TWI871474B - Composition, cured product and method for producing cured product - Google Patents

Abstract

The present invention is a composition comprising a cyclic ether component, a thiol component, and a compound represented by the following general formula (1). Preferably, the content of the cyclic ether component is 20 parts by mass or more and 80 parts by mass or less in 100 parts by mass of the total of the cyclic ether component and the thiol component. Preferably, the content of the compound represented by the general formula (1) is 3 parts by mass or more and 15 parts by mass or less in 100 parts by mass of the total of the cyclic ether component, the thiol component, and the compound represented by the general formula (1). (The definitions of the symbols in the formula are in the instruction manual)

Description

Composition, cured product and method for producing cured product

The present invention relates to a composition, a cured product thereof and a method for producing the cured product.

Generally, a photosensitive resin composition is formed by adding a photopolymerization initiator to a photosensitive resin. It can be polymerized and cured or developed by irradiation with energy rays (light). Therefore, it is used in photocurable inks, photosensitive printing plates, various photoresists, photocurable adhesives, etc.

Photopolymerization initiators are classified into photoradical generators, photoacid generators, and photoalkali generators according to the different active species generated by irradiation with energy rays (light). Photoradical generators have the advantages of fast curing speed and no residual active species after curing. On the other hand, since oxygen will hinder curing, it has the disadvantage that an oxygen barrier layer must be set when curing the film. Photoacid generators have the advantage of not being hindered by oxygen. On the other hand, they have the disadvantages of corrosion of metal substrates or modification of resins after curing due to residual acids of active species. Photoalkali generators have attracted attention because they are not prone to the above-mentioned problems of curing inhibition caused by oxygen and corrosion caused by residual active species. As photoalkali generators, there are known ionic types (Patent Document 1) and non-ionic types (Patent Documents 2 and 3). [Prior Art Documents] [Patent Documents]

Patent document 1: WO98/38195A1 Patent document 2: US20110233048A1 Patent document 3: WO2010/064632 specification

[The problem the invention is trying to solve]

However, resin compositions containing ionic photoalkali generators have the disadvantage of low storage stability. In addition, conventional resin compositions containing photoalkali generators have the disadvantage of low flexibility in subsequent conditions such as high temperature heating required for curing after exposure.

The present invention is made in view of the above-mentioned problems, and aims to provide a curable composition with excellent storage stability and low-temperature adhesion. [Technical means to solve the problem]

The inventors of the present invention have conducted diligent research and found that by combining a specific base generating agent, a thiol component, and a cyclic ether component, both storage stability and low-temperature adhesion can be achieved, thereby completing the present invention.

That is, the present invention provides a composition comprising a cyclic ether component, a thiol component, and a compound represented by the following general formula (1). (wherein Ar is an aromatic ring group, A is a a pyridine skeleton, ^B- is a monovalent anion, ^R1 and ^R2 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic alkyl group, the aromatic alkyl group or the heterocyclic group are substituted with a divalent group selected from the following group I-1, and the substituent replacing one or more hydrogen atoms in the aliphatic alkyl group having a substituent, the aromatic alkyl group having a substituent and the heterocyclic group having a substituent is an atom or group selected from the following group II-1; Group I-1: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO ₂ -, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'-, or -SiR'R''-; Group II-1: halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH ₂ , -C(R')=N-OH, -COOH, or -SO ₃ H; R' and R'' independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group. When there are plural R' or R'', they may be the same or different)

The composition of the present invention has an excellent balance between storage stability and low-temperature adhesion.

In the present invention, the aromatic ring group Ar is preferably an aromatic ring group represented by the following general formula (Ara1), (Arb1) or (Arc1). The reason is that the above composition will have a better balance between storage stability and low-temperature adhesion.

[Chemistry 2] ₍ wherein, ^Y1 is a sulfur atom, CO, SO, _SO2 , ^CR1012 , ^PR102 or ^NR102 , ^Y2 is a single bond, an oxygen atom, a sulfur atom, CO, SO, SO2, _CR1022 ^{, PR102} _or ^NR101 , ^Y3 is an oxygen atom, a sulfur atom, CO, SO, _SO2 , ^{CR1022 , PR102} or ^NR101 , _R ¹⁰¹ each independently represents an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic alkyl group, the aromatic alkyl group or the heterocyclic group are substituted with a divalent group selected from the following group I-2, R ^R102 each independently represents a hydrogen atom, an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic alkyl group, the aromatic alkyl group or the heterocyclic group are substituted with a divalent group selected from the following group I-2; ^R31 , ^R32 , ^R41 , ^R42 , ^R51 , ^R52 and ^R53 each independently represent a halogen atom, a nitro group, a cyano group, ^-OR121 , ^-COR121 , ^-OCOR121 , ^-COOR121 , ^-SR121 , -SOR ¹²¹ , -SO ₂ R ¹²¹ , -NR ¹²² R ¹²³ , -NR ¹²² COR ¹²³ , -CONR ¹²² R ¹²³ , an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or one or more methylene groups in the aliphatic alkyl group, the aromatic alkyl group or the heterocyclic group are substituted with a divalent group selected from the following group I-2, However, a plurality of R ⁴¹ may be bonded to each other to form a ring, and the ring is unsubstituted or substituted, R ¹²¹ , R ¹²² and R ^R121 , R122 or R123 each independently represent a hydrogen atom, an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the above-mentioned aliphatic alkyl group, the above-mentioned aromatic alkyl group or the above-mentioned heterocyclic group are substituted with a divalent group selected from the following group I-2. When there are plural numbers of ^R121 , ^{R122 or R123, they may be the same or different. The above-mentioned aliphatic alkyl group having a substituent, the above-mentioned aromatic alkyl group having a substituent, the above-mentioned heterocyclic group having a substituent, and the plural numbers of R121, R122 or} R123 may be substituted with a divalent group selected from the following group I-2. The substituents of one or more hydrogen atoms in the ring formed by mutual bonding of ⁴¹ are atoms or groups selected from the following Group II-2, a1 is an integer of 0 to 5, a2 is an integer of 0 to 4, b1 is an integer of 0 to 4, b2 is an integer of 0 to 3, c1 is an integer of 0 to 4, c2 is an integer of 0 to 1, * represents a bonding site; Group I-2: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO ₂ -, -NR'-, -NR'--CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R''-; Group II-2: halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH ₂ , -C(R')=N-OH, -COOH or -SO ₃ H; R' and R'' each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group; when there are multiple R' or R'', they may be the same or different)

In the present invention, the content of the cyclic ether component is preferably 20 parts by mass or more and 80 parts by mass or less in 100 parts by mass of the total of the cyclic ether component and the thiol component. The reason for this is that the composition has a better balance between storage stability and low-temperature adhesion.

In the present invention, it is preferred that the content of the compound represented by the general formula (1) is 3 parts by mass or more and 15 parts by mass or less in the total of 100 parts by mass of the cyclic ether component, the thiol component and the compound represented by the general formula (1). The reason for this is that the composition has a better balance between storage stability and low-temperature adhesiveness.

In the present invention, it is preferred that the content of the compound represented by the general formula (1) is 5 parts by mass or more and 30 parts by mass or less in 100 parts by mass of the total of the thiol component and the compound represented by the general formula (1). The reason for this is that the above composition has a better balance between storage stability and low-temperature adhesion.

In the present invention, it is preferred that the cyclic ether component comprises an epoxy compound because the composition has a better balance between storage stability and low-temperature adhesion.

In the present invention, it is preferred that the epoxy compound comprises an aromatic epoxy compound because the composition has a better balance between storage stability and low-temperature adhesion.

In the present invention, it is preferred that the thiol component is a compound having two or more primary thiol groups, because the composition has a better balance between storage stability and low-temperature adhesion.

In the present invention, it is preferred that the composition contains a free radical polymerizable component because the composition has a better balance between storage stability and low-temperature adhesiveness, and can increase the degree of freedom of adhesive conditions.

The present invention provides a cured product of the above-mentioned composition. According to the present invention, the above-mentioned composition is used and thus becomes a product that can be sufficiently bonded without causing deterioration of surrounding components as required.

The present invention provides a method for manufacturing a hardened product having a hardening step of hardening a composition. According to the present invention, a hardened product that is formed using the above-mentioned composition can be obtained, which is in a desired state without causing deterioration of peripheral components. [Effect of the invention]

The present invention provides a composition having an excellent balance between storage stability and low-temperature adhesion, a cured product thereof, and a method for producing the cured product using the composition.

The present invention relates to a composition, a cured product using the composition and a method for producing the cured product.

A. Composition First, the composition of the present invention is described. The composition of the present invention comprises a cyclic ether component, a thiol component and a compound represented by the above general formula (1).

According to the present invention, a composition having excellent storage stability and low-temperature adhesion can be obtained by containing a compound represented by general formula (1) (hereinafter, sometimes referred to as compound 1), a thiol component and a cyclic ether component. In addition, "storage stability" means that the reaction progress of the thiol component and the cyclic ether component before exposure is suppressed. Regarding storage stability, for example, compound 1, a thiol component and a cyclic ether component are mixed to form a composition, and the viscosity can be confirmed before and after a specific period of time. Here, the reason why the above effect is exerted by having the above specific structure is speculated as follows.

The aromatic ring group represented by Ar in the compound represented by general formula (1) has excellent absorption of light in the region below visible light and has The base of the pyridine skeleton is easily detached. The pyridine skeleton has a heterocyclic tertiary amine structure: three alkyl chains bonded to the nitrogen atom each form a ring structure, and one nitrogen atom is included as a ring skeleton forming atom. By having such a structure, When the pyridine skeleton is bonded to an aromatic cyclic group Ar, when used in combination with a cyclic ether component such as an epoxy compound or a thiol component, the reaction with the cyclic ether component or the thiol component can be suppressed, thereby exhibiting excellent storage stability. When the pyridine skeleton is detached from the aromatic ring group Ar, the non-shared electrons on the nitrogen atom become the base group with less steric hindrance to the surrounding area, which will exert excellent nucleophilicity. The pyridine skeleton structure, for example, can efficiently exert the catalytic effect generated by the base group, and will become a polymerizing catalyst with excellent ability. According to this situation, when the compound 1 is used together with the cyclic ether component and the thiol component, the curing reaction of the cyclic ether component and the thiol component can be started at a desired time, thereby efficiently allowing the curing reaction to proceed, and low-temperature adhesion can be exerted. In addition, the above composition has excellent freedom in bonding conditions, and even at a low temperature of 50°C to 100°C, the curing reaction can proceed quickly, thereby exerting a higher bonding force. Furthermore, by setting the temperature to a temperature range near room temperature such as 0°C to 50°C, the curing reaction can proceed slowly, thereby exerting a higher bonding force. Furthermore, the composition of the present invention has good bonding properties by combining compound 1 with a thiol component and a cyclic ether component. For these reasons, the composition of the present invention has excellent storage stability and low-temperature bonding properties. Furthermore, it has excellent freedom in bonding conditions.

The following is a detailed description of each component of the composition of the present invention.

1. Compound 1 The compound 1 used in the present invention is represented by the following general formula (1).

[Chemistry 3]

(wherein Ar is an aromatic ring group, A is a a pyridine skeleton, ^B- is a monovalent anion, ^R1 and ^R2 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic alkyl group, the aromatic alkyl group or the heterocyclic group are substituted with a divalent group selected from the following group I-1, and the substituent replacing one or more hydrogen atoms in the aliphatic alkyl group having a substituent, the aromatic alkyl group having a substituent and the heterocyclic group having a substituent is an atom or group selected from the following group II-1; Group I-1: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO ₂ -, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'-, or -SiR'R''-; Group II-1: halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH ₂ , -C(R')=N-OH, -COOH, or -SO ₃ H; R' and R'' independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group. When there are plural R' or R'', they may be the same or different)

Examples of the halogen atom represented by R ¹ and R ² and the halogen atom in Group II-1 (hereinafter also referred to as "halogen atom used in R ¹ , etc.") include fluorine atom, chlorine atom, bromine atom, iodine atom and the like.

The unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² in the general formula (1) (hereinafter also collectively referred to as "aliphatic alkyl group used in R ¹ , etc.") may be any group as long as it does not contain an aromatic hydrocarbon ring or a heterocyclic ring, and examples thereof include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, and groups in which one or more hydrogen atoms of these groups are substituted by a substituent described below.

Examples of the alkyl group having 1 to 20 carbon atoms used in the above ^R1 and the like include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, isobutyl, pentyl, isopentyl, t-pentyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, t-heptyl, 1-octyl, isooctyl, t-octyl, and adamantyl.

Examples of the alkenyl group having 2 to 20 carbon atoms used in the above ^R1 and the like include vinyl, ethylidene, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, 4,8,12-tetradecatrienyl, allyl, and cyclopentadienyl.

The cycloalkyl group having 3 to 20 carbon atoms used in the above ^R1 etc. means a saturated monocyclic or polycyclic alkyl group having 3 to 20 carbon atoms. Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentaene and bicyclo[1.1.1]pentyl.

The cycloalkylalkyl group having 4 to 20 carbon atoms used in the above ^R1 etc. means a group having 4 to 20 carbon atoms in which the hydrogen atom of the alkyl group is substituted by a cycloalkyl group. Examples of the above cycloalkylalkyl group having 4 to 20 carbon atoms include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-3-adamantylpropyl and decahydronaphthylpropyl.

In the present invention, regarding the number of carbon atoms in a group, when a hydrogen atom in the group is replaced by a substituent, it is defined as the number of carbon atoms in the group after the hydrogen atom is replaced. For example, in the case where a hydrogen atom in the above-mentioned alkyl group with 1 to 20 carbon atoms is replaced by a substituent, the number of carbon atoms of 1 to 20 refers to the number of carbon atoms after the hydrogen atom is replaced by the substituent, and does not refer to the number of carbon atoms before the hydrogen atom is replaced. In addition, in the present invention, regarding the definition of the number of carbon atoms in a group with a specific number of carbon atoms, the definition of the number of carbon atoms in the group before the substitution is the same as the definition of the number of carbon atoms in the group before the substitution. For example, in this specification, the number of carbon atoms in a group with 1 to 20 carbon atoms, when a methylene group in a group with a specific number of carbon atoms is replaced by a divalent group, is considered to be 1 to 20.

Furthermore, in the present invention, there may be a situation where a plurality of groups with the same symbol exist in one molecule in the general formula (such as R', etc.). In this case, the situation where the plurality of groups with the same symbol are the same or different is included in the present invention.

The unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms represented by R ¹ and R ² in the general formula (1) (hereinafter also collectively referred to as "aromatic hydrocarbon ring-containing group represented by R ¹ , etc.") may contain an aromatic hydrocarbon ring and not contain a heterocyclic ring, and examples thereof include an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a group having 6 to 20 carbon atoms in which an unsaturated aliphatic hydrocarbon group is substituted by an aryl group, and a group in which one or more hydrogen atoms of the group are substituted by a substituent described below. In the present specification, "aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms" specifies the carbon number of the "aromatic hydrocarbon ring-containing group" rather than the carbon number of the "aromatic hydrocarbon ring". The same applies to other numbers of carbon atoms.

The aryl group having 6 to 20 carbon atoms used in the above ^R1 etc. is a group having aromatic properties, and examples thereof include a group obtained by removing one hydrogen atom from a monocyclic aromatic ring such as phenyl (hereinafter sometimes referred to as a monocyclic aromatic cyclic group), and a group obtained by removing one hydrogen atom from a condensed ring of a monocyclic aromatic ring such as naphthyl, anthracenyl, phenanthrenyl, pyrenyl, fluorenyl, etc. (hereinafter sometimes referred to as a condensed aromatic alkyl group), In addition to a compound obtained by removing one or more hydrogen atoms from two or more monocyclic aromatic rings and their condensed rings bonded via a single bond, a carbonyl group (-CO-) or a sulfide group (-S-) such as biphenyl or benzophenone (hereinafter, sometimes referred to as a bonded aromatic alkyl group), a group in which the hydrogen atom in the aromatic ring is substituted with an aliphatic alkyl group such as tolyl can be exemplified. As the aliphatic alkyl group that replaces the hydrogen atom in the aromatic ring of the aryl group, the same groups as those exemplified above as the aliphatic alkyl group represented by ^R1 etc. can be exemplified.

Examples of the aralkyl group having 7 to 20 carbon atoms used in the above ^R1 etc. include groups in which one or more hydrogen atoms in the above alkyl group are substituted by the above aryl group, such as benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl and naphthylpropyl, or groups in which the hydrogen atoms in the rings of these groups are substituted by aliphatic alkyl groups. Examples of the aliphatic alkyl group that replaces the hydrogen atoms of the alkyl group and the aralkyl group in the aralkyl group include the same groups as those exemplified above as the aliphatic alkyl group having 1 to 20 carbon atoms represented by ^R1 etc. Examples of the unsaturated aliphatic alkyl group having 6 to 20 carbon atoms substituted with an aryl group include a group in which one or two or more hydrogen atoms of the alkenyl group are substituted with the aryl group.

The unsubstituted or substituted heterocyclic group having ² to ²⁰ carbon atoms (hereinafter also collectively referred to as "R ¹ , etc.), in addition to tetrahydrofuranyl, dioxolanyl, tetrahydropyranyl, oxazolidinyl, thienyl, methylthienyl, hexylthienyl, benzothienyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolidinyl, piperidinyl, piperidine, etc., or groups in which one or two or more hydrogen atoms of the heterocyclic ring are substituted with aliphatic alkyl groups, and groups in which one or two or more hydrogen atoms of the aliphatic alkyl groups are substituted with heterocyclic rings, groups in which one or two or more hydrogen atoms of the groups are substituted with substituents described below can be exemplified. Furthermore, the heterocyclic ring also includes an indole ring, a quinoline ring, a benzofuran ring, a carbazole ring, Cyclosulfuron A condensed ring of a heterocyclic ring such as a cyclopentane ring and an aromatic hydrocarbon ring (hereinafter, sometimes referred to as a condensed heterocyclic ring). As the aliphatic alkyl group, the aliphatic alkyl groups exemplified above as ^R1 , etc. can be cited. Furthermore, in this specification, "2 to 20" in "a heterocyclic group having 2 to 20 carbon atoms" specifies the number of carbon atoms in the "heterocyclic group" rather than the "heterocyclic group". The same applies to other numbers of carbon atoms.

In the case where two or more methylene groups of the above-mentioned aliphatic alkyl group, aromatic alkyl ring-containing group or heterocyclic group are substituted with divalent groups selected from the above-mentioned group I-1, the plurality of divalent groups may be the same or different, and the oxygen atoms, sulfur atoms or oxygen atoms and sulfur atoms are not adjacent to each other, and any divalent groups selected from group I-1 may not be adjacent to each other. This situation is the same in the following group I-2, group I-3 and other groups of divalent groups.

As the substituents for substituting the hydrogen atom in the aliphatic alkyl group, the aromatic alkyl ring-containing group and the heterocyclic group as described in the general formula (1) and one or more methylene groups in these groups are substituted with a divalent group selected from the above group I-1, as group II-1, there can be exemplified a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH ₂ , -C(R')=N-OH, -COOH and -SO ₃ H. As the unsubstituted aliphatic alkyl group used in the above group II-1 and R' and R'' in group II-1, there can be used those exemplified above as the aliphatic alkyl group used in R ¹ etc., as long as the number of carbon atoms satisfies the number of carbon atoms of R ¹ etc. Specifically, as the unsubstituted aliphatic alkyl group used in R' and R'', an unsubstituted aliphatic alkyl group having 1 to 19 carbon atoms can be used. As the unsubstituted aliphatic alkyl group having 1 to 19 carbon atoms used in R' and R'', an unsubstituted aliphatic alkyl group having 1 to 19 carbon atoms among the aliphatic alkyl groups used in ^R1 etc. can be used.

^R1 and ^R2 used in the general formula (1) are preferably independently hydrogen atoms, unsubstituted or substituted aliphatic alkyl groups having 1 to 20 carbon atoms, unsubstituted or substituted aromatic hydrocarbon-containing groups having 6 to 20 carbon atoms, unsubstituted or substituted heterocyclic groups having 2 to 20 carbon atoms, or groups in which one or more methylene groups in the aliphatic alkyl groups, aromatic hydrocarbon-containing groups, or heterocyclic groups are substituted with divalent groups selected from the above group I-1. The reason for this is that the storage stability and polymerization catalytic ability of the compound 1 are better, and the above composition will be better in storage stability and low-temperature adhesion. It is more preferred that ^{both R1} and ^R2 used in the general formula (1) are hydrogen atoms, or ^R1 is a hydrogen atom and ^R2 is a group other than a hydrogen atom. The reason is that the storage stability and polymerization catalytic ability of the compound 1 are better, and as a result, the above-mentioned composition will become one with better storage stability and low-temperature adhesion.

^R2 is preferably a hydrogen atom, an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic alkyl group or the aromatic hydrocarbon group are substituted with a divalent group selected from Group I-1, and more preferably a hydrogen atom, an unsubstituted or substituted aliphatic alkyl group having 1 to 10 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group in which one or more methylene groups in the aliphatic alkyl group or the aromatic hydrocarbon group are substituted with a divalent group selected from Group I-1, and more preferably a hydrogen atom, an unsubstituted or substituted aliphatic alkyl group having 1 to 10 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group in which one or more methylene groups in the aliphatic alkyl group or the aromatic hydrocarbon group are substituted with a divalent group selected from Group I-1, and more preferably a hydrogen atom, an unsubstituted or substituted aliphatic alkyl group having 1 to 10 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, An alkyl group which is substituted or has a substituent, an aryl group which is unsubstituted or has a substituent and has 6 to 10 carbon atoms, or a group in which one or more methylene groups in the alkyl group or the aryl group are substituted with a divalent group selected from Group I-1, particularly preferably a hydrogen atom, an alkyl group which is unsubstituted or has a substituent and has 1 to 5 carbon atoms, a benzene ring-containing group which is unsubstituted or has a substituent and has 6 to 10 carbon atoms, or a group in which one or more methylene groups in the alkyl group or the benzene ring-containing group are substituted with a divalent group selected from Group I-1, further preferably a hydrogen atom, an unsubstituted or substituted methyl or ethyl group, or an unsubstituted or substituted phenyl group, and most preferably a hydrogen atom, an unsubstituted methyl or ethyl group, or an unsubstituted phenyl group. The reason is that compound 1 has better storage stability and polymerization catalytic ability, and as a result, the above composition has better storage stability and low-temperature adhesion.

The compound used in A of the general formula (1) has In the base of the pyridine skeleton The pyridine skeleton is a heterocyclic tertiary amine structure containing one nitrogen atom as a heteroatom forming a ring skeleton and three alkyl chains bonded to the nitrogen atom forming a ring structure. The base of the pyridine skeleton has Pyridine or In terms of the balance between the storage stability and polymerization catalytic ability of the compound 1, the compound represented by A having The base of the pyridine skeleton is The unshared electron pair on the nitrogen atom of the pyridine ring is bonded to -CR ¹ R ² - of the general formula (1). In particular, the compound 1 is preferably represented by A having The base of the pyridine skeleton is a base represented by the following general formula (A1) or general formula (A2). The reason is that the storage stability and polymerization catalytic ability of compound 1 are better, and as a result, the above composition will become one with better storage stability and low-temperature adhesion.

[Chemistry 4] (wherein, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ (hereinafter, "R ¹¹ to R ¹⁹ " are also described as) are independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR ¹¹¹ , -COR ¹¹¹ , -OCOR ¹¹¹ , -COOR ¹¹¹ , -SR ¹¹¹ , -SOR ¹¹¹ , -SO ₂ R ¹¹¹ , -NR ¹¹² R ¹¹³ , -NR ¹¹² COR ¹¹³ , -CONR ¹¹² R ¹¹³ , an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or one or more methylene groups in the aliphatic alkyl group, the aromatic alkyl group or the heterocyclic group are substituted with a divalent group selected from the following group I-3, or two groups selected from R ¹¹ to R ¹⁹ are linked to each other to form a ring, X ¹¹ and X ¹² are each independently a divalent group represented by -CR ²⁰¹ R ²⁰² -, R ¹¹¹ , R ¹¹² and R ¹¹³ as well as R 201 and R ¹⁹ are each independently a divalent group represented by -CR 201 R 202 -, R 111 , R 112 , R 113 , R 201 ^{and R 202} each independently represent a hydrogen atom, an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic alkyl group, the aromatic alkyl group or the heterocyclic group are substituted with a divalent group selected from the above group I-3; when there are plural numbers of each of R ¹¹¹ , R ¹¹² , R ¹¹³ , R ²⁰¹ and R ²⁰² , they may be the same or different. The substituents replacing one or more hydrogen atoms in the above-mentioned aliphatic alkyl groups having a substituent, the above-mentioned aromatic alkyl ring-containing groups having a substituent and the above-mentioned heterocyclic ring-containing groups having a substituent are atoms or groups selected from the following Group II-3: * represents a bonding site; Group I-3: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO ₂ -, -NR'-, -NR'--CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R''-; Group II-3: halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH ₂ , -C(R')=N-OH, -COOH or -SO ₃ H; R' and R'' each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group. When there are multiple R' or R'', they may be the same or different.

[Chemistry 5] (wherein, R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ (hereinafter, "R ²¹ to R ²⁷ " are also described as) are independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR ¹¹¹ , -COR ¹¹¹ , -OCOR ¹¹¹ , -COOR ¹¹¹ , -SR ¹¹¹ , -SOR ¹¹¹ , -SO ₂ R ¹¹¹ , -NR ¹¹² R ¹¹³ , -NR ¹¹² COR ¹¹³ , -CONR ¹¹² R ¹¹³ , an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or one or more methylene groups in the aliphatic alkyl group, the aromatic alkyl group or the heterocyclic group are substituted with a divalent group selected from the following group I-4, or two groups selected from R ²¹ to R ²⁷ are linked to each other to form a ring, X ²¹ and X ²² are each independently a divalent group represented by -CR ²⁰¹ R ²⁰² -, R ¹¹¹ , R ¹¹² and R ¹¹³ as well as R ²⁰¹ and R R 111 , R 112 , R 113 , R 201 ^{and R 202} each independently represent a hydrogen atom, an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic alkyl group, the aromatic alkyl group or the heterocyclic group are substituted with a divalent group selected from the following group I-4; when there are plural numbers of each of R ¹¹¹ , R ¹¹² , R ¹¹³ , R ²⁰¹ and R ²⁰² , they may be the same or different. The substituents replacing one or more hydrogen atoms in the above-mentioned aliphatic alkyl groups having a substituent, the above-mentioned aromatic alkyl ring-containing groups having a substituent and the above-mentioned heterocyclic groups having a substituent are atoms or groups selected from the following Group II-4: ^X23 represents an oxygen atom, =CR'R'' or =N-OR'', R'R'' independently represent a hydrogen atom or an unsubstituted aliphatic alkyl group having 1 to 20 carbon atoms; * represents a bonding site; Group I-4: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO- _O- , -CS-, -S-, -SO-, -SO2-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R''-; Group II-4: halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH ₂ , -C(R')=N-OH, -COOH or -SO ₃ H; R' and R'' independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group. When there are multiple R' or R'', they may be the same or different.

As the halogen atom, the unsubstituted or substituted aliphatic alkyl group having ¹ to ^{20 carbon} atoms, the ^{unsubstituted} or substituted aromatic hydrocarbon ring-containing group having 6 to ²⁰ carbon atoms, or the unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms used in R11 ^to R19, R21 ^{to R27} , R111 ^{, R112} and R113 and R201 and ^R202 in the general formula (A1) or (A2), the halogen atom used in ^R1 etc., the aliphatic alkyl group used in ^R1 etc., the aromatic hydrocarbon ring-containing group used in ^R1 etc., and the heterocyclic group used in ^R1 etc. can be those listed above. As R' or R'' used in Groups I-3, I-4, II-3, II-4, and ^X23 of the general formula (A1) or (A2), the same groups as those used in Groups I-1, II-1, etc. can be used.

Examples of the ring formed by two groups selected from R ¹¹ to R ¹⁹ used in the general formula (A1) being linked to each other include aliphatic hydrocarbon rings and aromatic hydrocarbon rings. Examples of the aliphatic hydrocarbon ring include saturated aliphatic hydrocarbon rings or unsaturated aliphatic hydrocarbon rings. Examples of the saturated aliphatic hydrocarbon ring include cyclohexane ring and cyclopentane ring. Examples of the unsaturated aliphatic hydrocarbon ring include cyclohexene ring and cyclopentadiene ring. Examples of the aromatic hydrocarbon ring include benzene ring. Examples of the ring formed by two groups selected from R ²¹ to R ²⁷ used in the general formula (A2) that are linked to each other include those exemplified above as the ring formed by two groups selected from R ¹¹ , etc. that are linked to each other.

The one used in A has The group of the pyridine skeleton is preferably a group represented by formula (A1) or a group represented by formula (A2) in which ^X23 is an oxygen atom, and the most preferred group is a group represented by formula (A1). The reason is that the storage stability and polymerization catalytic ability of compound 1 are better, and as a result, the above-mentioned composition will become one with better storage stability and low-temperature adhesion.

In the general formula (A1), R ¹¹ to R ¹⁹ are hydrogen atoms or groups or atoms other than hydrogen atoms. Groups or atoms that are easily available as raw materials for producing compound 1 are halogen atoms, nitro groups, cyano groups, -OR ¹¹¹ , -COR ¹¹¹ , -OCOR ¹¹¹ , -COOR ¹¹¹ , -SR ¹¹¹ , -SOR ¹¹¹ , -SO ₂ R ¹¹¹ , -NR ¹¹² R ¹¹³ , -NR ¹¹² COR ¹¹³ , -CONR ¹¹² R ¹¹³ , unsubstituted alkyl groups having 1 to 10 carbon atoms, and unsubstituted aryl groups having 6 to 10 carbon atoms. Examples of R ¹¹¹ , R ¹¹² and R ¹¹³ are independently a hydrogen atom or an unsubstituted alkyl group having 1 to 10 carbon atoms. In view of the ease of production of compound 1, R ¹¹ to R ¹⁹ are preferably a hydrogen atom or a group having 6 or less carbon atoms.

In the present invention, it is preferred that R ¹¹ to R ¹⁹ in the general formula (A1) are all hydrogen atoms, or any 1 to 3 of them are hydroxyl, cyano, -SH group, or alkyl group having 1 to 3 carbon atoms which may be substituted or not substituted by hydroxyl, cyano or -SH group, which are preferred substituents other than hydrogen atoms; more preferably, they are all hydrogen atoms, or any 1 or 2 of them are hydroxyl, -SH group, cyano, or alkyl group having 1 to 3 carbon atoms which may be substituted or not substituted by hydroxyl, cyano or -SH group, and the rest are hydrogen atoms; further preferably, they are all hydrogen atoms, or any 1 or 2 of them are hydroxyl, cyano or -SH group, and the rest are hydrogen atoms; further most preferably, they are all hydrogen atoms, or any 1 or 2 of them are hydroxyl or cyano group, and the rest are hydrogen atoms. The reason is that the above-mentioned compound can be used as an initiator with a better balance between storage stability and polymerization catalytic ability. When at least one of R ¹¹ to R ¹⁹ in the general formula (A1) is a substituent other than a hydrogen atom, it is particularly preferred that any one of R ¹³ , R ¹⁴ , R ¹⁶ and R ¹⁷ is a group or atom other than the above-mentioned hydrogen atom, and it is particularly preferred that it is a preferred substituent other than hydrogen atom. In such cases, it is preferred that the rest of R ¹¹ to R ¹⁹ are hydrogen atoms. The reason is that the above-mentioned compound can be used as an initiator with a better balance between storage stability and polymerization catalytic ability.

As X ¹¹ and X ¹² in the general formula (A1), R ²⁰¹ and R ²⁰² are preferably hydrogen atoms or substituted or unsubstituted alkyl groups having 3 or less carbon atoms, more preferably R ²⁰¹ and R ²⁰² are hydrogen atoms or unsubstituted alkyl groups having 3 or less carbon atoms, particularly preferably R ²⁰¹ and R ²⁰² are hydrogen atoms or methyl groups, and most preferably R ²⁰¹ and R ²⁰² are hydrogen atoms. The reason for this is that the storage stability and polymerization catalytic ability of the compound 1 are better, and as a result, the above-mentioned composition will become one with better storage stability and low-temperature adhesiveness.

In the general formula (A2), R ²¹ to R ²⁷ are hydrogen atoms or groups or atoms other than hydrogen atoms. Groups or atoms that are easily available as raw materials for producing compound 1 are halogen atoms, nitro groups, cyano groups, -OR ¹¹¹ , -COR ¹¹¹ , -OCOR ¹¹¹ , -COOR ¹¹¹ , -SR ¹¹¹ , -SOR ¹¹¹ , -SO ₂ R ¹¹¹ , -NR ¹¹² R ¹¹³ , -NR ¹¹² COR ¹¹³ , -CONR ¹¹² R ¹¹³ , unsubstituted alkyl groups having 1 to 10 carbon atoms, and unsubstituted aryl groups having 6 to 10 carbon atoms. Examples of R ¹¹¹ , R ¹¹² and R R ²¹ to R ^{27 are preferably hydrogen atoms or groups having 6 or less carbon atoms from the viewpoint of the ease of production of compound 1. In addition, in terms of the ease of production, it is preferred that any 4 or more of R 21 to R 27 in formula (} A2) are hydrogen atoms, or all of them may be hydrogen atoms.

As X ²¹ and X ²² in the general formula (A2), R ²⁰¹ and R ²⁰² are preferably hydrogen atoms or substituted or unsubstituted alkyl groups having 3 or less carbon atoms, more preferably R ²⁰¹ and R ²⁰² are hydrogen atoms or unsubstituted alkyl groups having 3 or less carbon atoms, particularly preferably R ²⁰¹ and R ²⁰² are hydrogen atoms or methyl groups, and most preferably R ²⁰¹ and R ²⁰² are hydrogen atoms. The reason for this is that the storage stability and polymerization catalytic ability of the compound 1 are better, and as a result, the above-mentioned composition will become one with better storage stability and low-temperature adhesiveness.

The aromatic cyclic group Ar used in the general formula (1) is a group having aromatic properties. As the aromatic cyclic group ^Ar , there can be used a monocyclic aromatic alkyl group, a condensed aromatic alkyl group, a linked aromatic alkyl group, and a condensed heterocyclic group obtained by removing one hydrogen atom from a condensed heterocyclic group, which are exemplified as the aromatic alkyl ring-containing group used in ^R1 , etc., and the like. In the present invention, the aromatic cyclic group Ar is preferably a group having two or more ring structures and having aromatic properties, and is particularly preferably a condensed aromatic alkyl group, a linked aromatic alkyl group, a condensed heterocyclic group, etc., and is particularly preferably a group represented by the following general formula (Ara1), (Arb1) or (Arc1). The reason is that the above compounds can be used as initiators with a better balance between storage stability and polymerization catalyst ability.

[Chemistry 6]

₍ wherein, ^Y1 is a sulfur atom, CO, SO, _SO2 , ^CR1012 , ^PR102 or ^NR102 , ^Y2 is a single bond, an oxygen atom, a sulfur atom, CO, SO, SO2, _CR1022 ^{, PR102} _or ^NR101 , ^Y3 is an oxygen atom, a sulfur atom, CO, SO, _SO2 , ^{CR1022 , PR102} or ^NR101 , _R ¹⁰¹ each independently represents an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic alkyl group, the aromatic alkyl group or the heterocyclic group are substituted with a divalent group selected from the following group I-2, R ^R102 each independently represents a hydrogen atom, an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic alkyl group, the aromatic alkyl group or the heterocyclic group are substituted with a divalent group selected from the following group I-2; ^R31 , ^R32 , ^R41 , ^R42 , ^R51 , ^R52 and ^R53 each independently represent a halogen atom, a nitro group, a cyano group, ^-OR121 , ^-COR121 , ^-OCOR121 , ^-COOR121 , ^-SR121 , -SOR ¹²¹ , -SO ₂ R ¹²¹ , -NR ¹²² R ¹²³ , -NR ¹²² COR ¹²³ , -CONR ¹²² R ¹²³ , an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or one or more methylene groups in the aliphatic alkyl group, the aromatic alkyl group or the heterocyclic group are substituted with a divalent group selected from the following group I-2, However, a plurality of R ⁴¹ may be bonded to each other to form a ring, and the ring is unsubstituted or substituted, R ¹²¹ , R ¹²² and R ^R121 , R122 or R123 each independently represent a hydrogen atom, an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the above-mentioned aliphatic alkyl group, the above-mentioned aromatic alkyl group or the above-mentioned heterocyclic group are substituted with a divalent group selected from the following group I-2. When there are plural numbers of ^R121 , ^R122 or ^{R123, they may be the same or different. The above-mentioned aliphatic alkyl group having a substituent, the above-mentioned aromatic alkyl group having a substituent, the above-mentioned heterocyclic group having a substituent, and the plural numbers of R121, R122 or R123} may be substituted with a divalent group selected from the following group I-2. The substituents of one or more hydrogen atoms in the ring formed by mutual bonding of ⁴¹ are atoms or groups selected from the following Group II-2, a1 is an integer of 0 to 5, a2 is an integer of 0 to 4, b1 is an integer of 0 to 4, b2 is an integer of 0 to 3, c1 is an integer of 0 to 4, c2 is an integer of 0 to 1, * represents a bonding site; Group I-2: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO ₂ -, -NR'-, -NR'--CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R''-; Group II-2: halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH ₂ , -C(R')=N-OH, -COOH or -SO ₃ H; R' and R'' each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group; when there are multiple R' or R'', they may be the same or different)

Here, as the halogen atom, unsubstituted or substituted aliphatic alkyl group ^{having 1 to 20 carbon} atoms, unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, and unsubstituted or substituted heterocyclic group having 2 to ^{20 carbon atoms used in R101, R102, R31, R32, R41, R42, R51, R52 , R53 , R121 , R122 , and} R123 of (Ara1), (Arb1), or ( ^Arc1 ), the halogen atom, aliphatic alkyl group, aromatic hydrocarbon ring-containing group used in ^R1 , etc., ^R The mixed ring groups used in ¹ , etc. are those exemplified above. As for R' or R'' used in Groups I-2 and II-2 of the general formulae (Ara1), (Arb1), and (Arc1), the same groups as those used in Groups I-1, II-1, etc. can be used. As the ring formed by a plurality of R ^41s mutually bonding, a benzene ring condensed to a benzene ring located on the left side of Arb1 can be exemplified. As the structure of the formula Arb1 in which the ring is formed, the structures represented by the following formulae (Arb1α), (Arb1β), or (Arb1γ) can be exemplified.

[Chemistry 6A] (In (Arb1α) to (Arb1β), R ⁴³ is an atom or group selected from the above group II-2, b3 is a number from 0 to 4, b1' is a number from 0 to 2; Y ² , Y ³ , R ⁴² , and b2 are the same as in formula (Arb1); R ⁴¹ ' is the same as R ⁴¹ except that a plurality of R ⁴¹ ' do not bond to each other to form a ring)

In the present invention, the aromatic ring group Ar is preferably a group represented by the above general formula (Ara1) or formula (Arb1), and is particularly preferably a group represented by formula (Ara1). The reason is that the storage stability and polymerization catalytic ability of compound 1 are better, and as a result, the above composition will become one with better storage stability and low-temperature adhesion.

In the general formula (Ara1), ^R31 and ^R32 are preferably independently nitro, an unsubstituted or substituted aliphatic alkyl group having 1 to 10 carbon atoms, an unsubstituted or substituted heterocyclic group having 3 to 10 carbon atoms, or one or more methylene groups in the aliphatic alkyl group or heterocyclic group are substituted with a divalent group selected from the above group I-2, or ^-COR121 and ^R121 is an unsubstituted or substituted aryl group having 6 to 10 carbon atoms or a unsubstituted or substituted heterocyclic group having 3 to 10 carbon atoms. The reason is that the storage stability and polymerization catalytic ability of the compound 1 are better, and as a result, the above composition will be better in storage stability and low-temperature adhesion.

a1 in the general formula (Ara1) is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, particularly preferably an integer of 0 to 1, and most preferably 0. The reason is that the storage stability and polymerization catalytic ability of compound 1 are better, and as a result, the above composition will become one with better storage stability and low-temperature adhesion.

a2 in the general formula (Ara1) is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, and most preferably 0. The reason is that the storage stability and polymerization catalytic ability of compound 1 are better, and as a result, the above composition will become one with better storage stability and low-temperature adhesion.

The bonding site in the general formula (Ara1), i.e., the bonding site with -CO-CR ¹ R ² A ⁺ B ^-, can be a bonding site in the aromatic ring, preferably in the para position relative to Y ^1. The reason for this is that the storage stability and polymerization catalytic ability of the compound 1 are better, and as a result, the above composition will be better in storage stability and low-temperature adhesion. Therefore, when Y ¹ is a sulfur atom, it is preferred that the above compound 1 is a compound represented by the following general formula (11).

In the general formula (Ara1), Y ¹ is preferably a sulfur atom, CO, SO, NR ¹⁰² , and is particularly preferably a sulfur atom. The reason is that the storage stability and polymerization catalytic ability of the above-mentioned compound 1 are better, and as a result, the above-mentioned composition will become one with better storage stability and low-temperature adhesion. In addition, the reason is that the synthesis is easy. Based on the above reasons, among the compounds 1, the compound represented by the following formula (11) is more preferred.

[Chemistry 7] (wherein, A ⁺ , B ^- , R ¹ and R ² are the same as those in the above general formula (1), and R ³¹ , R ³² , a1 and a2 are the same as those in the above general formula (Ara1))

In the general formula (Arb1), ^R41 and ^R42 are preferably independently nitro, an unsubstituted or substituted aliphatic alkyl group having 1 to 10 carbon atoms, an unsubstituted or substituted heterocyclic group having 3 to 10 carbon atoms, or a group in which one or more methylene groups in the aliphatic alkyl group or the heterocyclic group are substituted with a divalent group selected from the above group I-2, or ^-COR121 and ^R121 is an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, or an unsubstituted or substituted heterocyclic group having 3 to 10 carbon atoms, or ^R41 are bonded to each other to have the groups represented by (Arb1α) to (Arb1γ) above. The reason is that compound 1 has better storage stability and polymerization catalytic ability, and as a result, the above composition has better storage stability and low-temperature adhesion.

When R ⁴¹ is not bonded to each other to form a ring, b1 in the general formula (Arb1) is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably an integer of 0 to 1. The reason is that the storage stability and polymerization catalytic ability of compound 1 are better, and as a result, the above composition will become one with better storage stability and low-temperature adhesion.

When R ⁴¹ are bonded to form a ring and represented by any of the formulas (Arb1α) to (Arb1β), b1' is preferably 0, and b3 is preferably an integer of 0 to 1. The reason is that the storage stability and polymerization catalytic ability of compound 1 are better, and as a result, the above composition will become better in storage stability and low-temperature adhesion.

b2 in the general formula (Arb1) is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, and most preferably 0. The reason is that the storage stability and polymerization catalytic ability of the compound 1 are better, and as a result, the above composition will become better in storage stability and low-temperature adhesion.

The bonding site of the general formula (Arb1), i.e., the bonding site with -CO-CR ¹ R ² A ⁺ B ^- , can be a bonding site in the aromatic ring, preferably in the para position relative to Y ^3. The reason is that the storage stability and polymerization catalytic ability of compound 1 are better, and as a result, the above composition will become better in storage stability and low-temperature adhesion.

In the general formula (Arb1), ^Y2 is preferably a single bond, and ^Y3 is preferably ^CR1022 or _NR101 . The reason is that the storage stability and polymerization catalytic ability of the above-mentioned compound 1 are better, and as a result ^, the above-mentioned composition will become one with better storage stability and low-temperature adhesion. Another reason is that the synthesis is easy.

R ¹⁰¹ is preferably an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms or a group in which one or more methylene groups in the aliphatic alkyl group are substituted with a divalent group selected from the above group I-2, and is particularly preferably an unsubstituted or substituted aliphatic alkyl group having 1 to 10 carbon atoms.

R ¹⁰² is preferably a hydrogen atom or an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic alkyl group are substituted with a divalent group selected from the above group I-2, and is particularly preferably a hydrogen atom or an unsubstituted or substituted aliphatic alkyl group having 1 to 8 carbon atoms. The reason is that the storage stability and polymerization catalytic ability of the above compound 1 are better, and as a result, the above composition will become one with better storage stability and low-temperature adhesion.

Among the compounds 1 in which the aromatic ring group is represented by the formula (Arb1), the compounds represented by the following formula (12) are particularly preferred.

[Chemical 7A] (wherein, Y ^3' is CR ¹⁰² ₂ or NR ¹⁰¹ , A ⁺ , B ^- , R ¹ and R ² are the same as those in the above general formula (1), and R ⁴¹ , R ⁴² , b1 and b2 are the same as those in the above general formula (Arb1))

Examples of the monovalent anion represented by ^B- in the general formula (1) include halide ions, inorganic halogenated anions, sulfonate anions, phosphorus-containing anions, imide ions, borate anions (sometimes also referred to as "borate anions"), carboxylate anions, dithiocarbamate anions, organic sulfonylmethide ions, thiocyanate anions, and dithiocarbamate anions.

Examples of the halogenide ions include chlorine anion, bromine anion, iodine anion, and fluorine anion.

Examples of the inorganic halogenated anion include perchlorate anion, chlorate anion, thiocyanate anion, hexafluorophosphate anion, hexafluoroantimony anion, hexafluoroarsenic anion, tetrafluoroboron anion and the like.

Examples of the sulfonate anion include methanesulfonate anion, fluorosulfonate anion, benzenesulfonate anion, toluenesulfonate anion, 1-naphthylsulfonate anion, 2-naphthylsulfonate anion, trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, heptafluoropropanesulfonate anion, nonafluorobutanesulfonate anion, undecafluoropentanesulfonate anion, tridecafluorohexanesulfonate anion, pentafluoroheptanesulfonate anion, heptadecafluorooctanesulfonate anion, perfluoro-4-ethylhexanesulfonate anion, and the like. The present invention also includes cyclohexanesulfonate anion, N-alkyl (or aryl) diphenylamine-4-sulfonate anion, 2-amino-4-methyl-5-chlorobenzenesulfonate anion, 2-amino-5-nitrobenzenesulfonate anion, sulfonate anions described in Japanese Patent Laid-Open No. 2004-53799, camphorsulfonate anion, fluorobenzenesulfonate anion, difluorobenzenesulfonate anion, trifluorobenzenesulfonate anion, tetrafluorobenzenesulfonate anion, pentafluorobenzenesulfonate anion, and the like.

Examples of phosphorus-containing anions include alkyl or aryl esters of phosphoric acid or phosphonic acid, and organic group-substituted phosphinate anions in which the hydrogen atom bonded to the phosphorus atom in phosphinic acid ((HO) _PH2 (=O)) is replaced by an alkyl group (e.g., having 1 to 20 carbon atoms) or an aryl group (e.g., having 6 to 20 carbon atoms), or the methylene group in the alkyl or aryl group is replaced by a divalent group selected from the above group I-1, such as -CO-. For example, the phosphorus-containing anion specifically includes phosphate anions such as octyl phosphate anion, dodecyl phosphate anion, octadecyl phosphate anion, phenyl phosphate anion, nonylphenyl phosphate anion, or phosphonate anions such as 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphonate anion, and organic group-substituted phosphinate anions such as (2,4,6-trimethylbenzyl)phenyl phosphite, dialkyl phosphite, and diphenyl phosphite.

Examples of the imide ion include bis(trifluoromethanesulfonyl)imide ion, bis(pentafluoroethanesulfonyl)imide ion, o-phenylenediformyl imide ion, o-sulfonylbenzyl imide, bis(heptafluoropropanesulfonyl)imide ion, bis(nonafluorobutanesulfonyl)imide ion, bis(undecafluoropentanesulfonyl)imide ion, bis(pentadecafluoropentanesulfonyl)imide ion, fluoroheptanesulfonyl)imide ion, bis(tridecafluorohexanesulfonyl)imide ion, bis(heptadecafluorooctanesulfonyl)imide ion, (trifluoromethanesulfonyl) (nonafluorobutanesulfonyl)imide ion, (methanesulfonyl) (trifluoromethanesulfonyl)imide ion, cyclo-hexafluoropropane-1,3-bis(sulfonyl)imide anion, etc.

Examples of borate anions include organic anions in which an alkyl group and/or an aryl group is bonded to any bond of a boron atom. Specific examples of borate anions include tetrakis(pentafluorophenyl)borate anion, tetrakis(4-fluorophenyl)borate anion, tetraphenylborate anion, borate anions described in Japanese Patent Laid-Open No. 2007-112854, tetraarylborate anions, and triarylalkylborane anions. In addition, borate anions described in Japanese Patent Laid-Open No. 6-184170 and borate anions described in Japanese Patent No. 2002-526391 can also be cited.

Examples of the carboxylate anion include a benzoate anion, a trifluoroacetate anion, and a 2-oxo-2-phenylacetate anion.

Examples of methide ions include organic sulfonyl methide ions such as tris(trifluoromethanesulfonyl)methide and tris(methanesulfonyl)methide. Examples of dithiocarbamate anions include N,N-diethyldithiocarbamate anions.

In addition, examples include: alkylsulfonate ions or fluorine-substituted alkylsulfonate ions, alkylsulfonimides, fluorine-substituted alkylsulfonimides substituted with an acryloxy group, a methacryloxy group, or aliphatic cyclic alkyl groups such as a norinyl group and an adamantyl group. In addition, quenching anions having the function of deexciting (quenching) active molecules in an excited state, or metallocene compound anions such as ferrocene and ruthenocene having an anionic group such as a carboxyl group, a phosphonic acid group, or a sulfonic group on the cyclopentadienyl ring, etc. can also be used as needed.

Among the monovalent anions represented by ^B- , in terms of the balance of low-temperature adhesiveness, storage stability, availability of raw materials, etc., more preferred are borate anions, thiocyanate anions, o-phthalimide anions, halide anions, sulfonylbenzalimide anions, tetrafluoroboron anions, phosphorus hexafluoride anions, trifluoromethanesulfonate anions, and phosphorus-containing anions. Among them, borate anions and phosphorus-containing anions are particularly preferred, and borate anions are particularly preferred. The most preferred is a borate anion represented by the following general formula (I). In the general formula (I), it is preferred that R ³⁰¹ to R ³⁰⁴ are anions of unsubstituted or substituted aromatic groups having 6 to 10 carbon atoms. The reason for this is that the storage stability and polymerization catalytic ability of the compound 1 are better, and as a result, the above-mentioned composition will have better storage stability and low-temperature adhesion.

[Chemistry 8] (R ³⁰¹ , R ³⁰² , R ³⁰³ and R ³⁰⁴ are independently an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted, or an aryl group having 6 to 20 carbon atoms which is unsubstituted or substituted, and the substituents are atoms or groups selected from the following Group II-5; Group II-5: halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH ₂ , -C(R')=N-OH, -COOH or -SO ₃ H; R' is independently a hydrogen atom or an unsubstituted aliphatic hydrocarbon group, and when there are plural R's, they may be the same or different)

Here, as the unsubstituted alkyl group having 1 to 20 carbon atoms and the unsubstituted aryl group having 6 to 20 carbon atoms used in R ³⁰¹ , R ³⁰² , R ³⁰³ and R ³⁰⁴ in the general formula (I), the alkyl group used in R ¹ etc. and the aryl group used in R ¹ etc. mentioned above can be used. As for R' used in group II-5 of the general formula (I), the same group as used in group II-1 can be used.

The method for preparing the compound represented by the general formula (I) is not particularly limited, and it can be prepared, for example, by the following method according to the following reaction formula 1. That is, by reacting a ketone having bromine bonded to the α-position of the carbonyl group with The reaction is carried out with pyridine or its derivatives to obtain compound 1 as a Br salt. Reaction formula 1 is a case where A is represented by general formula (A1), R ¹¹ to R ¹⁹ are hydrogen atoms, and X ¹¹ and X ¹² are -CH ₂ -. Other compounds 1 can also be used by changing It is made from pyridine derivatives.

[Chemistry 9] (wherein, R ¹ , R ² and Ar are the same as those in general formula (1))

Compound 1 other than Br salt can be obtained by reacting the target anion B ^- with a salt of a cation M ⁺ such as an alkali metal cation (the following reaction formula 2). Examples of the cation M ⁺ include sodium cation and the like.

[Chemistry 10] (wherein, R ¹ , R ² and Ar are the same as those in general formula (1))

According to the present invention, the content of compound 1 is preferably 1 to 20 parts by mass, preferably 3 to 15 parts by mass, and preferably 5 to 10 parts by mass, out of 100 parts by mass of the total of the cyclic ether component, the thiol component, and compound 1. The reason is that the composition has a better balance between storage stability and low-temperature adhesion.

In the composition of the present invention, the content of compound 1 is preferably 5 to 30 parts by mass, more preferably 7 to 25 parts by mass, and more preferably 10 to 20 parts by mass, relative to 100 parts by mass of the total of the thiol component and compound 1. The reason is that the above composition has a better balance between storage stability and low-temperature adhesion.

In the composition of the present invention, the content of the compound 1 can be any content that can obtain the desired storage stability and low-temperature adhesion, preferably 0.2 mass parts to 30 mass parts out of 100 mass parts of the solid components of the composition, preferably 0.5 mass parts to 20 mass parts, more preferably 2 mass parts to 15 mass parts, and preferably 3 mass parts to 10 mass parts. The reason is that the above composition will be a better balance between storage stability and low-temperature adhesion. Furthermore, the solid component refers to the total mass of all components except the solvent.

In the composition of the present invention, the content of the compound 1 can be any content that can obtain the desired storage stability and low-temperature adhesiveness, preferably 0.2 mass parts to 30 mass parts in 100 mass parts of the composition, preferably 0.5 mass parts to 20 mass parts, more preferably 2 mass parts to 15 mass parts, and even more preferably 3 mass parts to 10 mass parts. The reason is that the above composition will be a better balance between storage stability and low-temperature adhesiveness.

The content of the compound 1 can be any content that can obtain the desired storage stability and low-temperature adhesiveness. When the composition includes a cyclic ether component as a curable component, the thiol component, and a radical polymerizable component, the content is preferably 0.2 to 30 parts by mass, preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and most preferably 3 to 10 parts by mass, relative to 100 parts by mass of the total of the cyclic ether component, the thiol component, and the radical polymerizable component. The reason for this is that the composition has a better balance between storage stability and curability.

2. Thiol component A thiol component refers to one or more components of a compound having a thiol group (hereinafter, sometimes referred to as a thiol compound). A thiol compound is a component included in the composition other than the above-mentioned compound 1. A compound having both a thiol group and a cyclic ether group also belongs to a thiol compound.

Regarding the thiol component, only one thiol compound may be used, or two or more thiol compounds may be used in combination. In the present invention, by combining the thiol component with the above-mentioned compound 1, a composition having particularly excellent curability can be obtained.

As the type of thiol group in the thiol compound, a primary thiol group, a secondary thiol group, a tertiary thiol group, etc. can be used. From the viewpoint of more effectively exerting the effects of the present invention in terms of storage stability and excellent low-temperature adhesion, the type of thiol group is preferably a primary thiol group or a secondary thiol group, and preferably a primary thiol group.

As a thiol compound, in terms of further improving the effects of storage stability and excellent low-temperature adhesion, the number of thiol groups contained in one molecule is preferably 2 or more, and more preferably 3 or more. In terms of making a product with better storage stability, the number of thiol groups is preferably 10 or less, more preferably 8 or less, more preferably 7 or less, preferably 6 or less, preferably 5 or less, and preferably 4 or less. The primary thiol compound having the above number of thiol groups is particularly preferred, that is, the thiol compound is a compound having 2 or more primary thiol groups, preferably a compound having 2 or more and 10 or less primary thiol groups, and more preferably a compound having 2 or more and 8 or less, particularly 2 or more and 7 or less, particularly 2 or more and 6 or less, particularly 3 or more and 5 or less, particularly 3 or more and 4 or less primary thiol groups. The reason is that the above composition will be a better balance between storage stability and low-temperature adhesion. As an example of the above thiol compound having 2 or more and 10 or less thiol groups, it is preferred to use a compound represented by the following formula (A) (hereinafter, sometimes referred to as compound A). The reason is that the above composition will be a better balance between storage stability and low-temperature adhesion. In addition, it is better in terms of ease of acquisition or the balance between the storage stability and hardening properties of the composition.

[Chemistry 11] (wherein _X1 represents an unsubstituted or substituted aliphatic alkyl group having 1 to 40 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 40 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, having the same valence as n1, or represents a group in which one or more methylene groups in the aliphatic alkyl group, the aromatic alkyl group, or the heterocyclic group are substituted with a divalent group selected from the following Group III, and n1 represents an integer of 2 to 10; Group III: a group selected from -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'''-, -SS- or _-SO2- ; R''' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. When there are multiple R'''s, they may be the same or different.

The above _X1 is used as a linking group for bonding n1 -SH groups. The above _X1 represented by the aliphatic alkyl group having 1 to 40 carbon atoms, the group containing an aromatic alkyl ring having 6 to 40 carbon atoms, and the heterocyclic group containing 2 to 20 carbon atoms having the same valence as n1 are groups of structures obtained by removing (n1-1) hydrogen atoms from a monovalent aliphatic alkyl group having 1 to 40 carbon atoms, a monovalent aromatic alkyl ring containing 6 to 40 carbon atoms, and a monovalent heterocyclic group containing 2 to 20 carbon atoms. Regarding _X1 , in terms of the balance between the storage stability and low temperature adhesiveness of the composition, the aliphatic alkyl group having 1 to 40 carbon atoms and having the same valence as n1 is preferably 1 to 30 carbon atoms, and may be 1 to 20 carbon atoms. As the monovalent aliphatic alkyl group having 1 to 40 carbon atoms, the monovalent aromatic hydrocarbon ring-containing group having 6 to 40 carbon atoms, and the monovalent heterocyclic group having ² to 20 carbon atoms, the same groups as the aliphatic alkyl group having 1 to 20 carbon atoms, the aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, and the heterocyclic group having 2 ^to 20 carbon atoms used in ^R1 , etc. described above can be used. As the alkyl group having 1 to 8 carbon atoms used in R''' in the above group III, the alkyl group having 1 to 20 carbon atoms used in R ¹ etc. can be used. The alkyl group may be unsubstituted or substituted with a substituent described below. When two or more methylene groups in the above aliphatic alkyl group, the above aromatic alkyl ring-containing group or the above heterocyclic group are substituted with a divalent group selected from group III, the plurality of divalent groups are set to be non-adjacent to each other. The plurality of divalent groups may be the same or different from each other.

The substituents replacing one or more hydrogen atoms in the aliphatic alkyl group, aromatic alkyl ring-containing group, heterocyclic group or the like substituted with a group selected from Group III in _X1 and the substituents replacing one or more hydrogen atoms in the alkyl group having 1 to 8 carbon atoms used in R''' may be groups or atoms selected from Group II-1 except for thiol groups. Specifically, they may be halogen atoms, cyano groups, nitro groups, -CO-H, hydroxyl _groups , -NH2, -C(R')=N-OH, -COOH or _-SO3H .

Below, from the perspective of the balance between the storage stability and low-temperature adhesiveness of the composition, examples of preferred groups represented by _X1 are further described. As the divalent aliphatic alkyl group having ₁ to 40 carbon atoms, which is unsubstituted or substituted, represented by X1, for example, preferably alkylene groups such as methylene, ethylene, propylene, butylene, butanediyl, or groups in which the methylene groups are substituted with groups selected from the above group III, and groups in which these groups are substituted with the above substituents, can be exemplified. The reason is that the above composition will have a better balance between the storage stability and low-temperature adhesiveness.

As the trivalent aliphatic alkyl group having 1 to 40 carbon atoms represented by _X1 , preferably, alkylene groups such as propylene, 1,1,3-butylene, or one or more methylene groups thereof are substituted with groups selected from Group III, and groups in which one or two hydrogen atoms are substituted with the above-mentioned substituents. The reason for this is that the above-mentioned composition will have a better balance between storage stability and low-temperature adhesiveness.

Preferred examples of the _tetravalent aliphatic alkyl group having 1 to 40 carbon atoms, which is unsubstituted or has a substituent, or a group in which the methylene group in the aliphatic alkyl group is substituted with a group selected from Group III, include groups comprising a residual group of a polyol (for example, a group represented by the general formula (X3) described below) and groups in which these groups are substituted with the above-mentioned substituents.

Preferred examples of the _hexavalent aliphatic hydrocarbon group having 1 to 40 carbon atoms, which is unsubstituted or has a substituent, or a group in which the methylene group in the aliphatic hydrocarbon group is substituted with a group selected from Group III, include groups comprising a residual group of a polyol (for example, a group represented by the general formula (X4) described below) and groups in which these groups are substituted with the above-mentioned substituents.

Preferred examples of the divalent unsubstituted or substituted aromatic hydrocarbon-containing group having 6 to 40 carbon atoms represented by _X1 above, or a group in which the methylene group thereof is substituted with a group selected from Group III, include: arylene groups such as phenylene and naphthylene, residues of bifunctional phenols such as o-catechin, bisphenol, and oxirane adducts thereof; 2,4,8,10-tetraoxaspiro[5,5]undecane, and groups in which these groups are substituted with the above substituents.

Examples of the trivalent unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 40 carbon atoms represented by _X1 include phenyl-1,3,5-trimethylene and groups in which these groups are substituted by the above-mentioned substituents.

Examples of the _divalent heterocyclic group having 2 to 20 carbon atoms and not substituted or having a substituent include groups having a heterocyclic ring such as a pyridine ring, a pyrimidine ring, a piperidine ring, a piperidine ring, a trithion ring, a furan ring, a thiophene ring, an indole ring, and groups in which one or two or more hydrogen atoms of the groups are substituted by the above substituents. Examples of the trivalent heterocyclic group having 2 to 20 carbon atoms and not substituted or having a substituent include groups having an isocyanuric acid ring or a trithion ring, and groups in which _one or two or more hydrogen atoms of the groups are substituted by the above substituents.

Examples of the tetravalent unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms represented by _X1 include groups having a glycoluril group and groups in which the hydrogen atom of the group is substituted by the above-mentioned substituent.

In the present invention, from the viewpoint of the balance between the storage stability and low temperature adhesiveness of the composition, X ₁ is preferably an aliphatic alkyl group, an aromatic alkyl ring-containing group, or a heterocyclic group in which one or more methylene groups are substituted with a group selected from Group III, and more preferably one or more methylene groups are substituted with -O-CO- or -CO-O-, and particularly preferably n1 methylene groups are substituted with -O-CO- or -CO-O-.

In the present invention, n1 is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 3 to 4. The reason for this is that the above composition has a better balance between storage stability and low-temperature adhesion.

In the present invention, in terms of the balance between the storage stability and low-temperature adhesiveness of the composition, it is preferred that the above _X1 has a structure represented by any one of the following X1 to X6. In terms of the balance between the storage stability and curability of the composition, it is particularly preferred that it has a structure represented by any one of X2 to X6, and it is particularly preferred that it has a structure represented by X2, X3 or X5. The reason for this is that the above composition will have a better balance between the storage stability and low-temperature adhesiveness.

[Chemistry 12] (In the formula, a11 is an integer from 1 to 20; * indicates the bonding site)

In the present invention, in terms of the balance between the storage stability and low-temperature adhesion of the composition, the compound represented by the above formula (A) is preferably a compound represented by any one of the following formulas (A1) to (A6), more preferably represented by any one of (A2) to (A6), and particularly preferably represented by any one of (A2), (A3) or (A5). The reason is that the above composition will have a better balance between the storage stability and low-temperature adhesion. [Chemistry 13] ⁽ wherein, ^L11 , L12, ^L21 , ^L22 , ^L23 , L31, ^L32 , ^L33 , ^L34 , ^L41 , ^L42 , ^L43 , ^L44 , ^L45 , ^L46 , ^L51 , ^L52 , ^L53 , ^L61 , ^L62 , ^L63 and ^L64 (hereinafter also referred to as " ^L11 to ^L64 ") independently represent a linear or branched alkylene group having 1 to 10 carbon atoms; ^{R64 , R65} and ^R66 independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms; a21 represents an integer from 1 to 20)

Examples of the alkylene group having 1 to 10 carbon atoms represented by L ¹¹ to L ⁶⁴ include a divalent group having a structure obtained by removing one hydrogen atom from an alkyl group having 1 to 10 carbon atoms. As the alkyl group having 1 to 10 carbon atoms, for example, the alkyl group having 1 to 20 carbon atoms in R ¹ etc. mentioned above can be used. Furthermore, the aliphatic alkyl group having 1 to 20 carbon atoms used as R ⁶⁴ , R ⁶⁵ and R ⁶⁶ can be the same as the aliphatic alkyl group having 1 to 20 carbon atoms in R ¹ etc. mentioned above. With respect to the alkylene groups having 1 to 10 carbon atoms represented by L ¹¹ to L ⁶⁴ and the aliphatic alkyl groups having 1 to 20 carbon atoms represented by R ⁶⁴ , R ⁶⁵ and R ⁶⁶ , one or more hydrogen atoms in these groups may be substituted or unsubstituted. In the case of being substituted, the substituents may be the same as the substituents which replace one or more hydrogen atoms of the aliphatic alkyl group represented by X ₁ above.

In terms of the balance between storage stability and low temperature adhesiveness of the composition, L ¹¹ to L ⁶⁴ are preferably alkylene groups having 1 to 5 carbon atoms, preferably linear alkylene groups having 1 to 3 carbon atoms or branched alkylene groups having 3 to 5 carbon atoms, and more preferably linear alkylene groups having 1 to 3 carbon atoms. The reason is that the above composition has a better balance between storage stability and low temperature adhesiveness.

Specific examples of the linear alkylene groups having 1 to 3 carbon atoms represented by L ¹¹ to L ⁶⁴ include methylene, ethylene (ethane-1,2-diyl), propylene (propane-1,3-diyl), etc. Specific examples of the branched alkylene groups having 3 to 5 carbon atoms represented by L ¹¹ to L ⁶⁴ include propane-1,1-diyl, propane-1,2-diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, pentane-1,1-diyl, pentane-1,2-diyl, pentane-1,3-diyl, pentane-1,4-diyl, etc.

^L11 and ^L12 in (A1) may be the same group or different groups. From the viewpoint of easy synthesis, they are preferably the same group. The reason is that the above composition has a better balance between storage stability and low-temperature adhesion. The same applies to ^L21 to ^L23 in (A2), ^L31 to ^L34 in (A3), ^L41 to ^L46 in (A4), ^L51 to ^L53 in (A5), and ^L61 to ^L64 in (A6).

In the present invention, it is preferred that R ⁶⁴ is an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. The reason is that the above composition has a better balance between storage stability and low-temperature adhesion.

Regarding the thiol compound, in terms of the balance between storage stability and curability of the composition, the molecular weight is preferably 100 to 1,000, more preferably 300 to 900, and particularly preferably 350 to 800. The reason is that the above composition will have a better balance between storage stability and low-temperature adhesiveness.

The thiol equivalent of the thiol compound, i.e., the value obtained by dividing the molecular weight of the thiol compound by the number of thiol groups (molecular weight of the thiol compound/number of thiol groups SH), is preferably 500 or less, more preferably 100 or more and 400 or less, and particularly preferably 120 or more and 300 or less. The reason is that by making the thiol equivalent of the thiol compound within the above range, the above composition has an excellent balance between storage stability and curing properties. The reason is that the above composition has an even better balance between storage stability and low-temperature adhesiveness.

As the thiol compound, a commercially available product may also be used. Examples of commercially available products of the thiol compound include: dodecanethiol (monofunctional thiol compound), Karenz MT (registered trademark) BD (trade name, bifunctional thiol compound, 1,4-bis(3-butylbutyryloxy)butane, Showa Denko KK), Karenz MT (registered trademark) NR (trade name, trifunctional thiol compound, 1,3,5-tris(3-butylbutyryloxyethyl)-1,3,5-tris(1H,3H,5H)-trione, Showa Denko KK), Karenz MT (registered trademark) PE (trade name, 4-functional thiol compound, pentaerythritol tetra(3-butylbutyrate), Showa Denko Co., Ltd.), EGMP-4 (trade name, 2-functional thiol compound, tetraethylene glycol bis(3-butylpropionate), SC Organic Chemical Co., Ltd.), TMMP (trade name, 3-functional thiol compound, trihydroxymethylpropane tri(3-butylpropionate), SC Organic Chemical Co., Ltd.), TE MPIC (trade name, trifunctional thiol compound, tris-[(3-butylpropionyloxy)-ethyl]-isocyanurate, SC Organic Chemicals (Co., Ltd.)), PEMP (trade name, quadrifunctional thiol compound, pentaerythritol tetrakis(3-butylpropionate), SC Organic Chemicals (Co., Ltd.)), DPMP (trade name, hexafunctional thiol compound, dipentaerythritol hexa(3-butylpropionate), SC Organic Chemicals (Co., Ltd.)), etc.

The content of the thiol component is preferably 1 to 80 parts by mass, more preferably 10 to 70 parts by mass, further preferably 20 to 50 parts by mass, and particularly preferably 25 to 45 parts by mass, in 100 parts by mass of the composition. The reason is that the composition has a better balance between storage stability and low-temperature adhesion.

The content of the thiol component is preferably 10 to 70 parts by mass, more preferably 20 to 50 parts by mass, and particularly preferably 25 to 45 parts by mass, based on 100 parts by mass of the solid component of the composition. The reason for this is that the composition has an excellent balance between storage stability and low-temperature adhesion.

The content of the thiol component is more preferably 10 parts by mass to 70 parts by mass, more preferably 20 parts by mass to 60 parts by mass, and particularly preferably 25 parts by mass to 50 parts by mass, based on 100 parts by mass of the total of compound 1, the thiol component, and the cyclic ether component. The reason for this is that the above composition has an excellent balance between storage stability and low-temperature adhesiveness.

The total number of thiol groups in the thiol component (unit: mol) is preferably 80 to 150, more preferably 90 to 120, and more preferably 95 to 110, when the total number of cyclic ether groups in the cyclic ether component in the composition is 100. The reason for this is that the above composition has excellent bonding strength.

3. Cyclic ether component The cyclic ether component refers to one or more components of a compound having a cyclic ether group (hereinafter, sometimes referred to as a cyclic ether compound). The cyclic ether compound is included in the composition as a component other than the above-mentioned compound 1 and the thiol compound. A compound having both a thiol group and a cyclic ether group does not belong to the cyclic ether compound but to the thiol component. As the cyclic ether group, any one having at least one ether bond in the ring structure may be used, and examples thereof include an epoxy group and an oxycyclobutyl group. That is, as the cyclic ether compound, examples thereof include an epoxy compound having an epoxy group and an oxycyclobutane compound having an oxycyclobutyl group. As a cyclic ether compound, it is preferred to use one that does not have the ability to generate a base group in terms of storage stability. In addition, compounds having a cyclic ether group and a hydroxyl group such as an ethylenic unsaturated group, a carboxyl group, an anhydride structure, and a phenol group are also considered to belong to the cyclic ether compound. As an ethylenic unsaturated group, examples include: an acryloyl group, a methacryloyl group, a vinyl group, etc. In addition, a compound having a cyclic ether group and an alkoxysilyl group is generally classified as a silane coupling agent and is considered not to belong to the above-mentioned cyclic ether compound. For example, compounds with both epoxy groups and alkoxysilyl groups, such as γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropylmethyldiethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, are usually classified as silane coupling agents and are not considered epoxy compounds.

The amount of cyclic ether groups in the cyclic ether compound can be appropriately set according to the required curability, etc. The amount of cyclic ether groups can be set to more than 1 per molecule of the cyclic ether compound, and can be set to more than 2 and less than 10, preferably more than 2 and less than 8. The reason is that the composition using such a cyclic ether compound has an excellent balance between preservation stability and curability. In addition, the reason is that when used as an adhesive, it will show excellent bonding ease and bonding properties. The cyclic ether group equivalent in the cyclic ether compound can be any amount that can achieve the desired storage stability and low-temperature adhesion, preferably 100 to 1,500, preferably 130 to 500, and particularly preferably 150 to 400. The reason is that the above composition will have a better balance between storage stability and low-temperature adhesion.

As one embodiment of the composition of the present invention, it is preferred to include an epoxy compound as the cyclic ether component. The reason is that the above composition will have a better balance between storage stability and low-temperature adhesion.

(1) Epoxy compounds Epoxy compounds include all compounds having an epoxy group as a cyclic ether group among cyclic ether compounds. For example, epoxy compounds include compounds containing an epoxy group and other cyclic ether groups such as cyclobutylene oxide in one molecule. Examples of such epoxy compounds include aromatic epoxy compounds, aliphatic epoxy compounds, and alicyclic epoxy compounds. (1-1) Aromatic epoxy compounds Aromatic epoxy compounds are compounds having an aromatic ring and an epoxy group but not an oxyolefin hydrocarbon structure. As such aromatic epoxy compounds, compounds having at least one aromatic hydrocarbon ring can also be used. Examples of the aromatic epoxy compound include: polyglycidyl ethers of polyphenols having at least one aromatic ring such as bisphenol A and bisphenol F or their alkylene oxide adducts; epoxy novolac resins (phenol novolac type epoxy compounds); polyglycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, or catechol; polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups such as phenyl dimethanol, phenyl diethanol, or phenyl dibutyl alcohol; polyglycidyl esters of polyacid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid, and trimellitic acid; divinylbenzene diepoxide, etc. In addition, a compound obtained by reacting an aromatic epoxy compound having two or more glycidyl ether groups on a main chain skeleton containing a rubber component and a group that can react with an epoxy group to form a covalent bond (hereinafter, also referred to as an "epoxy-reactive group") can also be cited. The epoxy equivalent of the aromatic epoxy compound can be any one that can obtain the required storage stability and low-temperature adhesion, preferably 100 to 500, preferably 130 to 400, and particularly preferably 150 to 350. The reason is that the above composition will have a better balance between storage stability and low-temperature adhesion.

As the aromatic epoxy compound, commercially available products can be used, for example, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, Oncoat EX-1020, Oncoat EX-1030, Oncoat EX-1040, Oncoat EX-1050, Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, Oncoat 1012 (manufactured by Nagase ChemteX Co., Ltd.); OGSOL PG-100, OGSOL EG-200, OGSOL EG-210, OGSOL EG-250 (manufactured by Osaka Gas Chemicals Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC Corporation); ESN-475V (manufactured by Tohto Kasei Corporation); YX8800 (manufactured by Mitsubishi Chemical Corporation); Marproof G-0105SA, Marproof G-0130SP (manufactured by NOF Corporation); EPICLON N-665, EPICLON HP-7200 (manufactured by DIC Corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (manufactured by Nippon Kayaku Co., Ltd.); Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (manufactured by ADEKA Corporation); TECHMORE VG-3101L (manufactured by Printec Corporation), etc.

In the present invention, the aromatic epoxy compound preferably comprises a polyglycidyl ether of a polyphenol having at least one aromatic ring or an alkylene oxide adduct thereof, and more preferably comprises a compound represented by the following general formula (14). The reason is that by including the above compound, the above composition has a better balance between storage stability and low-temperature adhesion, and the composition also has a better balance between ease of preparation and coating properties.

[Chemistry 14]

In the general formula (14), ^X11 can be exemplified by a group containing an aromatic hydrocarbon ring having 6 to 40 carbon atoms. One or more methylene groups in the group containing an aromatic hydrocarbon ring having 6 to 40 carbon atoms may be substituted by -O-, and one or more hydrogen atoms in the group containing an aromatic hydrocarbon ring having 6 to 40 carbon atoms may be substituted by a hydroxyl group. n11 represents an integer of 1 to 10.

As the aromatic hydrocarbon ring-containing group having 6 to 40 carbon atoms, a group obtained by removing "n11-1" hydrogen atoms from a monovalent aromatic hydrocarbon ring-containing group having 6 to 40 carbon atoms can be used.

The monovalent aromatic hydrocarbon ring-containing group having 6 to 40 carbon atoms represented by ^X11 may be any alkyl group containing an aromatic hydrocarbon ring but not containing a heterocyclic ring, and examples thereof include the same groups as the aromatic hydrocarbon ring-containing group having 6 to 40 carbon atoms used in _X1 , etc. More specifically, the aromatic hydrocarbon ring-containing group represented by ^X11 may be a group formed by combining an aryl group with a linear or branched alkyl group. For example, there can be mentioned: a group in which one or two or more hydrogen atoms in a straight or branched alkyl group are replaced by an aryl group, a group in which one or two or more methylene groups in a straight or branched alkyl group are replaced by a group obtained by removing one hydrogen atom from an aryl group, a group in which one or two or more hydrogen atoms in an aryl group are replaced by a straight or branched alkyl group, a residue of phenol novolac, etc. Furthermore, regarding the above-mentioned aryl group and alkyl group, the same groups as the aryl group and alkyl group used in the above-mentioned ^R1 , etc. can also be used.

n11 is preferably an integer of 1 to 7, more preferably an integer of 2 to 3, and particularly preferably 2. The reason is that the composition has a better balance between storage stability and low-temperature adhesion, and also has a better balance between ease of preparation and coating properties.

As the monovalent aromatic hydrocarbon ring-containing group having 6 to 40 carbon atoms represented by ^X11 , it is preferably a group in which one or more methylene groups in a linear or branched alkyl group having 6 to 20 carbon atoms are replaced by a group obtained by removing one hydrogen atom from an aryl group, and it is more preferably a group in which one or more methylene groups in a linear or branched alkyl group having 13 to 18 carbon atoms are replaced by a group obtained by removing one hydrogen atom from an aryl group. When n11 is 2, the compound represented by the general formula (14) is particularly preferably a group in which ^X11 is represented by the general formula (6-1). The reason for this is that the above-mentioned composition has a better balance between storage stability and low-temperature adhesiveness, and the composition also has a better balance between ease of preparation and coating properties.

[Chemistry 15] (In the general formula (6-1), R ^62-1 and R ^63-1 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, r1 and s1 each independently represent a number from 0 to 5, R ^61-1 represents a divalent aromatic ring-containing group represented by the following general formula (7); * represents a bond)

[Chemistry 16]

(In the general formula (7), R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ^{85 , R 86 and} R ⁸⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z ³ and Z ⁴ each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, the hydrogen atom in the alkylene group may be substituted by a methyl group or a halogen atom, t represents an integer from 0 to 5, u represents an integer from 0 to 30, and * represents a bonding site)

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^62-1 and R ^63-1 in the general formula (6-1) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl and the like.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ and R ⁸⁷ in the general formula (7) include the same groups as the alkyl group having 1 to 4 carbon atoms represented by R ^62-1 and R ^63-1 in the general formula (6-1).

Examples of the alkylene group having 1 to 4 carbon atoms represented by ^Z3 and ^Z4 in the general formula (7) include methine, methylene, ethylene, ethylene, n-propylene, propylene, isopropylene, methylethylene, n-butylene, butylene, isobutylene, tert-butylene, 1,2-dimethylethylene, 1-methylpropylene, and 2-methylpropylene.

Examples of the halogen atom substituting for the hydrogen atom in the alkylene group having 1 to 4 carbon atoms represented by Z ³ and Z ⁴ in the general formula (7) include fluorine atom, chlorine atom, bromine atom and iodine atom.

In the general formula (6-1), r1 and s1 are preferably independently integers of 0 to 3, preferably integers of 0 to 2, more preferably integers of 0 to 1, and most preferably 0. The reason is that the above composition has a better balance between storage stability and low-temperature adhesion.

In the general formula (7), preferably, R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ and R ⁸⁷ are hydrogen atoms or alkyl groups having 1 to 2 carbon atoms, i.e., hydrogen atoms, methyl groups or ethyl groups, and hydrogen atoms are preferred. The reason for this is that the above composition has a better balance between storage stability and low-temperature adhesiveness.

In the general formula (7), ^Z3 and ^Z4 are preferably independently an alkylene group having 1 to 4 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an alkylene group having 2 to 3 carbon atoms. The alkylene groups used in ^Z3 and ^Z4 are preferably alkylene groups such as methylene, ethylene, propylene, propylene, isopropylene, etc., that is, the aromatic epoxy compound is a compound having a bisphenol structure such as a bisphenol A structure, a bisphenol E structure, or a bisphenol F structure. The reason for this is that the above-mentioned composition will have a better balance between storage stability and low-temperature adhesiveness.

In general formula (7), t is preferably 0 to 3, and more preferably 0 to 1. Also, u is preferably 0 to 10, and more preferably 0 to 5, and more preferably 0 to 2, and most preferably 0. The reason for this is that the above composition has a better balance between storage stability and low-temperature adhesion.

(1-2) Aliphatic epoxides Aliphatic epoxides are compounds that have an epoxide group and do not contain an oxyethylene structure or an aromatic ring. Specific examples of such aliphatic epoxides include glycidyl ethers of aliphatic alcohols and polyglycidyl ethers of aliphatic polyols or their alkylene oxide adducts. More specifically, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerol, triglycidyl ether of trihydroxymethylpropane, tetraglycidyl ether of sorbitol, hexadecaned ether of dipentaerythritol, and tetraglycidyl ether of sorbitol. Glycidyl ethers of polyols such as diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and diglycidyl ether of neopentyl glycol, and polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyols such as propylene glycol, trihydroxymethylpropane, and glycerol, monoglycidyl ethers of aliphatic higher alcohols, or epoxidized polybutadiene, etc. In addition, compounds obtained by reacting aliphatic glycidyl ether-type epoxy compounds containing a rubber component and having two or more glycidyl ether groups on the main chain skeleton containing a group that can react with an epoxy group to form a covalent bond (hereinafter also referred to as an "epoxy-reactive group") can also be cited. Furthermore, as the above-mentioned aliphatic epoxy compound, a hydride of an aromatic epoxy compound such as hydrogen-added bisphenol A diglycidyl ether may be used. As the above-mentioned aliphatic epoxy compound, a compound having a structure in which an oxirane group is directly bonded to a cycloalkyl ring derived from an oxirane alkyl ring via a single bond as a structural unit and having a structure in which oxirane groups of an oxirane alkyl ring are polymerized with each other, such as 1,2-epoxy-4-(2-epoxyethylene) oxirane adduct of 2,2-bis(hydroxymethyl)-1-butanol, as a main chain structure may be used.

As the above-mentioned aliphatic epoxy compound, any one of an aliphatic ring-containing epoxy compound having an aliphatic ring such as an aliphatic hydrocarbon ring, an aliphatic heterocyclic ring, and a chain aliphatic epoxy compound without an aliphatic ring can be used, among which the aliphatic epoxy compound preferably includes an aliphatic ring-containing epoxy compound having an aliphatic hydrocarbon ring and a chain aliphatic epoxy compound. The reason is that the above-mentioned composition will become a better balance between storage stability and low-temperature adhesion. The amount of epoxy groups in the aliphatic epoxy compound can be any amount that can achieve the desired storage stability and low-temperature adhesion, and can be at least 1 per molecule of the aliphatic epoxy compound, preferably at least 1 and at most 6, preferably at least 1 and at most 4, preferably at least 1 and at most 3, and preferably 1 or 2. The reason is that the composition has a better balance between storage stability and low-temperature adhesion. The epoxy equivalent of the aliphatic epoxy compound can be any amount that can achieve the desired storage stability and low-temperature adhesion, preferably at least 100 and at most 500, preferably at least 130 and at most 400, and particularly preferably at least 150 and at most 350. The reason is that the above composition will have a better balance between storage stability and low-temperature adhesion.

As the aliphatic epoxy compound, commercially available products can be used, for example, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase ChemteX Co., Ltd.); Epolight M-1230, Epolight 40E, Epolight 100E, Epolight 200E, Epolight 400E, Epolight 70P, Epolight 200P, Epolight 400P, Epolight 1500NP, Epolight 1600, Epolight 80MF, Epolight 100MF (manufactured by Kyoeisha Chemical Co., Ltd.); ADEKA GLYCIROL ED-503, ADEKA GLYCIROL ED-503G, ADEKA GLYCIROL ED-506, ADEKA GLYCIROL ED-523T (manufactured by ADEKA Co., Ltd.), etc.

(1-3) Alicyclic epoxy compounds Specific examples of alicyclic epoxy compounds include polyglycidyl ethers of polyols having at least one alicyclic ring and a hydroxyl group directly bonded to the alicyclic ring, or compounds containing an oxyalkylene hydrocarbon structure such as oxirane or oxirane obtained by epoxidizing a compound containing a cyclohexene or cyclopentene ring with an oxidizing agent. The epoxide equivalent of the alicyclic epoxy compound may be any one that can obtain the desired storage stability and low-temperature adhesion, preferably 80 to 500, more preferably 100 to 300, and particularly preferably 120 to 250. The reason is that the above composition will have a better balance between storage stability and low-temperature adhesion.

Examples of the alicyclic epoxy compound include 3,4-epoxyepoxyhexylmethyl-3,4-epoxyepoxyhexanecarboxylate, 3,4-epoxy-1-methylepoxyhexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxyepoxyhexylmethyl-6-methyl-3,4-epoxyepoxyhexanecarboxylate, 3,4-epoxy-3-methylepoxyhexylmethyl-3,4-epoxy-3-methylepoxyhexanecarboxylate, 3,4-epoxy-5-methylepoxyhexylmethyl-3,4-epoxy-5-methylepoxyhexanecarboxylate, 2-(3,4-epoxyepoxyhexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-diol oxane, bis(3,4-epoxycyclohexylmethyl) adipate, methylenebis(3,4-epoxycyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene dicyclooxide, ethylenebis(3,4-epoxycyclohexane carboxylate ), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinene oxide, ε-caprolactone-modified 3,4-epoxycyclohexanecarboxylic acid 3',4'-epoxycyclohexyl methyl ester, etc.

Examples of commercially available products that can be preferably used as the alicyclic epoxy compound include those described in Japanese Patent No. 6103653 and the like.

(2) Oxycyclobutane compounds Specific examples of the above-mentioned oxycyclobutane compounds include the following compounds. Examples include: 3-ethyl-3-hydroxymethyloxycyclobutane, 3-(methyl)allyloxymethyl-3-ethyloxycyclobutane, (3-ethyl-3-oxycyclobutylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl-3-oxycyclobutylmethoxy)methyl]benzene, 4-methoxy-[1-(3-ethyl-3-oxycyclobutylmethoxy)methyl]benzene, [1-(3-ethyl-3-oxycyclobutylmethoxy)ethyl]phenyl ether, isobutoxymethyl (3-ethyl- 3-Oxycyclobutylmethyl) ether, isothiocyanate (3-ethyl-3-oxycyclobutylmethyl) ether, isothiocyanate (3-ethyl-3-oxycyclobutylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxycyclobutylmethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxycyclobutylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxycyclobutylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxycyclobutylmethyl) ether, dicyclopentene (3-ethyl-3-oxycyclobutylmethyl) ether 3-ethyl-3-oxocyclobutylmethyl) ether, tetrahydrofuranylmethyl (3-ethyl-3-oxocyclobutylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxocyclobutylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxocyclobutylmethyl) ether, tribromophenyl (3-ethyl-3-oxocyclobutylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxocyclobutylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxocyclobutylmethyl) ether, 2-hydroxy propyl (3-ethyl-3-oxocyclobutyl methyl) ether, butoxyethyl (3-ethyl-3-oxocyclobutyl methyl) ether, pentachlorophenyl (3-ethyl-3-oxocyclobutyl methyl) ether, pentabromophenyl (3-ethyl-3-oxocyclobutyl methyl) ether, iodophenyl (3-ethyl-3-oxocyclobutyl methyl) ether, 3,7-bis (3-oxocyclobutyl) -5-oxo-nonane, 3,3'- (1,3- (2-methylenyl) propanediyl bis (oxymethylene)) bis- (3-ethyloxycyclobutane), 1,4-bis[(3-ethyl-3-oxycyclobutylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxycyclobutylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxycyclobutylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxycyclobutylmethyl)ether, dicyclopentene bis(3-ethyl-3-oxycyclobutylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxycyclobutylmethyl)ether ) ether, tetraethylene glycol bis(3-ethyl-3-oxocyclobutyl methyl) ether, tricyclodecanediyl dimethylene(3-ethyl-3-oxocyclobutyl methyl) ether, trihydroxymethylpropane tris(3-ethyl-3-oxocyclobutyl methyl) ether, 1,4-bis(3-ethyl-3-oxocyclobutyl methoxy) butane, 1,6-bis(3-ethyl-3-oxocyclobutyl methoxy) hexane, pentaerythritol tris(3-ethyl-3-oxocyclobutyl methyl) ether, pentaerythritol tetra(3-ethyl- 3-Oxycyclobutylmethyl) ether, polyethylene glycol bis(3-ethyl-3-oxycyclobutylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxycyclobutylmethyl) ether, dipentaerythritol penta(3-ethyl-3-oxycyclobutylmethyl) ether, dipentaerythritol tetra(3-ethyl-3-oxycyclobutylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxycyclobutylmethyl) ether, caprolactone-modified dipentaerythritol penta(3-ethyl-3-oxycyclobutylmethyl) Ether, di-trihydroxymethylpropane tetra(3-ethyl-3-oxocyclobutyl methyl) ether, EO-modified bisphenol A bis(3-ethyl-3-oxocyclobutyl methyl) ether, PO-modified bisphenol A bis(3-ethyl-3-oxocyclobutyl methyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxocyclobutyl methyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxocyclobutyl methyl) ether, EO-modified bisphenol F(3-ethyl-3-oxocyclobutyl methyl) ether, etc.

(3) Cyclic ether compound As one embodiment of the composition of the present invention, the molecular weight of the cyclic ether compound is not particularly limited as long as it can obtain the desired curing properties, etc., and can be set to, for example, 50 or more and 20,000 or less. From the perspective of the balance between the storage stability and low-temperature adhesion of the composition, and the ease of coating and adhesion of the composition, it is more preferably 100 or more and 2,000 or less, and more preferably 200 or more and 1,500 or less.

When the compound is a polymer, the molecular weight refers to the weight average molecular weight (Mw). The weight average molecular weight can be determined by gel permeation chromatography (GPC) in terms of standard polystyrene.

The weight average molecular weight can be obtained by measuring, for example, using a GPC (LC-2000plus series) manufactured by JASCO Corporation, setting the elution solvent to tetrahydrofuran, setting the calibration curve to polystyrene standards of Mw1, 110,000, 707,000, 397,000, 189,000, 98,900, 37,200, 13,700, 9,490, 5,430, 3,120, 1,010, 589 (TSKgel standard polystyrene manufactured by Tosoh Corporation), and setting the measurement column to KF-804, KF-803, KF-802 (manufactured by Showa Denko Co., Ltd.). The measurement temperature can be set to 40°C, and the flow rate can be set to 1.0 mL/min.

As one embodiment of the composition of the present invention, it is preferred that the cyclic ether component includes a glycidyl ether type epoxy compound having a glycidyl ether group as the epoxy compound. The reason is that the above composition will be a better balance between storage stability and low-temperature adhesion. In addition, the reason is that since the glycidyl ether type epoxy compound has excellent curing properties, the composition will exhibit excellent curing properties. The composition of the present invention is preferably a cyclic ether component that includes at least one of an aromatic epoxy compound and an aliphatic epoxy compound as the epoxy compound, and preferably contains an aromatic epoxy compound. The reason is that the above composition will be a better balance between storage stability and low-temperature adhesion. In addition, it is better from the perspective of producing a product with an excellent balance between preservation stability and hardening properties.

As an embodiment of the composition of the present invention, from the perspective of the balance between the storage stability and low-temperature adhesiveness of the composition, it is preferred that the cyclic ether component includes a glycidyl ether type compound, and in particular, from the perspective of improving the curability of the composition, the content of the glycidyl ether type epoxy compound in 100 parts by mass of the cyclic ether component is preferably 30 parts by mass or more, preferably 80 parts by mass or more, and particularly preferably 90 parts by mass or more. In the present invention, it is preferred that the aromatic epoxy compound in 100 parts by mass of the cyclic ether component is 30 parts by mass or more, preferably 80 parts by mass or more, and particularly preferably 90 parts by mass or more. The reason is that the above-mentioned composition will be a better balance between storage stability and low-temperature adhesiveness.

In particular, among aromatic epoxy compounds, the content of the compound represented by the general formula (14) is preferably 30 parts by mass or more, preferably 40 parts by mass or more, particularly preferably 50 parts by mass or more, and particularly preferably 60 parts by mass or more in 100 parts by mass of the cyclic ether component. In particular, the compound wherein ^X11 in the formula (14) is a group represented by the general formula (6-1) is preferably 30 parts by mass or more, preferably 40 parts by mass or more, particularly preferably 50 parts by mass or more, and particularly preferably 60 parts by mass or more in 100 parts by mass of the cyclic ether component. The reason for this is that the above-mentioned composition has a better balance between storage stability and low-temperature adhesiveness.

When an aromatic epoxy compound and an aliphatic epoxy compound are used as the epoxy compound in the cyclic ether component, the content of the aliphatic epoxy compound is preferably 1 to 30 parts by mass, preferably 5 to 20 parts by mass, based on 100 parts by mass of the cyclic ether component. The reason is that the above composition will have a better balance between storage stability and low-temperature adhesion. When an aromatic epoxy compound and an alicyclic epoxy compound are used as the epoxy compound in the cyclic ether component, the content of the alicyclic epoxy compound is preferably 0.1 to 30 parts by mass, preferably 0.2 to 20 parts by mass, and preferably 0.3 to 10 parts by mass in 100 parts by mass of the cyclic ether component. The reason is that the above composition will have a better balance between storage stability and low-temperature adhesion.

According to the present invention, the content of the cyclic ether component is preferably 20 to 80 parts by mass, more preferably 40 to 75 parts by mass, out of 100 parts by mass of the total of the cyclic ether component and the thiol component. The reason is that the composition has a better balance between storage stability and low-temperature adhesion.

In terms of the balance between the storage stability and low-temperature adhesiveness of the composition, the content of the cyclic ether component is preferably 10 parts by mass to 90 parts by mass, more preferably 15 parts by mass to 80 parts by mass, further preferably 20 parts by mass to 75 parts by mass, and particularly preferably 30 parts by mass to 70 parts by mass, based on 100 parts by mass of the composition of the present invention.

In terms of the balance between the storage stability and low-temperature adhesiveness of the composition, the content of the cyclic ether component is preferably 10 parts by mass to 90 parts by mass, more preferably 15 parts by mass to 80 parts by mass, further preferably 20 parts by mass to 75 parts by mass, and particularly preferably 30 parts by mass to 70 parts by mass, based on 100 parts by mass of the solid components of the composition of the present invention.

4. Radical polymerizable components The above composition contains a cyclic ether component and a thiol component, and may also contain a radical polymerizable component as a curing component. The radical polymerizable component refers to one or more compounds having a radical polymerizable group (hereinafter also described as "radical polymerizable compounds"). Radical polymerizable compounds are superior to cyclic ether components in curing speed and other properties. Therefore, it is sometimes easy to set the bonding conditions according to the application by curing the radical polymerizable compounds with each other. Compound 1 can generate free radicals when generating a base group, so it is possible to polymerize the radical polymerizable compounds with each other without adding a radical polymerization initiator or adding a radical polymerization initiator in a smaller amount than usual. In addition, compounds with ethylenic unsaturated groups and thiol compounds, which are representative examples of free radical polymerizable compounds, are cured by alkali groups generated by alkali generators through Michel addition reactions. Therefore, it is easy to adjust the curing speed, durability of the cured product, etc.

As the free radical polymerizable compound, a compound having an ethylenically unsaturated group such as an acryl group, a methacryl group, or a vinyl group can be used. As the above-mentioned free radical polymerizable compound, a compound having one or more ethylenically unsaturated groups can be used, a monofunctional compound having one ethylenically unsaturated group, and a polyfunctional compound having two or more ethylenically unsaturated groups can be used. In addition, the free radical polymerizable compound is a compound having no cyclic ether group and no thiol group.

Examples of such free radical polymerizable compounds include polyethylene glycol diacrylate, polypropylene glycol diacrylate, propoxylated ethoxylated bisphenol A diacrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, tricyclodecanedimethanol diacrylate, 1,10-decanediol diacrylate, 1,9-nonanediol diacrylate, tripropylene glycol diacrylate, polytetramethylene glycol #650 diacrylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone-modified tri-(2-acryloyloxyethyl) isocyanurate, pentaerythritol triacrylate, trihydroxymethylpropane triacrylate, di-trihydroxymethylpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc. Furthermore, as the above-mentioned radical polymerizable compound, compounds described as radical polymerizable compounds in International Publication No. 2016/136752, Japanese Patent Publication No. 2016-210849, Japanese Patent Publication No. 2016-176009, etc. can also be used.

From the viewpoint of obtaining a compound with a superior curing speed, the number of functional groups such as ethylenically unsaturated groups in the radical polymerizable compound is preferably 2 to 8, more preferably 3 to 7, and particularly preferably 3 to 6.

As the radical polymerizable compound, a compound represented by the following general formula (15) can be preferably used because the low-temperature adhesiveness of the composition can be easily improved by using the compound.

[Chemistry 17]

(wherein, R ¹⁵⁰¹ represents a hydrogen atom or a methyl group, X ¹⁵ represents an unsubstituted or substituted aliphatic alkyl group having 1 to 40 carbon atoms and having the same valence as n15; an unsubstituted or substituted aromatic alkyl group having 6 to 40 carbon atoms and having the same valence as n15; an unsubstituted or substituted heterocyclic group having 2 to 40 carbon atoms and having the same valence as n15; or one or more methylene groups in the aliphatic alkyl group, the aromatic alkyl group or the heterocyclic group are substituted with a divalent group selected from the following group IV, and n15 represents an integer from 1 to 10; Group IV: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO ₂ -, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R''-)

The unsubstituted or substituted aliphatic alkyl group having the same valence as ⁿ¹⁵ , the unsubstituted or substituted aromatic hydrocarbon ring-containing group having the same valence as n15, and the unsubstituted or substituted heterocyclic group having the same valence as n15 represented by X15 may be the same groups as the unsubstituted or substituted aliphatic alkyl group having ₁ to 40 carbon atoms, the unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 40 carbon atoms, or the unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, having the same valence as n1 represented by X1 in the above general formula (A). As R' or R'' used in Group IV of the general formula (15), the same groups as R' or R'' used in Groups I-1, II-1, etc. can be used.

n15 is preferably in the same range as the preferred number of functional groups such as ethylenically unsaturated groups in the free radical polymerizable compound.

When the radical polymerizable component is a compound not containing an aromatic ring or a heterocyclic ring, the radical polymerizable component may be a compound represented by the above formula (15) and wherein ^X15 is an aliphatic alkyl group or one or more methylene groups of an aliphatic alkyl group are substituted with a group selected from Group IV under the condition that they are not adjacent to each other. For example, preferably, ^X15 is an aliphatic alkyl group or one or more methylene groups of an aliphatic alkyl group are substituted with -O-. The reason for this is that the radical polymerizable component is easy to purchase and the curing speed of the composition can be easily increased. In terms of the above aspects, in the case where ^X15 is an aliphatic alkyl group or one or more methylene groups of an aliphatic alkyl group are substituted with groups selected from Group IV, preferably the compound is represented by formula (15) and ^X15 is a branched alkyl group having 5 to 16 carbon atoms or a methylene group of the alkyl group is substituted with -O-.

When the radical polymerizable component contains an aromatic ring, it is preferred to use a compound represented by the above formula (15) in which X15 is a group exemplified ^above as ^X11 in the above formula (14) from the perspective of the ease of obtaining the radical polymerizable component or the curing speed of the composition. In this case, for example, ^X15 may also be a group represented by the above formula (6-1).

The content of the radical polymerizable component may be, for example, 0 parts by mass in 100 parts by mass of the total of the radical polymerizable component and the cyclic ether component, but when contained, it is preferably 1 part by mass to 70 parts by mass, more preferably 5 parts by mass to 40 parts by mass, and particularly preferably 8 parts by mass to 30 parts by mass. By making the content within this range, the composition can easily improve low-temperature adhesion.

The content of the radical polymerizable component may be, for example, 0 parts by mass in 100 parts by mass of the total of the radical polymerizable component, the cyclic ether component, and the thiol component. When contained, it is preferably 1 part by mass to 50 parts by mass, more preferably 5 parts by mass to 30 parts by mass, and particularly preferably 10 parts by mass to 20 parts by mass. When the content is within this range, low-temperature adhesion is likely to be improved.

5. Other resin components The present invention may also contain resin components other than cyclic ether components, free radical polymerizable components, and thiol components (hereinafter, also referred to as other resin components). Examples of other resin components include photosensitive resins. Specifically, examples include compounds having anionic polymerizable functional groups or resins whose curing temperatures are lowered by using alkali groups as catalysts. Specifically, examples include photosensitive resins that are cured by polymerization by irradiation with energy rays such as ultraviolet rays or curing resins whose curing temperatures are lowered. Examples of other resin components include phenolic resins, polyamide resins, polyurethane resins, nylon resins, polyester resins, and silicone resins. These resins can be used alone or in combination of two or more. When the composition of the present invention contains other resin components, the appropriate amount is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less, relative to 100 parts by mass of the total amount of the free radical polymerizable compound and the cyclic ether compound. The reason is that setting the amount of the thiol component and the cyclic ether component to a fixed amount or more can easily improve the storage stability and low-temperature adhesion of the composition.

6. Radical polymerization initiator The above composition may contain a radical polymerizable component and a radical polymerization initiator. As the radical polymerization initiator, for example, acetophenone compounds, benzoyl compounds, benzophenone compounds, 9-oxysulfide compounds described in International Publication No. 2018/012383, etc. can be used. The invention relates to a photoradical polymerization initiator of azo compounds and oxime ester compounds; a thermal radical polymerization initiator such as azo compounds, peroxides and persulfates; and a photoradical polymerization initiator described in Japanese Patent Laid-Open No. 2016-210849.

7. Solvent The above solvent is liquid at room temperature (25°C) and atmospheric pressure, and is capable of dispersing or dissolving each component in the composition. Therefore, even if it is liquid at room temperature (25°C) and atmospheric pressure, the above compound 1, cyclic ether component, thiol component, and free radical polymerizable component are not included in the solvent. As the above solvent, any of water and organic solvents can be used. In the present invention, the above solvent is preferably an organic solvent. The reason is that the above compound 1, cyclic ether component and thiol component are easily dissolved or dispersed.

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

The content of the solvent is preferably 1 to 70 parts by mass based on 100 parts by mass of the composition, and is more preferably 2 to 50 parts by mass in terms of ease of use and coating properties of the composition.

8. Additives The above composition contains compound 1, a thiol component, a cyclic ether component, and may contain a free radical polymerizable component and a solvent as needed, and may further contain an additive as needed. As the above-mentioned additives, those described as additives in International Publication No. 2019/117162 can be used, for example: inorganic compounds, pigments, latent epoxy curing agents, chain transfer agents, sensitizers, surfactants, silane coupling agents, melamine compounds, ultraviolet absorbers, antioxidants, antistatic agents, halogen compounds, phosphate compounds, phosphoamide compounds, fluororesins, metal oxides, flame retardants, hydrocarbons, lubricants, nucleating agents, crystallization promoters and other crystallization agents, silane coupling agents, rubber elasticity imparting agents such as flexible polymers, acid diffusion control agents, etc. can be cited.

The total content of the additives (but excluding inorganic compounds and colorants) is appropriately selected depending on the purpose of use and is not particularly limited. It is preferably set to 50 parts by mass or less relative to 100 parts by mass of the total of compound 1, cyclic ether component and thiol component. The reason is that the above-mentioned composition is likely to be more excellent in storage stability and low-temperature adhesion.

9. Applications The composition of the present invention can form a film with high storage stability and uniform film thickness, and has high hardening properties and no metal corrosion. In terms of these aspects, the composition of the present invention can be used particularly well as an adhesive or wiring protection. As a wiring protection, it can also be used as a protective material that directly contacts metal wiring.

In addition to adhesives and wiring protection, it can be used in the following applications: light-curing coatings or varnishes; coatings for metals; printed circuit boards; color filters for liquid crystal display elements of color displays such as color TVs, PC (PERSONAL COMPUTER) monitors, portable information terminals, and digital cameras; color filters for CCD (Charge Coupled Device) image sensors; electrode materials for plasma display panels; powder coatings (powder coatings); coating); printing ink; printing plate; adhesive; dental composition; gel coating; photoresist for electronic engineering; electroplating resist; etching resist; dry film; solder resist; used in the manufacture of color filters for various display purposes or in plasma display panels, electroluminescent display devices, and LCD (Liquid Crystal Display) Display, liquid crystal display device) manufacturing steps used to form its structure; used to package electrical and electronic components of the composition; solder resist; magnetic recording materials; micro-mechanical parts; waveguide; optical switch; coating mask; etching mask; color test system; glass fiber cable coating; screen printing template; used to produce three-dimensional objects by stereolithography; holographic recording material materials; image recording materials; microelectronic circuits; decolorizing materials; decolorizing materials for image recording materials; decolorizing materials for image recording materials using microcapsules; photoresist materials for printed wiring boards; photoresist materials for UV (Ultraviolet) and visible laser direct imaging systems; and photoresist materials or protective films used in the formation of dielectric layers in the sequential lamination of printed circuit substrates.

B. Cured product Next, the cured product of the present invention will be described. The cured product of the present invention is a cured product of the above-mentioned composition. According to the cured product of the present invention, since it is formed using the above-mentioned composition, it will be sufficiently bonded to the required place without causing deterioration of the surrounding components.

The contents of the above composition can be the same as those described in the above "A. Composition", so the description is omitted here. In addition, as a cured product, it is sufficient to be a high molecular weight body obtained by polymerization reaction of cyclic ether components, cyclic ether components and thiol components. The top view shape of the above cured product can be appropriately set according to the use of the above cured product, for example, it can be a pattern such as dots or lines.

The uses of the above-mentioned cured product can be the same as those described in the above-mentioned "A. Composition".

The method for producing the above-mentioned cured product is not particularly limited as long as it is a method that can form the cured product of the above-mentioned composition into a desired shape. As such a production method, for example, the production method described in the item "C. Production method of cured product" described below can be used.

C. Method for producing a cured product Next, the method for producing a cured product of the present invention is described. The method for producing a cured product of the present invention has a curing step of curing the above-mentioned composition. According to the present invention, since the above-mentioned composition is used to form the cured product, a cured product that is sufficiently bonded to the desired location without causing deterioration of the surrounding components can be obtained. According to the present invention, since the above-mentioned composition is used to form the cured product, a cured product that is sufficiently bonded to the desired location without causing deterioration of the surrounding components can be obtained. Each step of the method for producing the present invention is described in detail below.

1. Curing step The curing step is a step of curing the above-mentioned composition. As a method for curing the above-mentioned composition, any method can be used as long as the cyclic ether components in the above-mentioned composition, the cyclic ether component and the thiol component undergo polymerization reaction to obtain a high molecular weight body. As such a polymerization method, a method of subjecting the above-mentioned composition to light irradiation treatment to generate an alkali group or a free radical in compound 1 can be used. The light irradiated to the composition can be set to include light with a wavelength of 300 nm to 450 nm. As a light source for the above-mentioned light irradiation, for example, ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, etc. can be cited. As the above-mentioned irradiated light, laser light can also be used. As laser light, light with a wavelength of 340 to 430 nm can be used. As the light source of laser light, argon ion laser, helium-neon laser, YAG (Yttrium Aluminum Garnet) laser, semiconductor laser and the like which emit light in the visible to infrared region can also be used. Furthermore, when such lasers are used, the above-mentioned composition may contain a sensitizing dye which absorbs light in the visible to infrared region.

Since compound 1 has excellent photoalkali generation ability, when curing the composition of the present invention, after irradiating the above energy line, the coating film may be heated or not. Furthermore, if heating is performed, in terms of the curing rate, it is preferably heated to about 40 to 150°C. In the present invention, it can be set to a low temperature of 100°C or less, and further, it can be set to a low temperature of 80°C or less. In addition, when heating is performed, the heating time is usually 1 minute to 120 minutes.

2. Other steps The method for producing the hardened product may also include other steps as needed in addition to the hardening step. Examples of the other steps include: a developing step, which is to remove the unpolymerized part of the coating of the composition after the hardening step to obtain a patterned hardened product; a post-baking step, which is to heat the hardened product after the hardening step; a pre-baking step, which is to heat the composition before the hardening step to remove the solvent in the composition; and a step of forming a coating of the composition before the hardening step, etc.

As a method for removing the unpolymerized portion in the above-mentioned developing step, for example, a method of applying an alkaline developer to the unpolymerized portion can be cited. As the above-mentioned alkaline developer, tetramethylammonium hydroxide (TMAH) aqueous solution or potassium hydroxide aqueous solution, which are commonly used as alkaline developers, can be used. As the time point for implementing the above-mentioned developing step, it can be after the above-mentioned curing step. As the heating conditions in the above-mentioned post-baking step, as long as the strength of the cured product obtained by the curing step can be improved, for example, it can be set to 200°C or more and 250°C or less and 20 minutes to 90 minutes. As the heating conditions in the above-mentioned pre-baking step, any conditions are sufficient as long as the solvent in the composition can be removed, for example, it can be set to 70°C or more and 150°C or less and for 30 seconds to 300 seconds. As the method of applying the composition in the above-mentioned step of forming the coating film, a rotary coater, a roll coater, a rod coater, a die coater, a curtain coater, various printing, dipping and other known methods can be used. The above-mentioned coating film can be formed on a substrate. As the above-mentioned substrate, it can be appropriately set depending on the purpose of the cured product, and examples thereof include sodium glass, quartz glass, semiconductor substrate, wiring substrate, metal, paper, plastic, etc. Furthermore, the above-mentioned cured product can be peeled off from the substrate after being formed on the substrate and used, or can be transferred from the substrate to other adherends and used.

3. Others The cured product produced by the above-mentioned production method and its uses, etc., may be the same as those described in the above-mentioned "A. Composition".

The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are illustrative only. Any embodiment having substantially the same structure as the technical concept described in the scope of the patent application of the present invention and exerting the same effect is included in the technical scope of the present invention. [Example]

The present invention is described in further detail below with reference to embodiments and comparative examples, but the present invention is not limited to these embodiments and the like.

[Preparation Example 1] Synthesis of Br Salt Intermediate 1 1.0 eq. of 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethane-1-one was added to a flask and dissolved in tetrahydrofuran (theoretical yield 1,000 wt%). 1.1 eq. of pyridine was added and stirred at room temperature for 2 hours. The reaction solution was concentrated to obtain the target compound as a light yellow powder with a yield of 100%.

[Chemistry 18]

[Preparation Example 2] Synthesis of Br Salt Intermediate 2 In addition to the above Except that pyridine was changed to 3-quininol, the same operation as in Preparation Example 1 was carried out until the reaction was completed. The precipitate was recovered by vacuum filtration to obtain the target compound as a white powdery compound with a yield of 93%.

[Chemistry 19]

[Production Example 3] Synthesis of Br Salt Intermediate 3 The same operation as in Production Example 2 was performed except that 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethane-1-one described in Production Example 2 was replaced with 2-bromo-1-(4-(phenylthio)phenyl)ethane-1-one. The target compound was obtained as a white powdery compound with a yield of 77%.

[Chemistry 20]

[Production Example 4] Synthesis of Br Salt Intermediate 4 The same operation as in Production Example 2 was performed except that 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethane-1-one described in Production Example 2 was replaced with 2-bromo-1-(4-(phenylthio)phenyl)butane-1-one and the reaction conditions were changed to reflux for 5 hours. The target compound was obtained as a white powdery compound with a yield of 62%.

[Chemistry 21]

[Production Example 1A] Synthesis of Compound (1) 1.0 eq. of Br salt intermediate 1 was added to a flask and dissolved in chloroform (theoretical yield 500 wt%). In addition, 1.1 eq. of sodium tetraphenylborate was dissolved in ion exchange water (theoretical yield 500 wt%) in another container and the solution was added to the side of the flask. After stirring at room temperature for 1 hour, the reaction solution was separated into oil and water, and the aqueous layer was discarded. The reaction mixture was then washed with ion exchange water three times, and the organic layer was concentrated to obtain the target compound as a light yellow powder with a yield of 95%. The obtained compounds were analyzed using ¹ H-NMR and UV-Vis. The results are shown in Tables 1 and 2.

[Chemistry 22]

[Preparation Example 2A] Synthesis of Compound (2) The same operation as in Example 1 was performed except that the Br salt intermediate 1 described in Preparation Example 1A was replaced with the Br salt intermediate 2. The target compound was obtained as a pale yellow powdery compound with a yield of 89%. The obtained compound was analyzed using ¹ H-NMR and UV-Vis, and the results are shown in Tables 1 and 2.

[Chemistry 23]

[Preparation Example 3A] Synthesis of Compound (3) The same operation as in Example 1 was performed except that the Br salt intermediate 1 described in Preparation Example 1A was replaced with the Br salt intermediate 3. The target compound was obtained as a white powdery compound with a yield of 84%. The obtained compound was analyzed using ¹ H-NMR and UV-Vis, and the results are shown in Tables 1 and 2.

[Chemistry 24]

[Preparation Example 4A] Synthesis of Compound (4) The same operation as in Example 1 was performed except that the Br salt intermediate 1 described in Preparation Example 1A was replaced with the Br salt intermediate 4. The target compound was obtained as a white powdery compound with a yield of 80%. The obtained compound was analyzed using ¹ H-NMR and UV-Vis, and the results are shown in Tables 1 and 2.

[Chemistry 25]

[Table 1]

[Table 2] UV-Vis measurement data of compounds Maximum absorption wavelength λ _max [nm] Molar Absorption Coefficient ε (365 nm) Compound (1) 327 2230 Compound (2) 328 2390 Compound (3) 316 670 Compound (4) 328 2750

[Evaluation] The compositions shown in Tables 3 to 6 below were used to prepare the compositions. The numerical values in the tables represent weight percentages. The symbols of the components in the tables represent the following components. The structures of some of the following components are shown below.

(Cyclic ether component (epoxide)) A1: Compound represented by the following formula (A-1) (aromatic epoxy compound, glycidyl ether type, bisphenol A type epoxy compound) A2: Compound represented by the following formula (A-2) (aromatic epoxy compound, glycidyl ether type, bisphenol E type epoxy compound) A3: Compound represented by the following formula (A-3) (aromatic epoxy compound, glycidyl ether type, EPPN201, Nippon Kayaku Co., Ltd.) A4: Compound represented by the following formula (A-4) (aliphatic epoxy compound, glycidyl ether type, epoxy compound containing aliphatic ring with aliphatic hydrocarbon ring, hydrogenated bisphenol A type epoxy compound) A5: Compound represented by the following formula (A-5) (aliphatic epoxy compound, Daicel, Celloxide 2021P) A6: Compound represented by the following formula (A-6) (aliphatic epoxy compound, glycidyl ether type, chain aliphatic epoxy compound, ED-506 manufactured by ADEKA, epoxy equivalent 300 g/eq) A7: Acrylonitrile butadiene modified epoxy compound (glycidyl ether type epoxy compound, EPR-4030 manufactured by ADEKA, epoxy equivalent 365 g/eq) A8: Compound represented by the following formula (A-8) (4-hydroxybutyl acrylate glycidyl ether, aliphatic epoxy compound, glycidyl ether type, 4HBAGE) A9: A compound represented by the following formula (A-9) (aromatic epoxy compound, glycidyl ether type, compound having a bisphenol structure, a reaction product of a compound represented by the following formula (A-1) and acrylic acid

[Chemistry 26]

(Thiol component) B1: Compound represented by the following formula (B-1) (PEMP, molecular weight 488.64, functional group 4, SC Organic Chemicals) B2: Compound represented by the following formula (B-2) (TEMPIC, molecular weight 525.6, functional group 3, SC Organic Chemicals) B3: Compound represented by the following formula (B-3) (TMMP, molecular weight 398.5, functional group 3, SC Organic Chemicals)

[Chemistry 27]

(Free radical polymerizable component) C1: Compound represented by the following formula (C-1) (DPHA, Nippon Kayaku Co., Ltd.) C2: Compound represented by the following formula (C-2) (Viscoat#295, Osaka Organic Chemical Co., Ltd.) C3: Compound represented by the following formula (C-3) (ABE300, Shin-Nakamura Chemical Co., Ltd.) C4: Compound represented by the following formula (C-4) (4-HBA, Mitsubishi Chemical Co., Ltd.)

[Chemistry 28]

(Initiator: Photoinitiator) D1: Compound (1) (Compound 1 produced in Production Example 1A) D2: Compound (2) (Compound 1 produced in Production Example 2A) D3: Compound (3) (Compound 1 produced in Production Example 3A) D4: Compound (4) (Compound 1 produced in Production Example 4A) E1: Comparative compound 1 represented by the following formula

[Chemistry 29]

(Solvent) F1: γ-butyrolactone

[Evaluation method] Evaluate 1 to 5 as follows. The results are shown in Tables 3 to 6.

1. Adhesion after exposure The composition of each embodiment and comparative example was applied to a SUS (Steel Use Stainless, Japanese stainless steel standard) substrate by a dispenser in a manner to a thickness of 100 μm, and irradiated with 3,000 mJ/cm ² (cumulative light quantity in the wavelength range of 315 nm to 400 nm) by a high-pressure mercury lamp. After irradiation, it was left to stand for 1 hour under atmospheric pressure conditions at 25°C, then palpated and evaluated according to the following criteria. The results are shown in the following Tables 3 to 6. ++: Viscous and in a solid state (adherent solid). +: Viscous and in a viscous liquid state. -: No viscosity. Furthermore, the more stickiness a dimension has, the more adhesion it will have, which can be judged as the easier it is to connect the components.

2. Storage stability The compositions of each example and comparative example were prepared in a brown spiral tube using a 10 g vernier. The viscosity (Pa・s) at 25°C was measured and then stored at 23°C. Then, the viscosity at 25°C was measured again after 1 week. The viscosity increase rate (viscosity after storage/viscosity before storage × 100 (%)) was calculated and evaluated according to the following criteria. The results are shown in Tables 3 to 6 below. +: The viscosity increase rate is less than 110%. -: The viscosity increase rate exceeds 110%. The lower the viscosity increase rate, the better the storage stability.

3. Adhesion 1 The composition obtained in the embodiment and the comparative example was applied to a SUS substrate as the first substrate by a dispenser in such a manner that the thickness after curing (thickness of the adhesive layer) became 100 μm, and irradiated with 3,000 mJ/cm ² (cumulative light quantity in the wavelength range of 315 nm to 400 nm) by a high-pressure mercury lamp. Then, a SUS substrate as the second substrate was arranged on the coating film, and then heat-treated at 60°C for 60 minutes to obtain an evaluation sample. The peel strength was measured using the evaluation sample. The bonding of the first substrate and the second substrate was adjusted in such a manner that the contact area between the cured product of the composition and the first substrate and the second substrate became a circular shape with a diameter of 100 mm. A small tabletop tester EZ-X (manufactured by Shimadzu Corporation) was used as a measuring device to measure the compressive shear adhesion (MPa) at a measuring temperature of 25°C and a compression speed of 15 mm/min. The adhesion was evaluated according to the following criteria based on the measurement results. The results are shown in the following Tables 3 to 6. ++: Material damage or above 5 MPa +: Less than 5 MPa but hardened. -: Poor hardening, but exhibits an adhesion of less than 5 MPa. --: Unhardened or non-adhesive state, unable to bond. Furthermore, the greater the adhesion (MPa), the more sufficient the hardening can be judged, and the better the low-temperature adhesion.

4. Adhesion 2 The adhesion was evaluated in the same manner as in "3. Adhesion 1" above, except that a SUS substrate was placed on the coating film after light irradiation as the second substrate and then left at 25°C for 24 hours to obtain an evaluation sample. The results are shown in Tables 3 to 6 below.

5. Compatibility The compositions obtained in the examples and comparative examples were stirred for 30 minutes with a magnetic stirrer and then left to stand. The state of the composition was visually confirmed when the bubbles disappeared and evaluated according to the following criteria. +: Transparent. -: Turbid, with precipitates.

[Table 3] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Cyclic ether components A1 50 50 50 50 50 30 40 40 A2 20 A3 10 10 A4 A5 A6 A7 A8 A9 Thiol components B1 32 32 32 32 32 32 32 32 B2 B3 Free radical polymerizable ingredients C1 C2 C3 C4 Photoinitiator D1 5 5 D2 5 10 5 5 D3 5 D4 5 E1 Solvent F1 5 5 5 5 10 5 5 5 Reviews Adhesion after exposure + + + + + + + + Preserve stability + + + + + + + + Adhesion 1 ++ ++ ++ ++ ++ ++ ++ ++ Continuity 2 ++ ++ ++ ++ ++ ++ ++ ++ Compatibility + + + + + + + +

[Table 4] Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16 Cyclic ether components A1 45 49 45 45 45 45 A2 49 45 A3 A4 5 A5 1 A6 5 A7 1 A8 5 A9 5 Thiol components B1 32 32 32 32 30 30 30 30 B2 B3 Free radical polymerizable ingredients C1 10 15 C2 10 15 C3 C4 Photoinitiator D1 D2 5 5 5 5 5 5 5 5 D3 D4 E1 Solvent F1 5 5 5 5 5 5 5 5 Reviews Adhesion after exposure + + + + ++ ++ ++ ++ Preserve stability + + + + + + + + Adhesion 1 ++ ++ ++ ++ ++ ++ ++ ++ Continuity 2 ++ ++ ++ ++ ++ ++ ++ ++ Compatibility + + + + + + + +

[Table 5] Embodiment 17 Embodiment 18 Embodiment 19 Embodiment 20 Embodiment 21 Embodiment 22 Embodiment 23 Cyclic ether components A1 45 45 45 45 20 50 A2 A3 A4 50 A5 A6 A7 A8 A9 Thiol components B1 30 30 32 32 32 B2 30 B3 30 Free radical polymerizable ingredients C1 10 10 10 10 30 C2 C3 5 5 C4 5 5 5 Photoinitiator D1 5 5 5 5 5 5 1 D2 D3 D4 E1 Solvent F1 5 5 5 5 5 5 5 Reviews Adhesion after exposure ++ ++ ++ ++ + ++ + Preserve stability + + + + + + + Adhesion 1 ++ ++ ++ ++ + + + Continuity 2 ++ ++ ++ ++ + + + Compatibility + + + + + + +

[Table 6] Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 Comparison Example 6 Cyclic ether components A1 50 45 45 50 A2 A3 A4 A5 A6 A7 A8 A9 5 Thiol components B1 32 30 30 50 B2 B3 Free radical polymerizable ingredients C1 15 C2 10 C3 30 C4 Photoinitiator D1 D2 5 5 5 D3 D4 E1 5 5 5 Solvent F1 5 5 5 5 5 5 Reviews Adhesion after exposure + + + + + - Preserve stability - - - + + + Adhesion 1 -- -- -- -- -- -- Continuity 2 -- -- -- -- -- -- Compatibility + + + + + +

As can be seen from the evaluation results of the embodiments and comparative examples in Tables 3 to 6, the composition of the present invention has excellent curing properties at room temperature to low temperature and stability of adhesion after exposure after light irradiation, and has higher adhesion when bonding components to each other, and excellent low-temperature adhesion.

[Preparation Example 5] Synthesis of Br Salt Intermediate 5 The same operation as in Preparation Example 2 was performed except that 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethane-1-one described in Preparation Example 2 was changed to 2-bromo-1-(4-(phenylthio)phenyl)propane-1-one and the reaction conditions were changed to reflux for 3 hours. The target compound was obtained as a white powdery compound with a yield of 57%.

[Chemistry 30]

[Preparation Example 6] Synthesis of Br Salt Intermediate 6 The same operation as in Preparation Example 2 was performed except that 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethane-1-one described in Preparation Example 2 was replaced with 2-bromo-1-(9-ethyl-6-nitro-9H-carbazole-3-yl)butane-1-one and the reaction conditions were changed to reflux for 9 hours. The target compound was obtained as a yellow powder compound with a yield of 64%.

[Chemistry 31]

[Preparation Example 7] Synthesis of Br Salt Intermediate 7 The same operation as in Preparation Example 2 was performed except that 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethane-1-one described in Preparation Example 2 was replaced with 2-(6-(2-bromobutyl)-9-ethyl-9H-carbazole-3-yl)-2-oxoacetic acid methyl ester and the reaction conditions were changed to reflux for 9 hours. The target compound was obtained as a light yellow powder compound with a yield of 57%.

[Chemistry 32]

[Preparation Example 8] Synthesis of Br Salt Intermediate 8 The same operation as in Preparation Example 2 was performed except that 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethane-1-one described in Preparation Example 2 was replaced with 2-bromo-1-(7-(2-methylbenzoyl)-9H-fluoren-2-yl)butane-1-one and the reaction conditions were changed to reflux for 8 hours. The target compound was obtained as a yellow powder compound with a yield of 80%.

[Chemistry 33]

[Production Example 9] Synthesis of Br Salt Intermediate 9 The same operation as in Production Example 2 was performed except that 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethane-1-one described in Production Example 2 was replaced with 2-(7-(2-bromobutylyl)-9H-fluoren-2-yl)-2-oxoacetic acid methyl ester and the reaction conditions were changed to reflux for 8 hours. The target compound was obtained as a yellow powder compound with a yield of 75%.

[Chemistry 34]

[Preparation Example 10] Synthesis of Br intermediate 10 The same procedure as in Preparation Example 2 was followed except that 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethane-1-one described in Preparation Example 2 was replaced with 2-bromo-1-(4-bromo-11-(2-ethylhexyl)-11H-benzo[a]carbazole-8-yl)butane-1-one and the reaction conditions were changed to reflux for 9 hours. The target compound was obtained as a white powdery compound with a yield of 33%.

[Chemistry 35]

[Preparation Example 11] Synthesis of Br Salt Intermediate 11 Except that 3-quininol described in Preparation Example 4 was changed to 3-quininone, the same operation as in Preparation Example 4 was performed until the reaction. The precipitate was recovered by vacuum filtration, and the target compound was obtained as a white powdery compound with a yield of 60%.

[Chemistry 36]

[Preparation Example 12] Synthesis of Br Salt Intermediate 12 except that the 3-quininol described in Preparation Example 4 was replaced by 4-cyano Except for pyridine, the same operation as in Preparation Example 4 was carried out until the reaction was completed. The precipitate was recovered by vacuum filtration, and the target compound was obtained as a white powdery compound with a yield of 65%.

[Chemistry 37]

[Preparation Example 13] Synthesis of Br Salt Intermediate 13 The same procedure as in Preparation Example 2 was followed except that 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethane-1-one described in Preparation Example 2 was replaced with 4-(bromoethyl)-7-methoxy-2H-oxazolidin-2-one. The target compound was obtained as a light yellow powdery compound with a yield of 93%.

[Chemistry 38]

[Preparation Example 14] Synthesis of Br Salt Intermediate 14 The same operation as in Preparation Example 3 was performed except that 3-quininol described in Preparation Example 3 was replaced with 1-methylpiperidine. The target compound was obtained as a white powdery compound with a yield of 87%.

[Chemistry 39]

[Production Example 5A] Synthesis of Compound (6) The same operation as in Production Example 1A was performed except that the Br salt intermediate 1 described in Production Example 1A was replaced with the Br salt intermediate 5. The target compound was obtained as a white powdery compound with a yield of 67%.

[Chemistry 40]

[Preparation Example 6A] Synthesis of Compound (7) The same operation as in Preparation Example 1A was performed except that the Br salt intermediate 1 described in Preparation Example 1A was replaced with Br salt intermediate 6. The target compound was obtained as a white powdery compound with a yield of 78%.

[Chemistry 41]

[Production Example 7A] Synthesis of Compound (8) The same operation as in Production Example 1A was performed except that the Br salt intermediate 1 described in Production Example 1A was replaced with Br salt intermediate 7. The target compound was obtained as a white powdery compound with a yield of 70%.

[Chemistry 42]

[Preparation Example 8A] Synthesis of Compound (9) The same operation as in Preparation Example 1A was performed except that the Br salt intermediate 1 described in Preparation Example 1A was replaced with Br salt intermediate 8. The target compound was obtained as a white powdery compound with a yield of 68%.

[Chemistry 43]

[Preparation Example 9A] Synthesis of Compound (10) The same operation as in Preparation Example 1A was performed except that the Br salt intermediate 1 described in Preparation Example 1A was replaced with Br salt intermediate 9. The target compound was obtained as a white powdery compound with a yield of 72%.

[Chemistry 44]

[Preparation Example 10A] Synthesis of Compound (11) The same operation as in Preparation Example 1A was performed except that the Br salt intermediate 1 described in Preparation Example 1A was replaced with the Br salt intermediate 10. The target compound was obtained as a yellow solid compound with a yield of 86%.

[Chemistry 45]

[Production Example 11A] Synthesis of Compound (12) The same operation as in Production Example 3A was performed except that the sodium tetraphenylborate described in Production Example 3A was replaced with sodium phenyl (2,4,6-trimethylbenzyl) phosphinate. The target compound was obtained as a white powdery compound with a yield of 92%.

[Chemistry 46]

[Preparation Example 12A] Synthesis of Compound (13) The same operation as in Preparation Example 1A was performed except that the Br salt intermediate 1 described in Preparation Example 1A was replaced with the Br salt intermediate 11. The target compound was obtained as a white powdery compound with a yield of 68%.

[Chemistry 47]

[Preparation Example 13A] Synthesis of Compound (14) The same operation as in Preparation Example 1A was performed except that the Br salt intermediate 1 described in Preparation Example 1A was replaced with the Br salt intermediate 12. The target compound was obtained as a white powdery compound with a yield of 67%.

[Chemistry 48]

[Production Example 14A] Synthesis of Compound (15) The same operation as in Production Example 2A was performed except that the sodium tetraphenylborate described in Production Example 2A was replaced with sodium thiocyanate. The target compound was obtained as a white powdery compound with a yield of 80%.

[Chemistry 49]

[Production Example 15A] Synthesis of Comparative Compound 2 The same operation as in Production Example 1A was performed except that the Br salt intermediate 1 described in Production Example 1A was replaced with Br salt intermediate 13. The target compound was obtained as a light yellow powder with a yield of 96%.

[Chemistry 50]

[Production Example 16A] Synthesis of Comparative Compound 3 The same operation as in Production Example 1A was performed except that the Br salt intermediate 1 described in Production Example 1A was replaced with Br salt intermediate 14. The target compound was obtained as a white powdery compound with a yield of 98%.

[Chemistry 51]

The compounds obtained in Production Examples 5A to 16A were analyzed using ¹ H-NMR and UV-Vis. The results are shown in Tables 7 and 8. In addition, compound (5) in Tables 7 and 8 represents Br salt intermediate 2.

[Table 7]

[Table 8] UV-Vis measurement data of compounds Maximum absorption wavelength λ _max [nm] Molar Absorption Coefficient ε (365 nm) Compound (5) 329 2290 Compound (6) 323 1000 Compound (7) 367 19730 Compound (8) 345 9200 Compound (9) 328 420 Compound (10) 337 3310 Compound (11) 350 8480 Compound (12) 316 790 Compound (13) 328 2750 Compound (14) 328 2750 Compound (15) 329 2300 Comparison with compound 2 332 2390 Comparison with compound 3 317 1380

The compositions shown in Tables 9 to 13 below were used to prepare the compositions. The numerical values in the tables represent weight percentages. The symbols of the components in the tables represent the following components. The structures of some of the following components are shown below.

(Cyclic ether component (epoxy compound)) A10: Compound represented by the following formula (A-10) (aliphatic epoxy compound, glycidyl ether type, ED-523T manufactured by ADEKA Co., Ltd.) A11: Compound represented by the following formula (A-11) (aliphatic epoxy compound, glycidyl ether type, Epogosey 2EH manufactured by Yokkaichi Kogyo Co., Ltd.) A12: Compound represented by the following formula (A-12) (aliphatic epoxy compound, ED-505 manufactured by ADEKA Co., Ltd.) A13: Compound represented by the following formula (A-13) (aliphatic epoxy compound, glycidyl ether type, DY-022 manufactured by Nagase ChemteX Co., Ltd.)

[Chemistry 52]

(Free radical polymerizable component) C5: Compound represented by the following formula (C-5) (KAYARAD DPCA-60 manufactured by Nippon Kayaku Co., Ltd.)

[Chemistry 53]

(Initiator: photoinitiator) D5: Compound (5) (Compound 1 produced in Preparation Example 2) D6: Compound (6) (Compound 1 produced in Preparation Example 5A) D7: Compound (7) (Compound 1 produced in Preparation Example 6A) D8: Compound (8) (Compound 1 produced in Preparation Example 7A) D9: Compound (9) (Compound 1 produced in Preparation Example 8A) D10: Compound (10) (Compound 1 produced in Preparation Example 9A) D11: Compound (11) (Compound 1 produced in Preparation Example 10A) D12: Compound (12) (Compound 1 produced in Preparation Example 11A) D13: Compound (13) (Compound 1 produced in Preparation Example 12A) D14: Compound (14) (Compound 1 produced in Preparation Example 13A) D15: Compound (15) (Compound 1 produced in Production Example 14A) E2: Comparative Compound 2 produced in Production Example 15A E3: Comparative Compound 3 produced in Production Example 16A

(Solvent) F2: DMSO

The above evaluations 1 to 5 were performed on the compositions shown in Tables 9 to 13. The results are shown in Tables 9 to 13. In addition, the slash indicates that no evaluation was performed.

[Table 9] Embodiment 24 Embodiment 25 Embodiment 26 Embodiment 27 Embodiment 28 Embodiment 29 Embodiment 30 Embodiment 31 Cyclic ether components A1 45 50 50 50 50 50 50 50 Thiol components B1 30 32 32 32 32 32 32 32 Free radical polymerizable ingredients C1 10 C5 5 Photoinitiator D2 5 D5 5 D6 5 D7 5 D8 5 D9 5 D10 5 D11 5 Solvent F1 5 5 5 5 5 5 5 5 Reviews Adhesion after exposure ++ + + + + + + Preserve stability + + + + + + + Adhesion 1 ++ ++ + + + + + Continuity 2 ++ ++ + + + + + Compatibility + + + + + + +

[Table 10] Embodiment 32 Embodiment 33 Embodiment 34 Embodiment 35 Embodiment 36 Embodiment 37 Embodiment 38 Embodiment 39 Cyclic ether components A1 50 50 50 50 45 45 45 45 Thiol components B1 32 32 32 32 30 30 30 30 Free radical polymerizable ingredients C1 10 10 10 10 C4 5 5 5 5 Photoinitiator D4 5 D5 5 D6 5 D7 5 D12 5 D13 5 D14 5 D15 5 Solvent F1 5 5 5 5 5 5 5 5 Reviews Adhesion after exposure + + + ++ ++ ++ Preserve stability + + + + + + Adhesion 1 + + + ++ ++ ++ Continuity 2 + + + ++ ++ ++ Compatibility + + + + + +

[Table 11] Embodiment 40 Embodiment 41 Embodiment 42 Embodiment 43 Embodiment 44 Embodiment 45 Embodiment 46 Embodiment 47 Cyclic ether components A1 45 45 45 45 45 45 45 45 Thiol components B1 30 30 30 30 30 30 30 30 Free radical polymerizable ingredients C1 10 10 10 10 10 10 10 10 C4 5 5 5 5 5 5 5 5 Photoinitiator D8 5 D9 5 D10 5 D11 5 D12 5 D13 5 D14 5 D15 5 Solvent F1 5 5 5 5 5 5 5 5 Reviews Adhesion after exposure ++ ++ ++ ++ ++ ++ ++ Preserve stability + + + + + + + Adhesion 1 ++ ++ ++ ++ ++ ++ ++ Continuity 2 ++ ++ ++ ++ ++ ++ ++ Compatibility + + + + + + +

[Table 12] Embodiment 48 Embodiment 49 Embodiment 50 Embodiment 51 Embodiment 52 Embodiment 53 Embodiment 54 Embodiment 55 Cyclic ether components A1 30 30 30 55 A2 30 30 30 55 A10 20 20 A11 5 5 5 5 5 5 A12 20 20 A13 20 20 Thiol components B1 40 40 40 40 40 40 40 40 Photoinitiator D4 5 5 5 5 5 5 5 5 Solvent F1 5 5 5 5 5 5 5 5 Reviews Adhesion after exposure + + + + + + + + Preserve stability + + + + + + + + Adhesion 1 + + + + + + + + Continuity 2 + + + + + + + + Compatibility + + + + + + + +

[Table 13] Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Cyclic ether components A1 50 50 45 45 Thiol components B1 32 32 30 30 Free radical polymerizable ingredients C1 10 10 C4 5 5 Photoinitiator E2 5 5 E3 5 5 Solvent F1 5 5 F2 10 10 Reviews Adhesion after exposure + ++ + ++ Preserve stability - + - + Adhesion 1 - - - - Continuity 2 - - - - Compatibility - + - +

Claims (11)

A composition comprising a cyclic ether component, a thiol component, and a compound represented by the following general formula (1): (wherein Ar is an aromatic ring group, A is a a pyridine skeleton, ^B- is a monovalent anion, ^R1 and ^R2 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic alkyl group, the aromatic alkyl group or the heterocyclic group are substituted with a divalent group selected from the following group I-1, and the substituent replacing one or more hydrogen atoms in the aliphatic alkyl group having a substituent, the aromatic alkyl group having a substituent and the heterocyclic group having a substituent is an atom or group selected from the following group II-1; Group I-1: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO ₂ -, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'-, or -SiR'R''-; Group II-1: halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH ₂ , -C(R')=N-OH, -COOH, or -SO ₃ H; R' and R'' each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group, and when there are plural R' or R'', they may be the same or different). The composition of claim 1, wherein the aromatic cyclic group Ar is an aromatic cyclic group represented by the following general formula (Ara1), (Arb1) or (Arc1); [Chemical 2] ₍ wherein, ^Y1 is a sulfur atom, CO, SO, _SO2 , ^CR1012 , ^PR102 or ^NR102 , ^Y2 is a single bond, an oxygen atom, a sulfur atom, CO, SO, SO2, _CR1022 ^{, PR102} _or ^NR101 , ^Y3 is an oxygen atom, a sulfur atom, CO, SO, _SO2 , ^{CR1022 , PR102} or ^NR101 , _R ¹⁰¹ each independently represents an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic alkyl group, the aromatic alkyl group or the heterocyclic group are substituted with a divalent group selected from the following group I-2, R ^R102 each independently represents a hydrogen atom, an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic alkyl group, the aromatic alkyl group or the heterocyclic group are substituted with a divalent group selected from the following group I-2; ^R31 , ^R32 , ^R41 , ^R42 , ^R51 , ^R52 and ^R53 each independently represent a halogen atom, a nitro group, a cyano group, ^-OR121 , ^-COR121 , ^-OCOR121 , ^-COOR121 , ^-SR121 , -SOR ¹²¹ , -SO ₂ R ¹²¹ , -NR ¹²² R ¹²³ , -NR ¹²² COR ¹²³ , -CONR ¹²² R ¹²³ , an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or one or more methylene groups in the aliphatic alkyl group, the aromatic alkyl group or the heterocyclic group are substituted with a divalent group selected from the following group I-2, However, a plurality of R ⁴¹ may be bonded to each other to form a ring, and the ring is unsubstituted or substituted, R ¹²¹ , R ¹²² and R ^R121 , R122 or R123 each independently represent a hydrogen atom, an unsubstituted or substituted aliphatic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic alkyl group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the above-mentioned aliphatic alkyl group, the above-mentioned aromatic alkyl group or the above-mentioned heterocyclic group are substituted with a divalent group selected from the following group I-2. When there are plural numbers of ^R121 , ^{R122 or R123, they may be the same or different. The above-mentioned aliphatic alkyl group having a substituent, the above-mentioned aromatic alkyl group having a substituent, the above-mentioned heterocyclic group having a substituent, and the plural numbers of R121, R122 or} R123 may be substituted with a divalent group selected from the following group I-2. The substituents of one or more hydrogen atoms in the ring formed by mutual bonding of ⁴¹ are atoms or groups selected from the following Group II-2, a1 is an integer of 0 to 5, a2 is an integer of 0 to 4, b1 is an integer of 0 to 4, b2 is an integer of 0 to 3, c1 is an integer of 0 to 4, c2 is an integer of 0 to 1, * represents a bonding site; Group I-2: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO ₂ -, -NR'-, -NR'--CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R''-; Group II-2: halogen atom, cyano group, nitro group, -CO-H, -OH, -SH, -NH ₂ , -C(R')=N-OH, -COOH or -SO ₃ H; R' and R'' each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group, and when there are multiple R' or R'', they may be the same or different). The composition of claim 1 or 2, wherein the content of the cyclic ether component is 20 parts by mass or more and 80 parts by mass or less in 100 parts by mass of the total of the cyclic ether component and the thiol component. The composition of claim 1 or 2, wherein the content of the compound represented by the general formula (1) is 3 parts by mass or more and 15 parts by mass or less in 100 parts by mass of the total of the cyclic ether component, the thiol component and the compound represented by the general formula (1). The composition of claim 1 or 2, wherein the content of the compound represented by the general formula (1) is 5 parts by mass or more and 30 parts by mass or less in 100 parts by mass of the total of the thiol component and the compound represented by the general formula (1). The composition of claim 1 or 2, wherein the cyclic ether component comprises an epoxy compound. The composition of claim 6, wherein the epoxy compound comprises an aromatic epoxy compound. The composition of claim 1 or 2, wherein the thiol component is a compound having two or more primary thiol groups. The composition of claim 1 or 2, wherein the composition comprises a free radical polymerizable component. A hardened material, which is a hardened material of the composition according to any one of claims 1 to 9. A method for producing a hardened article, comprising the following hardening step: hardening the composition of any one of claims 1 to 9.