equivalent relative to the compound represented by general formula (2), as long as the desired reaction proceeds; however, it is preferably between 1 and 3 equivalents. Compounds represented by general formula (3) include, for example, fluorobenzyl, benzyl chloride, benzyl bromide, benzyl iodide, 4-methylbenzyl fluoride, 4-methylbenzyl chloride, 4-methylbenzyl bromide, 4-methylbenzyl iodide, 1-(fluoromethyl)naphthalene, 1-(chloromethyl)naphthalene, 1-(bromomethyl)naphthalene, 1-(methyl iodide)naphthalene, 4-phenylbenzyl fluoride, 4-phenylbenzyl chloride, and 4-phenyl bromide. Examples include alkyl halides having aromatic groups such as benzyl and 4-phenylbenzyl iodide; alkyl halides such as fluoromethyl, methyl chloride, methyl bromide, and methyl iodide; and alkyl halides having alicyclic hydrocarbon groups such as cyclopentyl fluoride, cyclopentyl chloride, cyclopentyl bromide, cyclopentyl iodide, 1-adamantyl fluoride, 1-adamantyl chloride, 1-adamantyl bromide, and 1-adamantyl iodide.

[0217] In addition, instead of using the compound represented by general formula (3), a compound having a double bond can be used to carry out an addition reaction with the compound represented by general formula (2) (thiol compound). Examples of such double-bonded compounds (3) that can undergo addition reactions include oxirane compounds such as methyloxirane and phenyloxirane; and unsaturated hydrocarbons such as styrene, indene, N-phenylmaleimide, methyl acrylate, and methyl methacrylate.

[0218] In step I, the acid or base used can be carried out in catalytic amounts and is not particularly limited as long as the desired reaction proceeds, but preferably it is 0.01 equivalents or more and 3 equivalents or less relative to the compound represented by general formula (3). There are no particular limitations on the type of acid, but examples include hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, methanesulfonic acid, tosylic acid, hypochlorous acid, hypobromous acid, hypoiodic acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate, acetic acid, formic acid, oxalic acid, boron trifluoride, boron tribromide, titanium tetrachloride, titanium tetrabromide, aluminum chloride, aluminum bromide, zinc chloride, zinc bromide, copper chloride, copper bromide, copper iodide, titanium chloride, tin chloride, etc. These acids can be used individually or in any mixture of two or more in any proportion. There are no particular limitations on the type of base, and examples include inorganic salts such as lithium carbonate, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, cesium carbonate, calcium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium hydride, and potassium hydride; and organic bases such as triethylamine, diisopropylethylamine, 1,8-diazabicyclo[5.4.0]-7-undecene, imidazole, guanidine, pyridine, 1,4-diazabicyclo[2.2.2]octane, and 4-dimethylaminopyridine. These bases can be used individually or in any mixture of two or more in any proportion.

[0219] In step I, the solvents used include ether-based solvents such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, 4-methyltetrahydropyran, and dioxane; alcohol-based solvents such as methanol, ethanol, n-propanol, and i-propanol; benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene; ester-based solvents such as ethyl acetate, isopropyl acetate, and butyl acetate; nitrile-based solvents such as acetonitrile; amide-based solvents such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide; urea-based solvents such as 1,3-dimethyl-2-imidazolidinone; halogen-based solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; sulfur-based solvents such as dimethyl sulfoxide and sulfolane; organic solvents such as ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; organic solvents such as nitro-based solvents such as nitromethane; and water. These solvents can be used individually or in any mixture of two or more in any proportion. Preferred solvents include, for example, ethyl acetate, tetrahydrofuran, nitromethane, acetonitrile, N,N-dimethylformamide, N-methylpyrrolidone, methyl ethyl ketone, water, and dimethyl sulfoxide.

[0220] The amount of solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but is usually 10 to 20,000 parts by mass per 100 parts by mass of the compound represented by general formula (2).

[0221] In step I, there are no particular limitations on the reaction temperature; for example, it is typically around 20°C to 100°C. There are no particular limitations on the reaction time; for example, it is typically around 1 to 72 hours.

[0222] As a post-treatment of the reaction, liquid-liquid extraction can be performed by adding water or a suitable aqueous solution to the reaction mixture. When using an aqueous solution, acidic aqueous solutions such as hydrochloric acid, sulfuric acid, or ammonium chloride can be used; alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, or potassium bicarbonate can be used; or saline solution can be used as desired. During liquid-liquid extraction, solvents that are immiscible with water can be added as needed, such as benzene-based solvents such as toluene, xylene, benzene, chlorobenzene, and dichlorobenzene; ester-based solvents such as ethyl acetate, isopropyl acetate, and butyl acetate; ether-based solvents such as diethyl ether, diisopropyl ether, and methyl-t-butyl ether; halogen-based solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; and hydrocarbon-based solvents such as hexane, heptane, cyclohexane, and methylcyclohexane. These solvents can be used individually or mixed in any proportion. There is no particular limit to the number of liquid-liquid extractions, and it can be performed according to the desired purity or yield.

[0223] The reaction mixture containing the compound represented by general formula (4) obtained above can be dehydrated with a desiccant such as sodium sulfate or magnesium sulfate, but this is not essential.

[0224] The reaction mixture containing the compound represented by general formula (4) obtained above can be desolvated under reduced pressure, provided that the compound does not decompose. The reaction mixture containing the compound represented by general formula (4) obtained after solvent removal can be purified by washing, reprecipitation, recrystallization, distillation, column chromatography, etc., using a suitable solvent.

[0225] (Process II) Process II is the process shown in Scheme II below.

[0226] [ka]

[0227] In the formula, R A , R 4 , R 5 , R 6 Y and the dotted line are the same as described above.

[0228] Step II is a step in which the compound represented by general formula (4) obtained in Step I is reacted with the compound represented by general formula (5) to produce the compound represented by general formula (6). Step II can be carried out, for example, in the presence of a solvent.

[0229] In step II, the amount of the compound represented by general formula (5) is not particularly limited as long as the desired reaction proceeds, but is usually about 0.5 to 10 equivalents relative to the compound represented by general formula (4). Compounds represented by general formula (5) include, for example, alkyl halides such as methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, propyl chloride, propyl bromide, propyl iodide, butyl chloride, butyl bromide, and butyl iodide; dialkyl sulfates such as dimethyl sulfate and diethyl sulfate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; aryl halides such as fluorobenzyl, benzyl chloride, benzyl bromide, and benzyl iodide; methylated compounds such as methyl tosylate, methyl trifluoroacetate, methyl trifluorosulfonate, methyl hypochlorite, methyl formate, and methyl orthoformate; and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

[0230] The solvents used in step II include ether-based solvents such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, 4-methyltetrahydropyran, and dioxane; alcohol-based solvents such as methanol, ethanol, n-propanol, and i-propanol; benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene; ester-based solvents such as ethyl acetate, isopropyl acetate, and butyl acetate; nitrile-based solvents such as acetonitrile; amide-based solvents such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide; urea-based solvents such as 1,3-dimethyl-2-imidazolidinone; halogen-based solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; sulfur-based solvents such as dimethyl sulfoxide and sulfolane; organic solvents such as ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; organic solvents such as nitro-based solvents such as nitromethane; and water. These solvents can be used individually or in any mixture of two or more in any proportion. The solvents are preferably ethyl acetate, isopropyl acetate, butyl acetate, tetrahydrofuran, nitromethane, acetonitrile, N,N-dimethylformamide, N-methylpyrrolidone, methyl ethyl ketone, dimethyl sulfoxide, methanol, and water.

[0231] The amount of solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but is usually 10 to 20,000 parts by mass per 100 parts by mass of the compound represented by general formula (4).

[0232] In step II, there are no particular limitations on the reaction temperature, for example, it can be around 0°C to 70°C. There are no particular limitations on the reaction time, for example, it can be 0.5 to 72 hours.

[0233] In step II, a catalyst may be added to further accelerate the reaction, if necessary. The type of catalyst is not particularly limited and examples include alkali metal halides such as lithium bromide, lithium iodide, sodium bromide, sodium iodide, potassium bromide, and potassium iodide; and cesium halides such as cesium bromide and cesium iodide. These catalysts can be used individually or in any mixture of two or more in any proportion.

[0234] As a post-treatment of the reaction, liquid-liquid extraction can be performed by adding water or a suitable aqueous solution to the reaction mixture. When using an aqueous solution, acidic aqueous solutions such as hydrochloric acid, sulfuric acid, or ammonium chloride can be used; alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, or potassium bicarbonate can be used; or saline solution can be used as desired. During liquid-liquid extraction, solvents that are immiscible with water can be added as needed, such as benzene-based solvents such as toluene, xylene, benzene, chlorobenzene, and dichlorobenzene; ester-based solvents such as ethyl acetate, isopropyl acetate, and butyl acetate; ether-based solvents such as diethyl ether, diisopropyl ether, and methyl-t-butyl ether; halogen-based solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; and hydrocarbon-based solvents such as hexane, heptane, cyclohexane, and methylcyclohexane. These solvents can be used individually or mixed in any proportion. There is no particular limit to the number of liquid-liquid extractions, and it can be performed according to the desired purity or yield.

[0235] The reaction mixture containing the compound represented by general formula (6) obtained above can be dehydrated with a desiccant such as sodium sulfate or magnesium sulfate, but this is not essential.

[0236] The reaction mixture containing the compound represented by general formula (6) obtained above can be desolvated under reduced pressure, provided that the compound does not decompose. The reaction mixture containing the compound represented by general formula (6) obtained after solvent removal can be purified by washing, reprecipitation, recrystallization, column chromatography, etc., with a suitable solvent.

[0237] (Process III) Process III is the process shown in Scheme III below. [ka]

[0238] In the formula, R A , R 4 , R 5 , R 6 , X - Y, M, and the dotted line are the same as described above.

[0239] Step III is a step in which the compound represented by general formula (6) obtained in Step II is reacted with the compound represented by general formula (7) to produce the compound represented by general formula (1). Step III can be carried out, for example, in the presence of a solvent.

[0240] In step III, the amount of the compound represented by general formula (7) is not particularly limited as long as the desired reaction proceeds, but is usually about 0.5 to 3 equivalents relative to the compound represented by general formula (6).

[0241] In step III, the compound represented by general formula (7) is, for example, a boron compound containing a fluorine-containing aromatic ring such as MB(C6F5)4, MB(C6H4F)4, MB(C6H3(CF3)2)4; a gallium compound containing a fluorine-containing aromatic ring such as MGa(C6F5)4; a carbon compound containing a fluorine-containing sulfonyl group such as MC(SO2CF3)3; a cyclic sulfonimide compound having a fluorine atom such as MN(SO2CF2)2CF2; or a phosphorus compound containing a fluorine-containing alkyl group such as MPF3(C2F5)3. Here, M is preferably an alkali metal such as lithium, sodium, potassium, or rubidium; an alkaline earth metal such as magnesium or calcium; or an ammonium salt such as tetramethylammonium or tetrabutylammonium.

[0242] The solvents used in step III include ether-based solvents such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, 4-methyltetrahydropyran, and dioxane; alcohol-based solvents such as methanol, ethanol, n-propanol, and i-propanol; benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene; ester-based solvents such as ethyl acetate, isopropyl acetate, and butyl acetate; nitrile-based solvents such as acetonitrile; amide-based solvents such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide; urea-based solvents such as 1,3-dimethyl-2-imidazolidinone; halogen-based solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; sulfur-based solvents such as dimethyl sulfoxide and sulfolane; organic solvents such as ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; organic solvents such as nitro-based solvents such as nitromethane; and water. These solvents can be used individually or in any mixture of two or more in any proportion. From the viewpoint of subsequent purification processes, non-water-soluble solvents such as toluene, dichloromethane, ethyl acetate, nitromethane, and 4-methyltetrahydropyran are preferred as solvents.

[0243] The amount of solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but is usually 10 to 20,000 parts by mass per 100 parts by mass of the compound represented by general formula (6).

[0244] In step III, there are no particular limitations on the reaction temperature, for example, 0°C to 50°C. There are no particular limitations on the reaction time, for example, 0.5 to 24 hours. As a post-treatment of the reaction, liquid-liquid extraction can be performed by adding water or a suitable aqueous solution to the reaction mixture. When using an aqueous solution, acidic aqueous solutions such as hydrochloric acid, sulfuric acid, or ammonium chloride can be used; alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, or potassium bicarbonate can be used; or saline solution can be used as desired. During liquid-liquid extraction, solvents that are immiscible with water can be added as needed, such as benzene-based solvents such as toluene, xylene, benzene, chlorobenzene, and dichlorobenzene; ester-based solvents such as ethyl acetate, isopropyl acetate, and butyl acetate; ether-based solvents such as diethyl ether, diisopropyl ether, and methyl-t-butyl ether; halogen-based solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; and hydrocarbon-based solvents such as hexane, heptane, cyclohexane, and methylcyclohexane. These solvents can be used individually or mixed in any proportion. There is no particular limit to the number of liquid-liquid extractions, and it can be performed according to the desired purity or yield.

[0245] The reaction mixture containing the compound represented by general formula (1) obtained above can be dehydrated with a desiccant such as sodium sulfate or magnesium sulfate, but this is not essential.

[0246] The reaction mixture containing the compound represented by general formula (1) obtained above can be desolvated under reduced pressure, provided that the compound does not decompose. The reaction mixture containing the compound represented by general formula (1) obtained after solvent removal can be purified by washing, reprecipitation, recrystallization, column chromatography, etc., with a suitable solvent.

[0247] <Application> The onium salt compounds of this disclosure can be used in a variety of applications. These onium salt compounds can be used, for example, as acid generators, polymerization initiators, adhesives, encapsulants, resists, coatings, sealants, adhesives, surface modifiers, surface treatment agents, dye fixatives, ink fixatives, pigment dispersants, flocculants, pesticides, antibacterial agents, fungicides, paper strength enhancers, corrosion inhibitors, plating brighteners, optical materials, solubilizers, variable color materials, pesticides, colorants, etc.

[0248] Acidifying agent The onium salt compounds of this disclosure can be used as acid generators. The onium salt compounds of this disclosure have excellent solvent compatibility and excellent storage stability. Here, solvent compatibility means that it can be dissolved in various types of solvents. Solvents capable of dissolving the onium salt compounds of this disclosure include, for example, ether-based solvents such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, 4-methyltetrahydropyran, and dioxane; alcohol-based solvents such as methanol, ethanol, n-propanol, and i-propanol; benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene; nitrile-based solvents such as acetonitrile; and N-methylpyrrolidone, N,N- Amide solvents such as dimethylformamide and N,N-dimethylacetamide; urea solvents such as 1,3-dimethyl-2-imidazolidinone; halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; sulfur solvents such as dimethyl sulfoxide and sulfolane; organic solvents such as ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; nitro solvents such as nitromethane; carbonate solvents such as propylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and ethylene carbonate; PGMAc Ester solvents such as (propylene glycol 1-monomethyl ether 2-acetate), ethyl acetate, isopropyl acetate, and butyl acetate; "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "jER (registered trademark, may be abbreviated below) 828EL", "825", and "jER828 (bisphenol A-type epoxy resin)" manufactured by Mitsubishi Chemical Corporation; and "jER807" and "1750" (bisphenol F-type epoxy resin) manufactured by Mitsubishi Chemical Corporation. Epoxy resins); "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" and "630LSD" (glycidylamine type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "ZX-1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation; "Celoxide" (registered trademark, may be omitted below) manufactured by Daicel Corporation.Examples of liquid epoxy resins include "2021P" (a cycloaliphatic epoxy resin with an ester skeleton); "PB-3600" (an epoxy resin with a butadiene structure) manufactured by Daicel Corporation; and "ZX-1658" and "ZX-1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resins) manufactured by Nippon Steel Chemical & Material Corporation. These solvents may be used individually or mixed in any proportion. Among these, propylene carbonate, methyl isobutyl ketone, PGMAc (propylene glycol 1-monomethyl ether 2-acetate), toluene, celoxide 2021P, and jER828 are preferred solvents. Storage stability means that when a reactive composition containing the onium salt compound of this disclosure is stored, the onium salt remains stable without decomposition or the reactive composition gels. Furthermore, the onium salt compounds of this disclosure exhibit excellent photoreactivity and thermal reactivity.

[0249] <Polymerization initiator> The onium salt compounds of this disclosure can be used as polymerization initiators. The onium salt compounds of this disclosure can be used as photopolymerization initiators or thermal polymerization initiators. Furthermore, the onium salt compounds of this disclosure can be used as radical polymerization initiators. Specifically, examples of photopolymerization initiators include photoradical polymerization initiators, photocationic polymerization initiators, and photoanionic polymerization initiators. Among the above photopolymerization initiators, photoradical polymerization initiators or photocationic polymerization initiators are preferably used. Furthermore, the polymerization initiator in this disclosure may contain known polymerization initiators other than onium salt compounds. Known polymerization initiators include, for example, iodonium salts such as diazonium salts and diaryliodonium salts; sulfonium salts such as triarylsulfonium salts; cationic photopolymerization initiators such as benzylpyridinium thiocyanate, dialkylphenacylsulfonium salt, and dialkylhydroxyphenylphosphonium salt.

[0250] <Reactive composition> The reactive composition of this disclosure comprises the onium salt compound of this disclosure and a reactive compound. Here, the reactive composition can be rephrased as a reactive resin composition, a curable resin composition, a photosensitive resin composition, etc. The reactive compositions of this disclosure can be used in a variety of applications. Examples of applications for the reactive compositions of this disclosure include acid generators, polymerization initiators, adhesives, encapsulants, resists, solubilizers, variable color materials, pesticides, and colorants. Furthermore, a cured product obtained by mixing the onium salt compound and the reactive compound of this disclosure can form a film with excellent insulating properties and transparency.

[0251] There are no particular limitations on the types of reactive compounds; examples include compounds having acid-unstable groups and compounds having radical-reactive groups. Compounds having acid-unstable groups are not particularly limited as long as they are compounds that react or hydrolyze with acid. Examples include resins having acid-unstable groups as described in Japanese Patent Publication No. 2023-169223, etc., which have a leaving group, and upon contact with acid, the leaving group is removed, converting the constituent unit into a constituent unit having a hydrophilic group (e.g., a hydroxyl group or a carboxyl group); ester group-containing polymers having structural units derived from (meth)acrylic monomers as described in Japanese Patent Publication No. 2020-075903; epoxy compounds; oxetane compounds; vinyl compounds; silyl compounds; polyamic acids; and compounds that develop color upon reaction with acid (chromogenic compounds) such as leuco dyes, triarylmethane dyes, diphenylmethane dyes, fluorane dyes, spiropyran dyes, and rhodamine dyes as described in Japanese Patent Publication No. 2022-086976.

[0252] The term "compound having a radical-reactive group" is not particularly limited and refers to any compound that reacts with radicals. Examples of compounds that react with radicals include compounds that react with radicals and yield a cured product, such as those described in Japanese Patent No. 6464271. An example of such a compound that reacts with radicals is KAYARAD Examples include esterified polyols of (meth)acrylic acid such as DPHA, DPHA-2C, PET-30, TMPTA, TPA-320, TPA-330, RP-1040, T-1420, D-310, DPCA-20, DPCA-30, DPCA-60, GPO-303 (manufactured by Nippon Kayaku Co., Ltd.), NK esters A-TMPT, A-TMMT, A-TMM3, A-TMM3L, A-9550 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), V#3PA, V#400, V#36095D, V#1000, V#1080, and Viscoat #802 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), as well as dendrimer-type polyfunctional acrylates such as Sirius-501 and SUBARU-501 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).In addition, Shiko UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B, UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-32 10EA, UV-3310EA, UV-3310B, UV-3500BA, UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, UV-2250EA, UV-2750B (manufactured by Nippon Synthetic Chemical Co., Ltd.), UL-503LN (manufactured by Kyoeisha Chemical Co., Ltd.), Unidic 17-806, 17-813 , V-4030, V-4000BA (manufactured by Dainippon Ink and Chemicals, Inc.), EB-1290K, EB-220, EB-5129, EB-1830, EB-4858 (manufactured by Daicel UCB Corporation), Hycorp AU-2010, AU-2020 (manufactured by Tokushiki Co., Ltd.), Aronics M-1960 (manufactured by Toagosei Co., Ltd.), Artresin UN-3320HA, UN-3320HC, Urethane acrylate compounds with three or more functions, such as UN-3320HS, UN-904 (manufactured by Negami Kogyo Co., Ltd.), NK Oligo U-4HA, U-15HA (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and polyester compounds with three or more functions, such as Aronics M-8100, M-8030, M-9050 (manufactured by Toagosei Co., Ltd.) and KRM-8307 (manufactured by Daicel Cytec Co., Ltd.), can also be used.

[0253] The reactive compound is preferably liquid at 25°C because it offers excellent workability and low-temperature curing properties. The viscosity of the reactive compound at 25°C is preferably 0.1 to 30,000 mPa·s, more preferably 1 to 15,000 mPa·s, and particularly preferably 10 to 1,000 mPa·s. The reactive composition is preferably liquid at 25°C because it offers excellent workability and low-temperature curing properties. Furthermore, there are no particular limitations on the viscosity of the reactive compound at 25°C.

[0254] Among the reactive compounds mentioned above, there are no particular limitations on the epoxy compounds (which can also be called epoxy monomers), and examples include aromatic epoxy resins, hydrogenated epoxy resins, and alicyclic epoxy compounds.

[0255] There are no particular limitations on the hydrogenated epoxy resin, and examples include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol E type epoxy resin, diglycidyl ether of the alkylene oxide adduct of hydrogenated bisphenol A type, diglycidyl ether of the alkylene oxide adduct of hydrogenated bisphenol F, hydrogenated phenol novolac epoxy resin, and hydrogenated cresol novolac epoxy resin.

[0256] Examples of commercially available hydrogenated bisphenol A type epoxy resins include YX-8000, YX-8034 (manufactured by Mitsubishi Chemical Corporation), EXA-7015 (manufactured by DIC Corporation), ST-3000 (manufactured by Nippon Steel Chemical & Material Corporation), Rikaresin HBE-100 (manufactured by Shin Nippon Rika Co., Ltd.), and EX-252 (manufactured by Nagase ChemteX Corporation). Examples of commercially available hydrogenated bisphenol F type epoxy resins include YL-6753 (manufactured by Mitsubishi Chemical Corporation).

[0257] There are no particular limitations on the alicyclic epoxy compounds, and examples include 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, bis(3,4-epoxycyclohexyl) adipate, 1,2-epoxy-4-vinylcyclohexane, 1,4-cyclohexanedimethanol diglycidyl ether, epoxyethyl divinylcyclohexane, diepoxyvinylcyclohexane, 1,2,4-triepoxyethylcyclohexane, limonene dioxide, and alicyclic epoxy group-containing silicone oligomers.

[0258] Commercially available alicyclic epoxy compounds are not particularly limited and include, but are not limited to, examples such as Celoxide 2081, Celoxide 2021P, Celoxide 2000, Celoxide 3000, EHPE3150 (manufactured by Daicel Corporation), TTA21 (manufactured by Jiangsu TetraChem), Licarezin DME-100 (manufactured by Shin-Nippon Rika Co., Ltd.), X-40-2670, X-22-169AS, and X-22-169B (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0259] There are no particular limitations on the aromatic epoxy resin, and examples include aromatic bisphenol A type epoxy resin, aromatic bisphenol F type epoxy resin, aromatic bisphenol E type epoxy resin, diglycidyl ether of an alkylene oxide adduct of aromatic bisphenol A type, diglycidyl ether of an alkylene oxide adduct of aromatic bisphenol F type, diglycidyl ether of an alkylene oxide adduct of aromatic bisphenol E type, aromatic novolac type epoxy resin, urethane-modified aromatic epoxy resin, nitrogen-containing aromatic epoxy resin, rubber-modified aromatic epoxy resin containing polybutadiene or nitrile butadiene rubber (NBR), etc.

[0260] Examples of commercially available aromatic epoxy resins include jER825, 827, 828, 828EL, 828US, 828XA, 834, 806, 806H, 807, 604, 630 (manufactured by Mitsubishi Chemical Corporation), EPICLON830, EXA-830LVP, EXA-850CRP, 835LV, HP4032D, 703, 720, 726, HP820, N-660, N-680, N-695, N-655-EXP-S, N-665-EXP-S, N-685-EXP-S, N- Examples include, but are not limited to, 740, N-775, N-865 (manufactured by DIC Corporation), EP4100, EP4000, EP4080, EP4085, EP4088, EP4100HF, EP4901HF, EP4000S, EP4000L, EP4003S, EP4010S, EP4010L (manufactured by ADEKA Corporation), Denacol EX614B, EX411, EX314, EX201, EX212, EX252 (manufactured by Nagase ChemteX Corporation).

[0261] Examples of oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, 3-(meth)allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, [1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenyl ether, isobutoxymethyl(3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl(3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol(3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl(3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl(3-ethyl-3-oxetanylmethyl) ether, and 2-tetrabromophenoxyethyl(3-ethyl-3-oxetanylmethyl) ether. Examples include pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, and ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether.

[0262] Examples of commercially available oxetane compounds include, but are not limited to, OXT-212, OXT-221, OXT-213, and OXT-101 (manufactured by Toagosei Co., Ltd.).

[0263] The vinyl compounds are not particularly limited and include, for example, aryl vinyl ethers such as phenyl vinyl ether; alkyl vinyl ethers such as n-butyl vinyl ether and n-octyl vinyl ether; cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; vinyl ethers having a hydroxyl group such as 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, and 2-hydroxybutyl vinyl ether; hydroquinone divinyl ether; 1,4-butanediol divinyl ether; cyclohexane divinyl ether; cyclohexanedimethanol divinyl ether; ethylene glycol divinyl ether; diethylene glycol divinyl ether; triethylene glycol divinyl ether; tetraethylene glycol divinyl ether; n-butyl vinyl ether; isobutyl vinyl ether; 2-ethylhexyl vinyl ether; cyclohexyl vinyl ether; 2-hydroxyethyl vinyl ether; diethylene glycol monovinyl ether; 4-hydroxybutyl vinyl ether; polyfunctional vinyl ethers such as 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate; styrene, 4-methoxystyrene, 4-methylstyrene, etc. Examples of commercially available vinyl compounds include, but are not limited to, NPVE, IPVE, NBVE, IBVE, EHVECHVE (manufactured by Nippon Carbide Industries, Ltd.), HEVE, DEGV, HBVE (manufactured by Maruzen Petrochemical Co., Ltd.), VEEA, and VEEM (manufactured by Nippon Shokubai Co., Ltd.).

[0264] There are no particular limitations on the silyl compounds, and examples include dialkoxysilanes, trialkoxysilanes, tetraalkoxysilanes, and 3-glycidoxypropyltrimethoxysilanes. Specifically, commercially available silyl compounds include KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.

[0265] There are no particular limitations on the polyamic acid (polyimide precursor), and examples include the primary reaction product of disuccinic anhydride and diamine. Specifically, examples include the compounds described in Japanese Patent Publication No. 2021-138840.

[0266] In the reactive compositions of this disclosure, the onium salt compound or polymerization initiator is, for example, about 0.001 to 50 parts by mass, preferably 0.01 to 10 parts by mass, per 100 parts by mass of the reactive compound. In this specification, numerical ranges indicated by "~" include upper and lower limits unless otherwise specified. Reactive compounds can be used individually or in combination of two or more. Furthermore, the reactive composition of this disclosure may contain other optional components besides the onium salt compound and the reactive compound described above. There are no particular limitations on optional components, and examples include solvents for dilution, surfactants, etc. Other optional components include sensitizers, antioxidants, stabilizers, solvents, leveling agents, silane coupling agents, fillers, conductive particles, plasticizers, defoamers, foaming agents, UV absorbers, ion adsorbents, pigments, dyes, phosphors, mold release agents, antistatic agents, flame retardants, radical-curable compounds, etc.

[0267] Examples of solvents include ether-based solvents such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, 4-methyltetrahydropyran, and dioxane; alcohol-based solvents such as methanol, ethanol, n-propanol, and i-propanol; benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene; nitrile-based solvents such as acetonitrile; and N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetate. Amide solvents such as toamide; urea solvents such as 1,3-dimethyl-2-imidazolidinone; halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; sulfur solvents such as dimethyl sulfoxide and sulfolane; organic solvents such as ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; nitro solvents such as nitromethane; carbonate solvents such as propylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and ethylene carbonate; PGMAc(propylene glycol 1-monomethyl ether 2- Ester solvents such as acetate, ethyl acetate, isopropyl acetate, and butyl acetate; "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "jER828" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; and "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation. ; "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX-1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Corporation; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation; "Celoxide 2021P" (alicyclic epoxy resin with an ester skeleton) manufactured by Daicel Corporation; "PB-3600" (epoxy resin with a butadiene structure) manufactured by Daicel Corporation;Examples of liquid epoxy resins include "ZX-1658" and "ZX-1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd. These solvents may be used individually or mixed in any proportion. Among these, propylene carbonate, methyl isobutyl ketone, PGMAc (propylene glycol 1-monomethyl ether 2-acetate), toluene, celoxide 2021P, and jER828 are preferred solvents.

[0268] <Surfactants> The reactive compositions included in this disclosure may further include surfactants. The inclusion of surfactants improves wettability during coating, allowing for the creation of a uniform resin film and a cured film. The surfactants are not particularly limited and include, for example, fluorinated surfactants, silicone surfactants, alkyl surfactants, acrylic surfactants, and the like.

[0269] The surfactant described above preferably contains a surfactant that includes at least one of a fluorine atom and a silicon atom. This contributes to obtaining a uniform resin film (improved coatability), improved developability, and improved adhesive strength. Such a surfactant is preferably a nonionic surfactant that contains at least one of a fluorine atom and a silicon atom. Examples of commercially available surfactants that can be used include the "Megafac" series from DIC Corporation: F-251, F-253, F-281, F-430, F-477, F-551, F-552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563, F-565, F-568, F-569, F-570, F-572, and F-574. Examples include fluorine-containing oligomer surfactants such as F-575, F-576, R-40, R-40-LM, R-41, and R-94; fluorine-containing nonionic surfactants such as Futergent 250 and Futergent 251 manufactured by Neos Co., Ltd.; and silicone-based surfactants such as the SILFOAM® series (e.g., SD100TS, SD670, SD850, SD860, SD882) manufactured by Wacker Chemie.

[0270] The amount of the surfactant is not particularly limited, and can be, for example, 0.001 to 10% by mass, preferably 0.01 to 1% by mass, based on the total amount of non-volatile components of the reactive composition.

[0271] <Method for producing reactive compositions> The reactive composition can be produced by uniformly mixing the above-mentioned onium salt compound or polymerization initiator containing the onium salt compound with the above-mentioned reactive compound, and optionally with other additional components, using commonly known mixing equipment such as a self-rotating agitator, homogenizer, planetary mixer, three-roll mill, or bead mill. The components may be mixed simultaneously or sequentially.

[0272] <Polymers and methods for producing the same> The reactive compositions in this disclosure yield polymers by polymerization using known methods. The method for polymerizing the reactive composition is not particularly limited and includes methods such as polymerization using light such as ultraviolet light, radiation, or electron beams, and polymerization using heat. For example, a polymerization method using light irradiation may include a photopolymerization step in which the reactive composition is prepolymerized (pre-cured) by light irradiation, and a thermal polymerization step in which the main polymerization is carried out by heating. When using the acid generator of this disclosure, polymerization by light irradiation and subsequent heat treatment improve physical properties such as adhesion, uniformity, hardness, toughness, and durability.

[0273] In the photoreaction step, the irradiated light preferably includes light in the wavelength range of 10 nm to 500 nm, and more preferably includes ultraviolet light with a wavelength of 400 nm or less.

[0274] There are no particular limitations on the light source, and examples include ultraviolet LEDs, blue LEDs, white LEDs, lasers, metal halide lamps, xenon lamps, high-pressure or medium-pressure mercury lamps, etc.

[0275] There are no particular limitations on the amount of light irradiation; for example, the intensity at a wavelength of 313 nm can be 0.1 to 1000 mW / cm². 2 These are some examples.

[0276] There are no specific limitations on the duration of light exposure; for example, it can range from 0.1 seconds to 3 minutes.

[0277] In the thermal polymerization process, the heating temperature can be 60°C to 130°C, preferably 70°C to 120°C, and more preferably 80°C to 100°C. The heating time is not particularly limited, but can be, for example, 10 minutes to 4 hours.

[0278] The onium salt compounds, acid generators, polymerization initiators, reactive compositions, or polymers disclosed herein are not particularly limited in their applications and can be applied to various fields and products in which resin materials are used, and can be widely used in electrical and electronic materials, building, civil engineering, automotive, medical materials, and the like.

[0279] For example, in electrical and electronic materials applications, examples include adhesives, encapsulants (semiconductor encapsulants), sealants, insulating materials, thermally conductive materials, hot melt materials, paints, and potting agents. More specifically, examples include encapsulating materials for electronic components such as printed circuit boards, copper foil, copper-clad laminates, interlayer insulating materials, wiring coating films, resin-coated copper foil (RCC), and prepregs; layer-forming materials; materials for forming display devices such as color filters, flexible display films, resist materials, solder resist inks, and alignment films; materials for forming semiconductor devices such as resist materials and buffer coat films; and materials for forming optical components such as holograms, optical waveguides, optical circuits, optical circuit components, and anti-reflective films. As an optical component, it can be used, for example, as an adhesive for camera modules, LiDAR modules (light detection and ranging, detection and distance measurement using light (including laser or infrared)), lens materials for still cameras, finder prisms, target prisms, finder covers, light receiving sensor parts, photographic lenses, projection lenses for projection televisions, etc.

[0280] Examples of materials used in construction include, for example, sealants, coatings, and primers for joints of exterior materials such as various metal panels and siding boards; sealants, adhesives, injection materials, vibration damping materials, soundproofing materials, conductive materials for electromagnetic shielding, and putty materials used between exterior materials, substrates, ceiling materials, and interior materials; adhesives for bonding tiles and stone materials to exterior wall materials and substrates; adhesives and sealants for bonding wood flooring materials, polymer-based floor sheets, and floor tiles to various types of flooring; and injection materials for repairing cracks in various exterior and interior materials.

[0281] Examples of materials used in civil engineering include sealants, coatings, primers, paints, injection materials, putties, mold fillers, and spray materials for joints in roads, bridges, tunnels, breakwaters, and various concrete products.

[0282] Examples of materials used in automotive applications include sealants, coatings, cushioning materials, vibration damping materials, soundproofing materials, and spray materials for automobile bodies; adhesives, bonding agents, coatings, and foaming agents for automobile interiors; sealants and bonding agents for automobile parts; and sealants, bonding agents, and coatings for various steel plate joints in trucks, buses, etc.

[0283] Examples of applications in medical materials include medical rubber materials, medical adhesives, and medical device sealing materials. [Examples]

[0284] Examples and comparative examples of the present invention will be described below in detail. However, the present invention is not limited to these examples.

[0285] <Method for producing onium salt compounds>

[0286] Example 1 [ka]

[0287] Compound (1-1) of Example 1 was prepared by following steps 1, 2, and 3 below. [ka]

[0288] In a 100 ml four-necked flask, 4.0 g (33.5 mmol) of 2-mercaptothiazoline (2-1), 30 ml of ethyl acetate, 4.24 g (33.5 mmol) of benzyl chloride (3-1), and 1.87 g (33.5 mmol) of potassium hydroxide were placed and the mixture was stirred at 60°C for 24 hours. 30 ml of water was added to the resulting reaction mixture, and the organic layer was separated by liquid-liquid extraction. The resulting residue was concentrated to obtain intermediate compound (4-1).

[0289] [ka]

[0290] In a 100 ml four-necked flask, the obtained intermediate compound (4-1), 4.23 g (33.4 mmol) of dimethyl sulfate (5-1), and 10 ml of acetonitrile were placed and stirred at 50°C for 48 hours. To the resulting reaction mixture, 100 ml of water and 20 ml of ethyl acetate were added, and the aqueous layer containing intermediate compound (6-1) was separated by liquid-liquid extraction.

[0291] [ka]

[0292] In a 500 ml four-necked flask, the solution containing the obtained intermediate compound (6-1), 211 g of a 10% aqueous solution of tetrakis(pentafluorophenyl)borate sodium salt (7-1), and 100 ml of ethyl acetate were added and the mixture was stirred at 25°C for 2 hours. The organic layer of the resulting reaction solution was separated by liquid-liquid extraction. By concentrating the resulting residue, the product compound (1-1) was obtained in 90% yield. As an internal standard, 1 In HNMR, tetramethylsilane (TMS) 19 In the 1F-NMR spectrum, an appropriate amount of hexafluorobenzene was added.

[0293] 1 HNMR(400MHz,CD3CN)δ7.51~7.36(m,5H),4.59(s,2H),4.35(t,1H),3.66(t,1H),3.29(s,3H) 19 FNMR(376MHz,CD3CN)δ-132.12(s,2F),-162.30(t,1F),-166.72(t,2F)

[0294] Example 2 [ka]

[0295] Example 2 was synthesized using the same procedure as in Example 1, except that 2-mercaptothiazoline (2-1) in step 1 of Example 1 was replaced with 5.6 g (33.5 mmol) of 2-mercaptobenzothiazole (2-2). The yield of the resulting compound (1-2) was 86%.

[0296] 1 HNMR(400MHz,CD3CN)δ8.12(d,1H),7.94(d,1H),7.82(t,1H),7.70(t,1H),7.59(d,2H),7.50~7.37(m,3H),4.80(s,2H),4.04(s,3H) 19 FNMR(376MHz,CD3CN)δ-132.15(s,2F),-162.32(t,1F),-166.74(t,2F)

[0297] Example 3 [ka]

[0298] Example 3 was synthesized using the same procedure as in Example 2, except that benzyl chloride (3-1) in step 1 of Example 2 was replaced with 4.71 g of 4-methylbenzyl chloride (3-2). The yield of the resulting compounds (1-3) was 91%.

[0299] 1 HNMR(400MHz,CD3CN)δ8.13(d,1H),7.95(d,1H),7.82(t,1H),7.70(t,1H),7.46(d,2H),7.26(d,2H),4.76(s,2H),4.04(s,3H),2.34(s,3H) 19 FNMR(376MHz,CD3CN)δ-132.09(s,2F),-162.32(t,1F),-166.72(t,2F)

[0300] Example 4 [ka]

[0301] Example 4 was synthesized using the same procedure as in Example 2, except that benzyl chloride (3-1) in step 1 of Example 2 was replaced with 5.92 g of 1-(chloromethyl)naphthalene (3-3). The yield of the resulting compound (1-4) was 82%.

[0302] 1 HNMR(400MHz,CD3CN)δ8.18(t,2H),8.00(d,2H),7.94(d,1H),7.84(t,2H),7.72(t,1H),7.70~7.58(m,2H),7.54(t,1H),5.26(s,2H),4.01(s,3H) 19 FNMR(376MHz,CD3CN)δ-132.10(s,2F),-162.32(t,1F),-166.73(t,2F)

[0303] Example 5 [ka]

[0304] Example 5 was synthesized using the same procedure as in Example 2, except that benzyl chloride (3-1) in step 1 of Example 2 was replaced with 4.71 g of 2-phenylethyl chloride (3-4). The yield of the resulting compounds (1-5) was 90%.

[0305] 1 HNMR(400MHz,CD3CN)δ8.10(d,1H),7.92(d,1H),7.80(t,1H),7.68(t,1H),7.57(d,2H),7.48~7.35(m,3H),3.80(t,2H),3.40(t,2H),4.02(s,3H) 19 FNMR(376MHz,CD3CN)δ-132.13(s,2F),-162.33(t,1F),-166.73(t,2F)

[0306] Example 6 [ka]

[0307] Example 6 was synthesized using the same procedure as described in Example 2, except that benzyl chloride (3-1) in step 1 of Example 2 was replaced with 5.18 g of 2,4-dimethylbenzyl chloride (3-5). The yield of the resulting compounds (1-6) was 82%.

[0308] 1 HNMR(400MHz,CD3CN)δ8.16(d,1H),7.95(d,1H),7.83(t,1H),7.72(t,1H),7.40(d ,1H),7.14(s,1H),7.08(d,1H),4.76(s,2H),4.03(s,3H),2.43(s,3H),2.31(s,3H) 19 FNMR(376MHz,CD3CN)δ-132.09(s,2F),-162.32(t,1F),-166.73(t,2F)

[0309] Example 7 [ka]

[0310] Example 7 was synthesized using the same procedure as described in Example 2, except that benzyl chloride (3-1) in step 1 of Example 2 was replaced with 5.18 g of 3,4-dimethylbenzyl chloride (3-6). The yield of the resulting compounds (1-7) was 82%.

[0311] 1 HNMR(400MHz,CD3CN)δ8.12(d,1H),7.93(d,1H),7.82(t,1H),7.70(t,1H),7.34(s ,1H),7.29(d,1H),7.20(d,1H),4.73(s,2H),4.03(s,3H),2.27(s,3H),2.26(s,3H) 19FNMR(376MHz,CD3CN)δ-132.15(s,2F),-162.33(t,1F),-166.75(t,2F)

[0312] Example 8 [ka]

[0313] Example 8 was synthesized using the same procedure as described in Example 2, except that benzyl chloride (3-1) in step 1 of Example 2 was replaced with 5.1 g of 4-vinylbenzyl chloride (3-7). The yield of the resulting compounds (1-8) was 82%.

[0314] 1 HNMR(400MHz,CD3CN)δ8.14(d,1H),7.96(d,1H),7.82(t,1H),7.70(t,1H),7.45(d, 2H),7.22(d,2H),6.64(dd,1H),5.71(d,1H),5.25(d,1H),4.72(s,2H),4.04(s,3H) 19 FNMR(376MHz,CD3CN)δ-132.09(s,2F),-162.33(t,1F),-166.72(t,2F)

[0315] Example 9 [ka]

[0316] Example 9 was synthesized using the same procedure as in Example 2, except that the 10% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (7-1) in step 3 of Example 2 was replaced with 29.69 g of sodium tetrakis(3,5-ditrifluoromethylphenyl)borate (7-2). The yield of the resulting compounds (1-9) was 82%.

[0317] 1HNMR(400MHz,CD3CN)δ8.14(d,1H),7.95(d,1H),7.82(t,1H),7.73(s,8H),7.7 0(t,1H),7.68(s,4H),7.61(d,2H),7.51~7.36(m,3H),4.82(s,2H),4.06(s,3H) 19 FNMR (376 MHz, CD3CN) δ-61.91(s)

[0318] Example 10 [ka]

[0319] Example 10 was synthesized using the same procedure as described in Example 2, except that the 10% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (7-1) in step 3 of Example 2 was replaced with 13.87 g of sodium tetrakis(4-fluoromethylphenyl)borate (7-3). The yield of the resulting compounds (1-10) was 85%.

[0320] 1 HNMR(400MHz,CD3CN)δ8.05(d,1H),7.87(d,1H),7.78(t,1H),7.66(t,1H),7.55(d,2) H),7.48~7.43(t,3H),7.22~7.11(m,8H),6.79~6.69(t,8H),4.72(s,2H,3.96(s,3H) 19 FNMR(376MHz,CD3CN)δ-122.98(s)

[0321] Example 11 [ka]

[0322] Example 11 was synthesized using the same procedure as in Example 2, except that the 10% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (7-1) in step 3 of Example 2 was replaced with 10.02 g of lithium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide (7-4). The yield of the resulting compound (1-11) was 85%.

[0323] 1 HNMR(400MHz,CD3CN)δ8.11(d,1H),7.93(d,1H),7.81(t,1H),7.69(t,1H),7.59(d,2H),7.50~7.39(m,3H),4.79(s,2H),4.03(s,3H) 19 FNMR(376MHz,CD3CN)δ-119.01(s,2F),-125.47(s,1F)

[0324] Example 12 [ka]

[0325] Example 12 was synthesized using the same procedure as described in Example 2, except that the 10% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (7-1) in step 3 of Example 2 was replaced with 15.0 g of potassium tris(trifluoromethanesulfonyl)methanide (7-5). The yield of the resulting compound (1-12) was 81%.

[0326] 1 HNMR(400MHz,CD3CN)δ8.12(d,1H),7.94(d,1H),7.81(t,1H),7.70(t,1H),7.59(d,2H),7.50~7.39(m,3H),4.79(s,2H),4.03(s,3H) 19 FNMR (376 MHz, CD3CN) δ-75.96 (s)

[0327] Example 13 [ka]

[0328] Example 13 was synthesized using the same procedure as in Example 3, except that the 10% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (7-1) in step 3 of Example 3 was replaced with 10.02 g of lithium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide (7-4). The yield of the resulting compound (1-13) was 81%.

[0329] 1 HNMR(400MHz,CD3CN)δ8.12(d,1H),7.94(d,1H),7.82(t,1H),7.70(t,1H),7.47(d,2H),7.27(d,2H),4.76(s,2H),4.03(s,3H),2.35(s,3H) 19 FNMR(376MHz,CD3CN)δ-119.02(s,2F),-125.48(s,1F)

[0330] Example 14 [ka]

[0331] Example 14 was synthesized using the same procedure as in Example 3, except that the 10% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (7-1) in step 3 of Example 3 was replaced with 29.69 g of sodium tetrakis(3,5-ditrifluoromethylphenyl)borate (7-2). The yield of the resulting compound (1-14) was 82%.

[0332] 1 HNMR(400MHz,CD3CN)δ8.13(d,1H),7.95(d,1H),7.82(t,1H),7.74(s,8H),7.70(t ,1H),7.68(s,4H),7.48(d,2H),7.27(d,2H),4.78(s,2H),4.05(s,3H),2.35(s,3H) 19 FNMR (376 MHz, CD3CN) δ-61.68 (s)

[0333] Example 15 [ka]

[0334] Example 15 was synthesized using the same procedure as in Example 2, except that 4.23 g (33.4 mmol) of dimethyl(5-1) sulfate in step 2 of Example 2 was replaced with 5.17 g of diethyl(5-2) sulfate. The yield of the resulting compound (1-15) was 78%.

[0335] 1 HNMR(400MHz,CD3CN)δ8.14(d,1H),7.98(d,1H),7.82(t,1H),7.70(t,1H),7.60(d,2H),7.50~7.39(m,3H),4.81(s, 2H),4.60(q,2H),1.50(t,3H) 19 FNMR(376MHz,CD3CN)δ-132.11(s,2F),-162.33(t,1F),-166.74(t,2F)

[0336] Example 16 [ka]

[0337] Example 16 was synthesized using the same procedure as in Example 2, except that benzyl chloride (3-1) in step 1 of Example 2 was replaced with 5.71 g of 1-adamantyl chloride (3-8). The yield of the resulting compound (1-16) was 71%.

[0338] 1HNMR(400MHz,CD3CN)δ8.16(d,1H),8.03(d,1H),7.87(t,1H),7.77(t,1H),4.14(s,3H),2.32(s,6H),2.21(s,3H),1.80(s,6H) 19 FNMR(376MHz,CD3CN)δ-132.17(s,2F),-162.33(t,1F),-166.74(t,2F)

[0339] Example 17 [ka]

[0340] Example 17 was synthesized using the same procedure as in Example 2, except that benzyl chloride (3-1) in step 1 of Example 2 was replaced with 3.5 g of cyclopentyl chloride (3-9). The yield of the resulting compound (1-17) was 70%.

[0341] 1 HNMR(400MHz,CD3CN)δ8.15(d,1H),7.94(d,1H),7.82(t,1H),7.71(t,1H),4.25~4.11(m,1H),4.01(s,3H),2.48~2.43(m,2H),1.93~1.75(m,6H) 19 FNMR(376MHz,CD3CN)δ-132.11(s,2F),-162.32(t,1F),-166.73(t,2F)

[0342] Example 18 [ka]

[0343] Example 18 was synthesized using the same procedure as in Example 17, except that the 10% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (7-1) in step 3 of Example 17 was replaced with 10.02 g of lithium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide (7-4). The yield of the resulting compound (1-18) was 72%.

[0344] 1 HNMR(400MHz,CD3CN)δ8.15(d,1H),7.94(d,1H),7.82(t,1H),7.71(t,1H),4.23~4.13(m,1H),4.00(s,3H),2.51~2.38(m,2H),1.94~1.75(m,6H) 19 FNMR(376MHz,CD3CN)δ-119.01(s,2F),-125.46(s,1F)

[0345] Example 19 [ka]

[0346] Example 19 was synthesized using the same procedure as in Example 17, except that the 10% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (7-1) in step 3 of Example 17 was replaced with 29.69 g of sodium tetrakis(3,5-ditrifluoromethylphenyl)borate (7-2). The yield of the resulting compounds (1-19) was 73%.

[0347] 1 HNMR(400MHz,CD3CN)δ8.15(d,1H),7.95(d,1H),7.83(t,1H),7.73~7.68(m ,13H),4.24~4.14(m,1H),4.02(s,3H),2.51~2.37(m,2H),1.92~1.74(m,6H) 19 FNMR (376 MHz, CD3CN) δ-61.67 (s)

[0348] Example 20 [ka]

[0349] Example 20 was synthesized using the same procedure as in Example 2, except that benzyl chloride (3-1) in step 3 of Example 2 was replaced with 2.55 g of allyl chloride (3-10). The yield of the resulting compound (1-20) was 79%.

[0350] 1 HNMR(400MHz,CD3CN)δ8.15(d,1H),7.96(d,1H),7.83(t,1H),7.71(t,1H),6.08~5.98(m,1H),5.66(d,1H),5.49(d,1H),4.23(d,2H),4.06(s,3H) 19 FNMR(376MHz,CD3CN)δ-132.16(s,2F),-162.32(t,1F),-166.72(t,2F)

[0351] Example 21 [ka]

[0352] Example 21 was synthesized using the same procedure as in Example 2, except that benzyl chloride (3-1) in step 3 of Example 2 was replaced with 5.1 g of cinnamil chloride (3-11). The yield of the resulting compound (1-21) was 75%.

[0353] 1 HNMR(400MHz,CD3CN)δ8.14(d,1H),7.95(d,1H),7.82(t,1H),7.70(t,1H),7.47(d ,2H),7.38~7.34(m,3H),7.00(d,1H),6.42~6.34(m,1H),4.40(d,2H),4.05(s,3H) 19FNMR(376MHz,CD3CN)δ-132.13(s,2F),-162.32(t,1F),-166.73(t,2F)

[0354] Example 22 [ka]

[0355] Example 22 was synthesized using the same procedure as in Example 21, except that the 10% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (7-1) in step 3 of Example 21 was replaced with 10.02 g of lithium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide (7-4). The yield of the resulting compound (1-22) was 77%.

[0356] 1 HNMR(400MHz,CD3CN)δ8.13(d,1H),7.94(d,1H),7.81(t,1H),7.70(t,1H),7.48(d ,2H),7.41~7.28(m,3H),6.99(d,1H),6.42~6.34(m,1H),4.39(d,2H),4.04(s,3H) 19 FNMR(376MHz,CD3CN)δ-119.01(s,2F),-125.47(s,1F)

[0357] Example 23 [ka]

[0358] Example 23 was synthesized using the same procedure as in Example 21, except that the 10% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (7-1) in step 3 of Example 21 was replaced with 29.69 g of sodium tetrakis(3,5-ditrifluoromethylphenyl)borate (7-2). The yield of the resulting compound (1-23) was 76%.

[0359] 1 HNMR(400MHz,CD3CN)δ8.15(d,1H),7.95(d,1H),7.82(t,1H),7.78~7.61(m,13H),7.5 0(d,2H),7.41~7.27(m,3H),7.02(d,1H),6.48~6.34(m,1H),4.42(d,2H),4.07(s,3H) 19 FNMR (376 MHz, CD3CN) δ-61.68 (s)

[0360] Example 24 [ka]

[0361] Example 24 was synthesized using the same procedure as described in Example 2, except that benzyl chloride (3-1) in step 1 of Example 2 was replaced with 3.02 g of 3-chloro-1-butene (3-12). The yield of the resulting compound (1-24) was 70%.

[0362] 1 HNMR(400MHz,CD3CN)δ8.14(d,1H),7.96(d,1H),7.83(t,1H),7.72(t,1H),6.04~5 .97(m,1H),5.62(d,1H),5.43(d,1H),4.61~4.49(m,1H),4.05(s,3H),1.72(d,3H) 19 FNMR(376MHz,CD3CN)δ-132.04(s,2F),-162.32(t,1F),-166.71(t,2F)

[0363] Example 25 [ka]

[0364] Example 25 was synthesized using the same procedure as in Example 24, except that the 10% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (7-1) in step 3 of Example 24 was replaced with 10.02 g of lithium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide (7-4). The yield of the resulting compound (1-25) was 71%.

[0365] 1 HNMR(400MHz,CD3CN)δ8.14(d,1H),7.95(d,1H),7.82(t,2H),7.71(t,2H),6.05~5 .99(m,1H),5.63(d,1H),5.44(d,1H),4.57~4.53(m,1H),4.04(s,3H),1.72(d,3H) 19 FNMR(376MHz,CD3CN)δ-119.01(s,2F),-125.47(s,1F)

[0366] Example 26 [ka]

[0367] Example 26 was synthesized using the same procedure as in Example 24, except that the 10% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (7-1) in step 3 of Example 24 was replaced with 29.69 g of sodium tetrakis(3,5-ditrifluoromethylphenyl)borate (7-2). The yield of the resulting compound (1-26) was 75%.

[0368] 1 HNMR(400MHz,CD3CN)δ8.15(d,1H),7.96(d,1H),7.83(t,1H),7.76~7.66(m,13H),6.0 5~5.98(m,1H),5.63(d,1H),5.44(d,1H),4.58~4.54(m,1H),4.05(s,3H),1.72(d,3H) 19 FNMR (376 MHz, CD3CN) δ-61.67 (s)

[0369] Example 27 [ka]

[0370] Example 27 was synthesized using the same procedure as in Example 2, except that benzyl chloride (3-1) in step 1 of Example 2 was replaced with 4.1 g of (trimethylsilyl)methyl chloride (3-13). The yield of the resulting compound (1-27) was 76%.

[0371] 1 HNMR(400MHz,CD3CN)δ8.14(d,1H),7.92(d,1H),7.82(t,1H),7.69(t,1H),5.20(s,2H),4.03(s,3H),0.29(s,9H) 19 FNMR(376MHz,CD3CN)δ-132.05(s,2F),-162.33(t,1F),-166.72(t,2F)

[0372] Example 28 [ka]

[0373] Example 28 was synthesized using the same procedure as in Example 2, except that benzyl chloride (3-1) in step 1 of Example 2 was replaced with 5.3 g of chloromethylphenyl sulfide (3-14). The yield of the resulting compound (1-28) was 59%.

[0374] 1 HNMR(400MHz,CD3CN)δ8.16(d,1H),7.95(d,1H),7.83(t,1H),7.71(t,1H), 7.69~7.55(m,2H),7.43~7.35(m,2H),7.28(d,1H),4.04(s,2H),3.04(s,3H) 19FNMR(376MHz,CD3CN)δ-132.18(s,2F),-162.37(t,1F),-166.80(t,2F)

[0375] Example 29 [ka]

[0376] Example 29 was synthesized using the same procedure as in Example 2, except that benzyl chloride (3-1) in step 1 of Example 2 was replaced with 5.78 g of N-phenylmaleimide (3-15). The yield of the resulting compound (1-29) was 75%.

[0377] 1 HNMR(400MHz,CD3CN)δ8.21(d,1H),8.02(d,1H),7.89(t,1H),7.78(t,1H),7.59~7.49(m,5H),5.10(d,1H),4.04(s,3H),3.64(d,1H),3.13(m,1H) 19 FNMR(376MHz,CD3CN)δ-132.10(s,2F),-162.33(t,1F),-166.75(t,2F)

[0378] Example 30 [ka]

[0379] Example 30 was synthesized using the same procedure as described in Example 2, except that benzyl chloride (3-1) in step 1 of Example 2 was replaced with 3.56 g of 1-chloropentane (3-16). The yield of the resulting compound (1-30) was 90%.

[0380] 1HNMR(400MHz,CD3CN)δ8.15(d,1H),7.95(d,1H),7.83(t,1H),7.70(t,1H),4.04(s,3 H),3.54(t,2H),2.02~1.91(m,2H),1.61~1.47(m,2H),1.45~1.38(m,2H),0.94(t,3H) 19 FNMR(376MHz,CD3CN)δ-132.07(s,2F),-162.32(t,1F),-166.71(t,2F)

[0381] Example 31 [ka]

[0382] Example 31 was synthesized using the same procedure as in Example 2, except that benzyl chloride (3-1) in step 1 of Example 2 was replaced with indene (3-17) 3.88 g, potassium hydroxide 1.87 g was replaced with trifluoroacetic acid 7.62 g, and toluene was replaced with dichloromethane. The yield of the resulting compound (1-31) was 70%.

[0383] 1 HNMR(400MHz,CD3CN)δ8.30(d,1H),8.12(d,1H),7.94(t,1H),7.83(t,1H),7.53~7.41(m,2H ),7.38(d,1H),7.28(t,1H),6.88(d,1H),5.81(t,1H),4.04(s,3H),3.70(d,1H),3.04(s,2H) 19 FNMR(376MHz,CD3CN)δ-132.13(s,2F),-162.34(t,1F),-166.76(t,2F)

[0384] Example 32 [ka]

[0385] Example 32 was synthesized using the same procedure as described in Example 2, except that 5.6 g of 2-mercaptobenzothiazole (2-2) in step 1 of Example 2 was replaced with 6.05 g of 4-methyl-2-mercaptobenzothiazole (2-3). The yield of the resulting compound (1-32) was 87%.

[0386] 1 HNMR(400MHz,CD3CN)δ7.95~7.92(m,1H),7.62~7.51(m,4H),7.49~7.39(m,3H),4.78(s,2H),4.28(s,3H),2.87(s,3H) 19 FNMR(376MHz,CD3CN)δ-132.13(s,2F),-162.32(t,1F),-166.73(t,2F)

[0387] Example 33 [ka]

[0388] Example 33 was synthesized using the same procedure as described in Example 2, except that benzyl chloride (3-1) in step 1 of Example 2 was replaced with 3.89 g of 3-chlorocyclohexene (3-18). The yield of the resulting compound (1-33) was 67%.

[0389] 1 HNMR(400MHz,CD3CN)δ8.15(d,1H),7.97(d,1H),7.85(t,1H),7.72(t,1H),5.99~5.93(m ,1H),5.52(m,1H),4.59~4.47(m,1H),4.04(s,3H),3.01(m,2H),1.62(m,2H),1.42(m,2H) 19 FNMR(376MHz,CD3CN)δ-132.03(s,2F),-162.33(t,1F),-166.71(t,2F)

[0390] Comparative Example 1: Compound described in Patent Document 6 (Japanese Patent Publication No. 07-025863) [ka]

[0391] Comparative Example 1 was synthesized using the same procedure as in Example 2, except that the 10% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (7-1) in step 3 of Example 2 was replaced with 8.66 g of sodium hexafluoroantimonate. The yield of comparative compound (a1) was 82%.

[0392] 1 HNMR(400MHz,CD3CN)δ8.12(d,1H),7.94(d,1H),7.82(t,1H),7.70(t,1H),7.59(d,2H),7.50~7.40(m,3H),4.79(s,2H),4.03(s,3H) 19 FNMR(376MHz,CD3CN)δ-109.35~-135.11(m)

[0393] Comparative Example 2: Compound described in Patent Document 6 (Japanese Patent Publication No. 07-025863) [ka]

[0394] Comparative Example 2 was synthesized using the same procedure as in Example 2, except that the 10% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (7-1) in step 3 of Example 2 was replaced with 3.67 g of sodium tetrafluoroboro. The yield of comparative compound (a2) was 89%.

[0395] 1 HNMR(400MHz,CD3CN)δ8.13(d,1H),7.95(d,1H),7.82(t,1H),7.70(t,1H),7.60(dd,2H),7.50~7.40(m,3H),4.80(s,2H),4.04(s,3H) 19 FNMR(376MHz,CD3CN)δ-150.12(s)

[0396] Comparative Example 3: Compound described in Patent Document 6 (Japanese Patent Publication No. 07-025863) [ka]

[0397] Comparative Example 3 was synthesized using the same procedure as in Example 2, except that the 10% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (7-1) in step 3 of Example 2 was replaced with 5.61 g of sodium hexafluorophosphate. The yield of comparative compound (a3) ​​was 90%.

[0398] 1 HNMR(400MHz,CD3CN)δ8.12(d,1H),7.94(d,1H),7.82(t,1H),7.70(t,1H),7.59(d,2H),7.50~7.40(m,3H),4.79(s,2H),4.03(s,3H) 19 FNMR (376 MHz, CD3CN) δ-72.20 (s)

[0399] Comparative Example 4 [ka]

[0400] Comparative Example 4 was synthesized using the same procedure as in Example 2, except that the 10% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (7-1) in step 3 of Example 2 was replaced with 5.75 g of sodium triflate. The yield of comparative compound (a4) was 88%.

[0401] 1 HNMR(400MHz,CD3CN)δ8.14(d,1H),7.97(d,2H),7.82(t,1H),7.70(t,1H),7.60(dd,2H),7.50~7.39(m,3H),4.80(s,2H),4.04(s,3H) 19 FNMR (376 MHz, CD3CN) δ-77.67 (s)

[0402] Comparative Example 5 [ka]

[0403] Comparative Example 5 was synthesized using the same procedure as in Example 2, except that the 10% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (7-1) in step 3 of Example 2 was replaced with 11.43 g of sodium tetraphenylboro. The yield of comparative compound (a5) was 90%.

[0404] 1 HNMR(400MHz,CD3CN)δ7.97(d,1H),7.82~7.70(m,2H),7.63(t,1H),7.53(d,2H),7.4 7~7.37(m,3H),7.30~7.26(m,8H),6.96(t,8H),6.81(t,4H),4.65(s,2H),3.84(s,3H)

[0405] Comparative Example 6 [ka]

[0406] Comparative Example 6 was synthesized using the same procedure as in Example 2, except that the 10% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (7-1) in step 3 of Example 2 was replaced with 9.59 g of lithium bis(trifluoromethanesulfonyl)imide. The yield of comparative compound (a6) was 84%.

[0407] 1 HNMR(400MHz,CD3CN)δ8.12(d,1H),7.94(d,1H),7.82(t,1H),7.70(t,1H),7.59(d,2H),7.50~7.39(m,3H),4.79(s,2H),4.04(s,3H) 19 FNMR (376 MHz, CD3CN) δ-78.59 (s)

[0408] Evaluation test of onium salt compounds <Solvent compatibility> At 25°C, 1 g of either the onium salt compounds from Examples 1-33 or Comparative Examples 1-6 was placed in each 30 mL screw-cap tube. Then, 1 g of solvent was added to each container and mixed using a rotation-and-revolution type mixer "ARE-310" manufactured by Thinky Co., Ltd. The mass Ws (g) of solvent required for the onium salt compound to completely dissolve was measured.

[0409] The solubility (S), which is the mass of solute that can be dissolved in 100 g of solvent, was determined according to the following formula. Formula: S[%] = 1 / (Ws / 100) Table 1 shows that solubility when dissolved in 1 g of solvent is indicated as ">100", and solubility when it does not completely dissolve even when 200 g of solvent is added is indicated as ">0.5".

[0410] Solvent compatibility was evaluated by counting the number of solvents in which the solubility was 1% or more in the solvents measured in this study, and assigning points as follows. 5: There are 6 or more solvents with a solubility of 1% or more. 4: There are five types of solvents that have a solubility of 1% or more. 3: There are four types of solvents that have a solubility of 1% or more. 2: There are three types of solvents that have a solubility of 1% or more. 1: There are two types of solvents that have a solubility of 1% or more. 0: The number of solvents with a solubility of 1% or more is 1.

[0411] The following six solvents were selected. • Propylene carbonate Methyl isobutyl ketone • PGMAc (Propylene glycol 1-monomethyl ether 2-acetate) ·toluene • Ceroxide (registered trademark) 2021P • jER(registered trademark)828

[0412] The choice of solvent was based on the Hansen solubility parameter. Compounds with similar SP values ​​tend to be mutually compatible, and generally, higher SP values ​​indicate greater polarity. The solvents were selected to allow for the investigation of a wide range of solubility, from low to high SP values. For reference, the SP value of PC is 13.3 (MPa). 1 / 2 ), MIBK's SP value is 8.3 (MPa) 1 / 2 ), the SP value of toluene is 8.9 (MPa). 1 / 2 )

[0413] The aforementioned celloxide 2021P is 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexanecarboxylate.

[0414] The aforementioned jER828 is a so-called bisphenol A type epoxy resin produced by a condensation reaction between bisphenol A and epichlorohydrin.

[0415] <Storage stability> The onium salt compounds prepared in Examples 1-33 or Comparative Examples 1-6 were each placed in 30 mL light-shielding screw-cap tubes and left standing in a 25°C constant temperature bath. At regular intervals, the screw-cap tubes were tilted on their sides for 1 minute, and the number of days until the liquid stopped flowing was measured to determine gelation.

[0416] (5-point rating scale) 5. The solution has stopped flowing for 40 days or more. 4. The number of days since the solution stopped flowing is 30 to 39 days. 3. The number of days since the solution stopped flowing is 20 to 29 days. 2: The number of days since the solution stopped flowing is 10 to 19 days. 1: The number of days since the solution stopped flowing is within 9 days.

[0417] Evaluation test of reactive compositions containing onium salt compounds The reactive compositions described herein were prepared based on the following manufacturing methods. The photoreactivity and thermal reactivity of these reactive compositions were evaluated as follows.

[0418] <Example 1 of production of reactive composition> 20.0 mg of the onium salt compounds from Examples 1-33 or Comparative Examples 1-6 were added to each 10 mL light-shielding screw tube, along with 0.2 mg of 4-hydroxyphenyl)dimethylsulfonium triflate (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: DSP-Tf) as a polymerization inhibitor. Then, 20.0 mg of propylene carbonate was added to each container as a solvent and the mixture was completely dissolved to prepare Solution 1. Furthermore, 20.1 mg of the prepared solution 1 was placed in each of the 30 mL light-shielding screw tubes. In addition, 10 g of celoxide 2021P (trade name, manufactured by Daicel Corporation) was added to the container as a reactive compound, and the mixture was immediately mixed using the ARE-310 rotary-orbit mixer to prepare the reactive composition.

[0419] <Photoreactivity (1)> The prepared reactive compositions were subjected to UV-DSC measurements, and the total heat generated was measured by continuous light irradiation. A higher total heat generated indicates higher photoreactivity. (conditions) • Measuring instrument: Differential scanning calorimeter (DSC600, manufactured by Hitachi High-Tech Corporation) • Atmosphere: Nitrogen gas, 50 mL / min. • Lamp: LA-410UV, mercury xenon lamp • Sample amount: 1 mg ·Illuminance: 20mW / cm 2 (313nm) ·Measurement temperature: 25℃ • Total heat generation (J / g): The sum of the heat generated during light irradiation (W / g).

[0420] (evaluation) The photoreactivity was evaluated in two stages, as described below. A: Total calorific value is 1 J / g or more B: Total calorific value is less than 1 J / g The results are shown in Table 1.

[0421] <Thermal Reactivity (1)> The thermal properties of the prepared reactive compositions were measured using a differential scanning calorimetry (DSC). Note that a lower reaction temperature indicates higher thermal reactivity. (conditions) • Measuring instrument: Differential scanning calorimeter (X-DSC7000, manufactured by Hitachi High-Tech Corporation) • Atmosphere: Nitrogen gas, 40 mL / min. • Sample amount: 5mg ·Temperature conditions: 30~310℃, 10℃ / min. • Reaction temperature (°C): The temperature at the peak of the exothermic peak that appeared on the lowest temperature side among the exothermic peaks.

[0422] (evaluation) The thermal reactivity described above was evaluated using a two-stage assessment, as follows. A: Reaction temperature is less than 200°C B: Reaction temperature is 200°C or higher The results are shown in Table 1.

[0423] <Example 2 of production of reactive composition> 20.0 mg of the onium salt compounds from Examples 1-33 or Comparative Examples 1-6 were added to each 10 mL light-shielding screw tube. Then, 20.0 mg of propylene carbonate was added to each container as a solvent. The compounds were completely dissolved to prepare each solution 2. Furthermore, 20.0 mg of the prepared solution 2 was placed in each 30 mL light-shielding screw tube. In addition, 10 g of trimethylolpropane acrylate (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the container as a reactive compound, and the mixture was immediately mixed using the ARE-310 rotary-orbit mixer to prepare the reactive composition.

[0424] <Photoreactivity (2)> The prepared reactive compositions were subjected to UV-DSC measurements, and the total heat generated was measured by continuous light irradiation. A higher total heat generated indicates higher photoreactivity. (conditions) • Measuring instrument: Differential scanning calorimeter (DSC600, manufactured by Hitachi High-Tech Corporation) • Atmosphere: Nitrogen gas, 50 mL / min. • Lamp: LA-410UV, mercury xenon lamp • Sample amount: 1 mg ·Illuminance: 20mW / cm 2 (313nm) ·Measurement temperature: 25℃ • Total heat generation (J / g): The sum of the heat generated during light irradiation (W / g).

[0425] (evaluation) The photoreactivity was evaluated in two stages, as described below. A: Total calorific value of 150 J / g or more B: Total calorific value is less than 150 J / g The results are shown in Table 1.

[0426] [Table 1]

[0427] <Result> The onium salt compounds of Examples 1 to 33 exhibited excellent solvent compatibility and storage stability. On the other hand, the onium salt compounds of Comparative Examples 1 to 6 showed inferiority in at least one of the following: solvent compatibility and storage stability. Furthermore, the reactive compositions containing the onium salt compounds of Examples 1 to 33 were found to exhibit excellent photoreactivity and thermal reactivity. Therefore, the reactive compositions containing the onium salt compounds of this disclosure, possessing both photoreactivity and thermal reactivity, were found to be usable as dual-type acid generators.

[0428] Examples 34-72 Furthermore, the compounds listed in Table 2 below were produced according to the manufacturing methods described in Examples 1 to 33 above. Representative examples of compounds represented by the general formula (1B-3) of this disclosure are shown in Tables 2 and 3, and representative examples of compounds represented by the general formula (1A-3) are shown in Table 4, but this disclosure is not limited to these. In the tables, "Me" represents a methyl group, "Bn" represents a benzyl group, and "Ph" represents a phenyl group.

[0429] [Table 2]

[0430] [Table 3]

[0431] [Table 4]

[0432] As described above, the onium salt compounds of this disclosure exhibit excellent solvent compatibility and storage stability. Furthermore, the reactive compositions containing the onium salt compounds of this disclosure are photoreactive and thermally reactive, making them suitable for use as dual-type acid generators. Furthermore, it was found that the onium salt compounds in this disclosure are photoreactive and can function not only as acid generators but also as radical generators. Therefore, the onium salt compounds of this disclosure can be applied to a variety of applications, such as adhesives, sealants, and resists.

Claims

1. General formula (1): 【Chemistry 1】 (In the formula, R Ａ This represents a optionally substituted C1-15 alkyl group, an optionally substituted C2-15 alkenyl group, an optionally substituted C2-15 alkynyl group, an optionally substituted 3-15 member saturated or unsaturated carbocyclic group, or an optionally substituted heterocyclic group. R ４ This represents a hydrogen atom, a optionally substituted C1-15 alkyl group, an optionally substituted C2-15 alkenyl group, an optionally substituted C2-15 alkynyl group, an optionally substituted 3-15 member saturated or unsaturated carbocyclic group, an optionally substituted C1-15 alkylcarbonyl group, a optionally substituted 3-15 member saturated or unsaturated carbocyclic carbonyl group, an optionally substituted C1-15 alkoxycarbonyl group, an optionally substituted 3-15 member saturated or unsaturated carbocyclic oxycarbonyl group, an optionally substituted aminocarbonyl group, or a carboxyl group. R ５ and R ６ These are identical or different hydrogen atoms, halogen atoms, nitro groups, cyano groups, optionally substituted C1-15 alkyl groups, optionally substituted C2-15 alkenyl groups, optionally substituted C2-15 alkynyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring groups, optionally substituted C1-15 alkoxy groups, optionally substituted 3-15 member saturated or unsaturated carbon ring oxy groups, optionally substituted C1-15 alkylcarbonyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring carbonyl groups, optionally substituted C1-15 alkoxycarbonyl groups, and substituted This may represent an oxycarbonyl group having a 3-15 member saturated or unsaturated carbon ring, an optionally substituted aminocarbonyl group, a carboxyl group, an optionally substituted amino group, an optionally substituted C1-15 alkylthio group, an optionally substituted thio group having a 3-15 member saturated or unsaturated carbon ring, an optionally substituted C1-15 alkylsulfinyl group, an optionally substituted sulfinyl group having a 3-15 member saturated or unsaturated carbon ring, an optionally substituted C1-15 alkylsulfonyl group, an optionally substituted sulfonyl group having a 3-15 member saturated or unsaturated carbon ring, or an optionally substituted heterocyclic group; Alternatively, the aforementioned R ５ and R ６ These two groups may bond to each other with adjacent carbon atoms to form a saturated or unsaturated carbon ring. The saturated or unsaturated carbon ring may further have substituents. The dotted lines indicate single or double bonds. X － This refers to a boron anion containing a fluorine-containing aromatic ring, a gallium anion containing a fluorine-containing aromatic ring, a carbon anion containing a fluorine-containing sulfonyl group, a cyclic sulfonimide anion having a fluorine atom, or a phosphorus anion containing a fluorine-containing alkyl group. An onium salt compound represented by [the specified symbol].

2. The above-mentioned R Ａ is represented by the following general formula (1-R Ａ ): 【Chemistry 2】 【change】 (In the formula, R １ This includes hydrogen atoms, halogen atoms, nitro groups, cyano groups, optionally substituted C1-15 alkyl groups, optionally substituted C2-15 alkenyl groups, optionally substituted C2-15 alkynyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring groups, optionally substituted C1-15 alkoxy groups, optionally substituted C1-15 alkylcarbonyl groups, optionally substituted carbonyl groups having saturated or unsaturated carbon rings with 3-15 members, optionally substituted C1-15 alkoxycarbonyl groups, and optionally substituted oxycarbonyl groups having saturated or unsaturated carbon rings with 3-15 members. This represents a group, an optionally substituted aminocarbonyl group, a carboxyl group, an optionally substituted amino group, an optionally substituted C1-15 alkylthio group, an optionally substituted thio group having an optionally substituted 3-15 member saturated or unsaturated carbon ring, an optionally substituted C1-15 alkylsulfinyl group, an optionally substituted 3-15 member saturated or unsaturated carbon ring, an optionally substituted C1-15 alkylsulfonyl group, an optionally substituted 3-15 member saturated or unsaturated carbon ring, an optionally substituted heterocyclic group, or an optionally substituted silyl group. R ２ This represents a hydrogen atom, a halogen atom, an optionally substituted C1-15 alkyl group, an optionally substituted C2-15 alkenyl group, an optionally substituted 3-15 member saturated or unsaturated carbocyclic group, or an optionally substituted heterocyclic group. R ３ This represents a hydrogen atom, a halogen atom, a C1-15 alkyl group which may have substituents, or a saturated or unsaturated carbon ring group which may have substituents; Alternatively, the aforementioned R １ , R ２ and R ３ Of these, two or three adjacent groups may bond to each other to form a saturated or unsaturated carbon ring or a heterocycle. The saturated or unsaturated carbon ring or heterocycle may further have substituents. * indicates the bonding position with the sulfur atom in the general formula (1) above. The onium salt compound according to claim 1, wherein the group is represented by

3. The aforementioned R １ This includes hydrogen atoms, optionally substituted C1-15 alkyl groups, optionally substituted C2-15 alkenyl groups, optionally substituted C2-15 alkynyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring groups, optionally substituted C1-15 alkylcarbonyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring carbonyl groups, optionally substituted C1-15 alkoxycarbonyl groups, optionally substituted 3-15 member saturated or unsaturated carbon ring oxycarbonyl groups, and even if substituted... A good aminocarbonyl group, a carboxyl group, a C1-15 alkylthio group which may have substituents, a thio group having a 3-15 member saturated or unsaturated carbon ring which may have substituents, a C1-15 alkylsulfinyl group which may have substituents, a sulfinyl group having a 3-15 member saturated or unsaturated carbon ring which may have substituents, a C1-15 alkylsulfonyl group which may have substituents, a sulfonyl group having a 3-15 member saturated or unsaturated carbon ring which may have substituents, a heterocyclic group which may have substituents, or a silyl group which may have substituents; The aforementioned R ２ is a hydrogen atom, a C1-15 alkyl group which may have substituents, or a saturated or unsaturated carbon ring group which may have substituents; The aforementioned R ３ is a hydrogen atom, a C1-15 alkyl group which may have substituents, or a saturated or unsaturated carbon ring group which may have substituents; Alternatively, the aforementioned R １ , R ２ and R ３ The onium salt compound according to claim 2, wherein two or three adjacent groups may bond to each other to form a saturated or unsaturated carbon ring or heterocycle, and the saturated or unsaturated carbon ring or heterocycle may further have substituents.

4. The aforementioned X － The general formula is (XA1): － B(R) Ｘ１ ) a (R Ｘ２ ) The boron anion represented by b (In the formula, R Ｘ１ is a fluorine atom or C ｎ F ２ｎ＋１ R indicates the base. Ｘ２ This is an unsubstituted phenyl group, or a fluorine atom and C ｎ F ２ｎ＋１ This represents a phenyl group having at least one substituent selected from the group consisting of groups. n is an integer from 1 to 15. a is an integer from 0 to 3. b is an integer from 1 to 4. a + b is 4 (wherein the above R Ｘ２ If it is an unsubstituted phenyl group, then a represents an integer from 1 to 3. General formula (XC1): － C(R Ｘ５ ) (Caution Ｘ６ ) (Caution Ｘ７ ) Carbon anion (In the formula, R Ｘ５ , R Ｘ６ and R Ｘ７ C is the same or different. ｔ F ２ｔ＋１ A sulfonyl group having a group; or at least one C ｔ F ２ｔ＋１ This indicates a phenylsulfonyl group having a group. t is an integer from 1 to 15. ); or, General formula (XD1): 【Transformation 3】 The onium salt compound according to claim 1, which is a cyclic sulfonimide anion having a fluorine atom, represented by the formula (wherein r represents an integer from 1 to 6).

5. The aforementioned X － teeth, The following general formula (XA2): 【Chemistry 4】 (In the formula, R ３０ , R ３１ , R ３２ , R ３３ and R ３４ These are the same or different hydrogen atoms, fluorine atoms, or C ｎ F ２ｎ＋１ The base is shown. However, the R ３０ , R ３１ , R ３２ , R ３３ and R ３４ One of them is a fluorine atom or C ｎ F ２ｎ＋１ It is a boron anion represented by (where n is an integer from 1 to 15); The following general formula (XC2): 【Transformation 5】 (In the formula, R ４０ , R ４１ and R ４２ C is the same or different. ｔ F ２ｔ＋１ The base is shown. t is an integer from 1 to 15.) A carbon anion represented by ); or, General formula (XD1): 【Transformation 6】 The onium salt compound according to claim 1, which is a cyclic sulfonimide anion having a fluorine atom, represented by the formula (wherein r represents an integer from 1 to 6).

6. The aforementioned R ５ and R ６ The onium salt compound according to claim 1, wherein these two groups are bonded to each other with adjacent carbon atoms to form a saturated or unsaturated carbon ring, and the saturated or unsaturated carbon ring may further have substituents.

7. The aforementioned R ４ The onium salt compound according to claim 1, wherein is an unsubstituted C1-15 alkyl group.

8. An acid generator containing an onium salt compound according to any one of claims 1 to 7.

9. A polymerization initiator containing an onium salt compound according to any one of claims 1 to 7.

10. A reactive composition comprising an onium salt compound according to any one of claims 1 to 7 and a reactive compound.

11. A polymer obtained from the reactive composition described in claim 10.

12. An adhesive, encapsulant, or resist containing the reactive composition described in claim 10.

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