WO2021261498A1 - 組成物、硬化物及び硬化物の製造方法 - Google Patents

組成物、硬化物及び硬化物の製造方法 Download PDF

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WO2021261498A1
WO2021261498A1 PCT/JP2021/023678 JP2021023678W WO2021261498A1 WO 2021261498 A1 WO2021261498 A1 WO 2021261498A1 JP 2021023678 W JP2021023678 W JP 2021023678W WO 2021261498 A1 WO2021261498 A1 WO 2021261498A1
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group
compound
substituent
carbon atoms
unsubstituted
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English (en)
French (fr)
Japanese (ja)
Inventor
尭大 井上
和貴 友田
泰延 大野
拓也 松本
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Adeka Corp
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Adeka Corp
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Priority to KR1020227027473A priority Critical patent/KR20230029579A/ko
Priority to JP2022532503A priority patent/JPWO2021261498A1/ja
Priority to CN202180016000.9A priority patent/CN115151591B/zh
Publication of WO2021261498A1 publication Critical patent/WO2021261498A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D453/00—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids
    • C07D453/02—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids containing not further condensed quinuclidine ring systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/66—Mercaptans
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds

Definitions

  • the present disclosure relates to a composition, a cured product thereof, and a method for producing the cured product.
  • a photosensitive resin composition is a photosensitive resin to which a photopolymerization initiator is added, and can be polymerized and cured or developed by irradiation with energy rays (light). Therefore, photocurable inks and photosensitive printing It is used in plates, various types of photoresists, photocurable adhesives, and the like.
  • Photopolymerization initiators are divided into photoradical generators, photoacid generators, and photobase generators, depending on the active species generated by energy ray (light) irradiation.
  • the photoradical generator has advantages such as a high curing rate and no active species remaining after curing, but has a disadvantage that a layer or the like that blocks oxygen must be provided in the curing of the thin film because the curing is inhibited by oxygen.
  • the photoacid generator has an advantage that it is not inhibited by oxygen, but has a disadvantage that the residual active acid causes corrosion of the metal substrate and denatures the cured resin.
  • Photobase generators are attracting attention because they are less likely to cause problems such as inhibition of curing by oxygen and corrosion by residual active species.
  • ionic type Patent Document 1
  • non-ionic type Patent Documents 2 and 3 are known, respectively.
  • the resin composition containing the ionic photobase generator has a problem that the storage stability is low. Further, the conventional resin composition containing a photobase generator has a problem that the degree of freedom of adhesive conditions is low, such as the need for high-temperature heating for curing after exposure.
  • the present disclosure has been made in view of the above problems, and an object of the present disclosure is to provide a curable composition having excellent storage stability and low-temperature adhesiveness.
  • the present inventor has conducted diligent studies and found that by combining a specific base generator, a thiol component, and a cyclic ether component, both storage stability and low-temperature adhesiveness can be achieved, and the present disclosure has been completed. rice field.
  • the present disclosure describes the cyclic ether component and Thiol component and The compound represented by the following general formula (1) and A composition having the above is provided.
  • Ar is an aromatic ring group
  • A is a group having a quinuclidine skeleton
  • B - is a monovalent anion
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms, and 6 carbon atoms.
  • the substituent that replaces 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 "-.
  • R'and R independently represent hydrogen atoms or unsubstituted aliphatic hydrocarbon groups, and when a plurality of R'or R'are present, they may be the same or different.
  • composition of the present disclosure the balance between storage stability and low temperature adhesiveness is excellent.
  • the aromatic ring group Ar is an aromatic ring group represented by the following general formula (Ara1), (Arb1) or (Arc1). This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • Y 1 is a sulfur atom, CO, SO, SO 2 , CR 101 2 , PR 102 or NR 102 .
  • Y 2 is a single bond, oxygen atom, sulfur atom, CO, SO, SO 2 , CR 102 2 , PR 102 or NR 101 .
  • Y 3 is an oxygen atom, a sulfur atom, CO, SO, SO 2 , CR 102 2 , PR 102 or NR 101 .
  • R 101 is an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms and an aromatic having an unsubstituted or substituent having 6 to 20 carbon atoms, respectively.
  • it represents a group in which one or more of the methylene groups in the above heterocyclic-containing group is replaced with a divalent group selected from the following group I-2.
  • R 31 , R 32 , R 41 , R 42 , R 51 , R 52 and R 53 are independently halogen atoms, nitro groups, cyano groups, -OR 121 , -COR 121 , -OCOR 121 , -COOR 121, respectively.
  • One or more of the containing group or the methylene group in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group or the heterocyclic ring-containing group is replaced with a divalent group selected from the following group I-2.
  • a divalent group selected from the following group I-2 Represents a group However, a plurality of R 41s may be bonded to each other to form a ring, and the ring is unsubstituted or has a substituent.
  • R 121 , R 122 and R 123 are each independently a hydrogen atom, an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms, and an unsubstituted or unsubstituted group having 6 to 20 carbon atoms.
  • a group in which one or more of the methylene groups in the group hydrocarbon ring-containing group or the above heterocyclic ring-containing group is replaced with a divalent group selected from the following group I-2 is represented by R 121 , R 122 or R 123. If there are multiple of each, they may be the same or different.
  • An aliphatic hydrocarbon group having the above substituent, an aromatic hydrocarbon ring-containing group having the substituent, a heterocyclic ring-containing group having the above substituent, and a plurality of R 41s are mutually exclusive.
  • the substituent that replaces one or more of the hydrogen atoms in the ring formed by bonding is an atom or group selected from the following group II-2.
  • a1 is an integer from 0 to 5
  • a2 is an integer from 0 to 4
  • b1 is an integer from 0 to 4
  • b2 is an integer from 0 to 3
  • c1 is an integer from 0 to 4
  • c2 is an integer from 0 to 1 and * Represents the joint location.
  • 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 "-.
  • R'and R independently represent hydrogen atoms or unsubstituted aliphatic hydrocarbon groups, and when a plurality of R'or R'are present, they may be the same or different.
  • the content of the cyclic ether component is preferably 20 parts by mass or more and 80 parts by mass or less in a total of 100 parts by mass of the cyclic ether component and the thiol component. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the content of the compound represented by the general formula (1) is 3 in a total of 100 parts by mass of the cyclic ether component, the thiol component and the compound represented by the general formula (1). It is preferably 5 parts by mass or more and 15 parts by mass or less. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the content of the compound represented by the general formula (1) is 5 parts by mass or more and 30 parts by mass in a total of 100 parts by mass of the thiol component and the compound represented by the general formula (1). It is preferably less than or equal to a portion. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the cyclic ether component contains an epoxy compound. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the epoxy compound contains an aromatic epoxy compound. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the thiol component is a compound having two or more primary thiol groups. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the above composition contains a radically polymerizable component. This is because the composition may be excellent in the balance between storage stability and low-temperature adhesiveness, and the degree of freedom in adhesive conditions can be increased.
  • the present disclosure provides a cured product of the above composition. According to the present disclosure, since it is formed by using the above-mentioned composition, it is sufficiently adhered at a desired place without causing deterioration of peripheral members.
  • the present disclosure provides a method for producing a cured product, which comprises a curing step of curing the composition. According to the present disclosure, since it is formed by using the above-mentioned composition, it is possible to obtain a sufficiently adhered cured product at a desired place without causing deterioration of peripheral members.
  • the present disclosure provides a composition having an excellent balance between storage stability and low-temperature adhesiveness, a cured product thereof, and a method for producing a cured product using the same.
  • the present disclosure relates to a composition, a cured product using the composition, and a method for producing the cured product.
  • composition of the present disclosure contains a cyclic ether component, a thiol component, and a compound represented by the above general formula (1).
  • the compound represented by the general formula (1) (hereinafter, may be referred to as compound 1), and the thiol component and the cyclic ether component are contained, so that the storage stability and the low temperature adhesiveness are excellent.
  • the composition is obtained.
  • storage stability means that the reaction progress of the thiol component and the cyclic ether component before exposure is suppressed.
  • the storage stability can be confirmed, for example, by mixing compound 1, a thiol component and a cyclic ether component to form a composition, and checking the degree of increase in viscosity before and after the lapse of a predetermined time.
  • the reason why the above-mentioned effect is obtained by having the above-mentioned predetermined configuration is presumed as follows.
  • the aromatic ring group represented by Ar in the compound represented by the general formula (1) is excellent in light absorption in the region below visible light and facilitates elimination of the group having a quinuclidine skeleton.
  • the quinuclidine skeleton has a heterocyclic tertiary amine structure in which three alkyl chains bonded to a nitrogen atom each form a ring structure and contain one nitrogen atom as a ring skeleton forming atom.
  • the group having a quinuclidine skeleton has a cyclic ether component when it is used in combination with a cyclic ether component such as an epoxy compound, a thiol component or the like as a composition at the time of Ar bonding of an aromatic ring group. , The reaction with the thiol component is suppressed, and excellent storage stability is exhibited. Further, the group having a quinuclidine skeleton becomes a base having less steric hindrance around the unshared electron pair on the nitrogen atom when desorbed from the aromatic ring group Ar, and exhibits excellent nucleophilicity.
  • the catalytic action by a base can be efficiently exerted, and the polymerization catalytic ability is excellent. Therefore, when compound 1 is used in combination 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 timing to efficiently proceed the curing reaction. It can exhibit low temperature adhesiveness. In addition, the above composition shall rapidly proceed with the curing reaction even at a low temperature of 50 ° C. or higher and 100 ° C. or lower to exhibit high adhesive strength, and further, be in a temperature range near room temperature such as 0 ° C. or higher and 50 ° C. or lower.
  • the degree of freedom in the adhesive conditions is excellent, such as the ability to slowly proceed the curing reaction and exert a high adhesive force.
  • the composition of the present disclosure has good adhesiveness by combining compound 1 with a thiol component and a cyclic ether component. For these reasons, the compositions of the present disclosure are excellent in storage stability and low temperature adhesiveness. Further, the degree of freedom in the bonding conditions is excellent.
  • Ar is an aromatic ring group
  • A is a group having a quinuclidine skeleton
  • B - is a monovalent anion
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms, and 6 carbon atoms.
  • An aromatic hydrocarbon ring-containing group having up to 20 unsubstituted or substituents, a heterocyclic ring-containing group having 2 to 20 unsubstituted or substituents, or the above-mentioned aliphatic hydrocarbon.
  • the substituent that replaces 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 "-.
  • R'and R independently represent hydrogen atoms or unsubstituted aliphatic hydrocarbon groups, and when a plurality of R'or R'are present, they may be the same or different.
  • halogen atom represented by R 1 and R 2 and the halogen atom in group II-1 examples include a fluorine atom, a chlorine atom, and a bromine atom. Examples include iodine atoms.
  • An aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms represented by R 1 and R 2 in the general formula (1) (hereinafter collectively used for R 1 and the like).
  • the "aliphatic hydrocarbon group”) may be any as long as it does not contain an aromatic hydrocarbon ring or a heterocyclic ring, for example, an alkyl group having 1 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms. , Cycloalkyl groups having 3 to 20 carbon atoms, cycloalkylalkyl groups having 4 to 20 carbon atoms, and groups in which one or more of the hydrogen atoms of these groups are substituted with a substituent described later. Be done.
  • alkyl group having 1 to 20 carbon atoms used in R 1 and the like examples include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-pentyl, and tert.
  • -Pentyl cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert- Examples include octyl and adamantyl.
  • alkenyl group having 2 to 20 carbon atoms used in R 1 and the like examples include vinyl, ethylene, 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 and 4,8,12-tetradecatorienylallyl , Cyclopentadiniel and the like.
  • the cycloalkyl group having 3 to 20 carbon atoms used in R 1 and the like means a saturated monocyclic or saturated 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, octahydropentalene and bicyclo [1. 1.1] Pentanyl and the like can be mentioned.
  • the cycloalkylalkyl group having 4 to 20 carbon atoms used in R 1 and the like means a group having 4 to 20 carbon atoms in which the hydrogen atom of the alkyl group is replaced with a cycloalkyl group.
  • Examples of the cycloalkylalkyl group having 4 to 20 carbon atoms include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, and 2-cyclononylethyl. , 2-Cyclodecylethyl, 3-3-adamantylpropyl, decahydronaphthylpropyl and the like.
  • the number of carbon atoms of a group defines the number of carbon atoms of the group after the hydrogen atom in the group is substituted with a substituent.
  • the carbon atom number 1 to 20 refers to the number of carbon atoms after the hydrogen atom is substituted with the substituent.
  • the specification of the number of carbon atoms relating to a group in which the methylene group in the group having a predetermined number of carbon atoms is replaced with a divalent group is the specification of the number of carbon atoms of the group before the substitution. It shall be the same as the specification of the number of carbon atoms of the previous group.
  • the number of carbon atoms of a group in which a methylene group in an alkyl group having 1 to 20 carbon atoms is replaced with a divalent group is 1 to 20.
  • An aromatic hydrocarbon ring-containing group having an unsubstituted or substituent having 6 to 20 carbon atoms represented by R 1 and R 2 in the general formula (1) (hereinafter collectively referred to as "R 1 or the like".
  • the "aromatic hydrocarbon ring-containing group represented”) may be any as long as it contains an aromatic hydrocarbon ring and does not contain a heterocycle, for example, an aryl group having 6 to 20 carbon atoms and a carbon atom.
  • the "aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms” defines the number of carbon atoms of the "aromatic hydrocarbon ring-containing group” instead of the "aromatic hydrocarbon ring”. .. The same applies to other carbon atom numbers.
  • the aryl group having 6 to 20 carbon atoms used in R 1 and the like is a group having aromaticity, and is a group obtained by removing one hydrogen atom from a monocyclic aromatic ring such as phenyl (hereinafter, simple).
  • a group obtained by removing one hydrogen atom from the fused ring of a monocyclic aromatic ring such as naphthyl, anthracenyl, phenanthryl, pyrenyl, and fluorenyl (hereinafter, condensed aromatic hydrocarbon).
  • a group or two or more monocyclic aromatic rings such as biphenyl and benzophenone, and their fused rings are single bonds, carbonyl groups (-CO-), sulfide groups (-S-), etc.
  • Examples thereof include a group obtained by removing one or more hydrogen atoms from a compound bonded via a linking group (hereinafter, may be referred to as a linked aromatic hydrocarbon group), and in these aromatic rings such as a trill group.
  • a group in which the hydrogen atom of the above is substituted with an aliphatic hydrocarbon group.
  • the aliphatic hydrocarbon group that replaces the hydrogen atom in the aromatic ring of the aryl group include the same groups as those exemplified as the aliphatic hydrocarbon group represented by R 1 and the like.
  • Examples of the arylalkyl group having 7 to 20 carbon atoms used in R 1 and the like include a group in which one or more of the hydrogen atoms in the above-mentioned alkyl group are substituted with the above-mentioned aryl group.
  • Yes for example, benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl and naphthylpropyl and the hydrogen atoms in these rings are substituted with aliphatic hydrocarbon groups. Examples include the groups that have been used.
  • the aliphatic hydrocarbon group that replaces the hydrogen atom of the alkyl group and the arylalkyl group in the arylalkyl group is exemplified as the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R 1 or the like described above. Similar groups can be mentioned. Examples of the group having 6 to 20 carbon atoms in which the unsaturated aliphatic hydrocarbon group is 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. Can be mentioned.
  • Heterocyclic-containing groups having an unsubstituted or substituent having 2 to 20 carbon atoms represented by R 1 and R 2 in the general formula (1) (hereinafter collectively represented by "R 1 and the like”.
  • the heterocyclic group (also referred to as “heterocycle-containing group”) includes a tetrahydrofuran group, a dioxolanyl group, a tetrahydropyranyl group, a morphorylfuran group, a thiophene group, a methylthiophene group, a hexylthiophene group, a benzothiophene group, a pyrrole group, a pyrrolidine group, and an imidazole group.
  • a group in which one or more of the hydrogen atoms of a heterocycle such as an imidazolidine group, an imidazoline group, a pyrazole group, a pyrazolidine group, a piperidine group and a piperazine group is substituted with an aliphatic hydrocarbon group, and a fat.
  • a group in which one or more hydrogen atoms of a group hydrocarbon group are substituted with a heterocycle a group in which one or two or more of the hydrogen atoms of these groups are substituted with a substituent described later may be used. Can be mentioned.
  • a fused ring between a heterocycle and an aromatic hydrocarbon ring such as an indole ring, a quinoline ring, a benzofuran ring, a carbazole ring, a xanthene ring, and a thioxanthone ring is also a heterocycle. It is contained in the ring.
  • the aliphatic hydrocarbon group include those exemplified as the above-mentioned aliphatic hydrocarbon group represented by R 1 and the like.
  • "2 to 20" in “heterocyclic group having 2 to 20 carbon atoms” defines the number of carbon atoms of "heterocycle-containing group” instead of "heterocycle". The same applies to other carbon atom numbers.
  • Groups may be the same or different from each other, but any divalent group selected from Group I-1 assuming that the oxygen atoms are not adjacent to each other, the sulfur atoms are not adjacent to each other, or the oxygen atom and the sulfur atom are not adjacent to each other. May not be next to each other. This is the same in the following groups I-2, I-3 and other divalent groups.
  • One or more of the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group and the heterocyclic ring-containing group described in the general formula (1) and the methylene group in these groups are selected from the above group I-1.
  • unsubstituted aliphatic hydrocarbon group used in R'and R "in the above group II-1 and the group II-1 among those listed as the aliphatic hydrocarbon group used in the above-mentioned R 1 and the like. can be used as the number of carbon atoms to meet the number of carbon atoms, such as R 1.
  • An unsubstituted aliphatic hydrocarbon group of can be used.
  • the number of carbon atoms is 1 to 1. 19 can be used.
  • R 1 and R 2 used in the general formula (1) are each independently a hydrogen atom, an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms, and 6 to 6 carbon atoms.
  • both R 1 and R 2 used in the general formula (1) are hydrogen atoms, or R 1 is a hydrogen atom and R 2 is a group other than a hydrogen atom. This is because compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the above composition is more excellent in storage stability and low temperature adhesiveness.
  • R 2 is a hydrogen atom, an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms, and an aromatic having an unsubstituted or substituent having 6 to 20 carbon atoms.
  • the hydrogen atom is an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 10 carbon atoms, and an aromatic hydrocarbon having an unsubstituted or substituent having 6 to 10 carbon atoms.
  • a hydrogen atom, an alkyl group having an unsubstituted or substituent having 1 to 10 carbon atoms, an aryl group having an unsubstituted or substituent having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms is preferable.
  • a phenyl group having a substituted or substituent and most preferably a hydrogen atom, an unsubstituted methyl group or an ethyl group or an unsubstituted phenyl group. This is because compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the above composition is more excellent in storage stability and low temperature adhesiveness.
  • the quinuclidine skeleton in the group having a quinuclidine skeleton used in A of the general formula (1) contains one nitrogen atom as a ring skeleton forming heteroatom, and each of the three alkyl chains bonded to the nitrogen atom forms a ring structure. It is a heterocyclic tertiary amine structure.
  • the group having a quinuclidine skeleton represented by A has a quinuclidine ring or a fused ring of a quinuclidine ring and another ring.
  • the storage stability of compound 1 is that the group having a quinuclidine skeleton represented by A is bonded to ⁇ CR 1 R 2 ⁇ of the general formula (1) by an unshared electron pair on the nitrogen atom of the quinuclidine ring. It is particularly preferable in terms of the balance of polymerization catalytic ability.
  • the group having a quinuclidine skeleton represented by A is a group represented by the following general formula (A1) or general formula (A2). This is because compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the above composition is more excellent in storage stability and low temperature adhesiveness.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 (hereinafter, also referred to as “R 11 to R 19 ”) are independently described.
  • An aromatic hydrocarbon ring-containing group a heterocyclic ring-containing group having an unsubstituted or substituent having 2 to 20 carbon atoms, an aliphatic hydrocarbon group, an aromatic hydrocarbon ring-containing group, or the above. Whether one or more of the methylene groups in the heterocyclic-containing group is replaced with a divalent group selected from the following group I-3. Alternatively, two groups selected from R 11 to R 19 are linked to each other to form a ring.
  • X 11 and X 12 independently, -CR 201 R 202 - a divalent group represented by, R 111 , R 112 and R 113 and R 201 and R 202 each independently have a hydrogen atom, an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms, and 6 carbon atoms.
  • the substituent that replaces is an atom or group selected from the following group II-3. * Represents the joint location.
  • 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 "-.
  • R'and R independently represent hydrogen atoms or unsubstituted aliphatic hydrocarbon groups, and when a plurality of R'or R'are present, they may be the same or different.
  • R 21 , R 22 , R 23 , R 24 , R 25 , R 26 and R 27 are independently hydrogen atom and halogen atom, respectively.
  • the heterocyclic ring-containing group having an unsubstituted or substituent having 2 to 20 carbon atoms, the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocyclic ring-containing group.
  • one or more of the methylene groups is a group replaced with a divalent group selected from Group I-4 below.
  • Two groups selected from R 21 to R 27 are linked to each other to form a ring.
  • X 21 and X 22 each independently, -CR 201 R 202 - a divalent group represented by, R 111 , R 112 and R 113 and R 201 and R 202 each independently have a hydrogen atom, an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms, and 6 carbon atoms.
  • the substituent that replaces is an atom or group selected from the following group II-4.
  • R'R independently represents a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms. * Represents the joint location.
  • Group I-4 -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 "-.
  • R'and R independently represent hydrogen atoms or unsubstituted aliphatic hydrocarbon groups, and when a plurality of R'or R'are present, they may be the same or different.
  • R 1 and the like can be used as the above-mentioned hydrocarbon-containing groups, respectively.
  • Examples of the ring formed by connecting the two groups selected from R 11 to R 19 used in the general formula (A1) with each other include an aliphatic hydrocarbon ring and an aromatic hydrocarbon ring.
  • Examples of the aliphatic hydrocarbon ring include a saturated aliphatic hydrocarbon ring or an unsaturated aliphatic hydrocarbon ring.
  • Examples of the saturated aliphatic hydrocarbon ring include a cyclohexane ring and a cyclopentane ring.
  • Examples of the unsaturated aliphatic hydrocarbon ring include a cyclohexene ring and a cyclopentadiene ring.
  • Examples of the aromatic hydrocarbon ring include a benzene ring.
  • As a ring formed by connecting two groups selected from R 21 to R 27 used in the general formula (A2) two groups selected from R 11 and the like are formed by connecting each other. Examples of the ring to be used include those listed above.
  • Group having a quinuclidine skeleton used for A are particularly preferably the formula (A1) represented by the group or the formula (A2) represented by X 23 is a group which is an oxygen atom, represented by the formula (A1) It is most preferably a base. This is because compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the above composition is more excellent in storage stability and low temperature adhesiveness.
  • R 11 to R 19 are hydrogen atoms or other groups / atoms, but the groups / atoms for which the raw material for producing compound 1 is easily available include halogen atoms, nitro groups, and cyano atoms.
  • R 11 to R 19 preferably have a hydrogen atom or a group having 6 or less carbon atoms in terms of ease of production of the compound 1.
  • R 11 to R 19 in the general formula (A1) are all hydrogen atoms, or any one to three are preferable substituents other than the hydrogen atom, such as a hydroxyl group, a cyano group, and a ⁇ SH group.
  • it is preferably an alkyl group having 1 to 3 carbon atoms substituted with a hydroxyl group, a cyano group or a —SH group, and all of them are hydrogen atoms, or any one or two are hydroxyl groups.
  • any one of R 13 , R 14 , R 16 and R 17 is other than the above-mentioned hydrogen atom. It is preferable that it is a group / atom of, and it is particularly preferable that it is a preferable substituent other than the above-mentioned hydrogen. In those cases, it is preferable that the rest of R 11 to R 19 are hydrogen atoms. This is because the above compound can be used as an excellent initiator due to the balance between storage stability and polymerization catalytic ability.
  • R 201 and R 202 are preferably hydrogen atoms or substituted or unsubstituted alkyl groups having 3 or less carbon atoms, and R 201 and R 202 are hydrogen atoms or carbon. It is more preferably an unsubstituted alkyl group having 3 or less atoms, particularly preferably R 201 and R 202 being a hydrogen atom or a methyl group, and most preferably R 201 and R 202 being hydrogen atoms. This is because compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the above composition is more excellent in storage stability and low temperature adhesiveness.
  • R 21 to R 27 are hydrogen atoms or other groups / atoms, but the groups / atoms for which the raw material for producing compound 1 is easily available include halogen atoms, nitro groups, and cyano atoms.
  • R 21 to R 27 are hydrogen atoms or groups having 6 or less carbon atoms in terms of ease of production of compound 1. Further, in R 21 to R 27 in the formula (A2), it is preferable that four or more of them are hydrogen atoms in terms of ease of production, and all of them may be hydrogen atoms.
  • R 201 and R 202 are preferably hydrogen atoms or substituted or unsubstituted alkyl groups having 3 or less carbon atoms, and R 201 and R 202 are hydrogen atoms or carbon. It is more preferably an unsubstituted alkyl group having 3 or less atoms, particularly preferably R 201 and R 202 being a hydrogen atom or a methyl group, and most preferably R 201 and R 202 being hydrogen atoms. This is because compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the above composition is more excellent in storage stability and low temperature adhesiveness.
  • the aromatic ring group Ar used in the general formula (1) is a group having aromaticity.
  • the aromatic cyclic group Ar monocyclic aromatic hydrocarbon group exemplified as the aromatic hydrocarbon ring-containing group used in R 1 or the like, condensed aromatic hydrocarbon group, linked aromatic hydrocarbon group, R 1, etc.
  • the heterocyclic-containing group used in the above a fused heterocyclic group obtained by removing one hydrogen atom from the condensed heterocycle mentioned above can be used.
  • the aromatic ring group Ar is preferably a group having two or more ring structures and having aromaticity, and in particular, a condensed aromatic hydrocarbon group and a linked aromatic hydrocarbon group.
  • Y 1 is a sulfur atom, CO, SO, SO 2 , CR 101 2 , PR 102 or NR 102 .
  • Y 2 is a single bond, oxygen atom, sulfur atom, CO, SO, SO 2 , CR 102 2 , PR 102 or NR 101 .
  • Y 3 is an oxygen atom, a sulfur atom, CO, SO, SO 2 , CR 102 2 , PR 102 or NR 101 .
  • R 101 is an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms and an aromatic having an unsubstituted or substituent having 6 to 20 carbon atoms, respectively.
  • it represents a group in which one or more of the methylene groups in the above heterocyclic-containing group is replaced with a divalent group selected from the following group I-2.
  • R 31 , R 32 , R 41 , R 42 , R 51 , R 52 and R 53 are independently halogen atoms, nitro groups, cyano groups, -OR 121 , -COR 121 , -OCOR 121 , -COOR 121, respectively.
  • One or more of the containing group or the methylene group in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group or the heterocyclic ring-containing group is replaced with a divalent group selected from the following group I-2.
  • a divalent group selected from the following group I-2 Represents a group However, a plurality of R 41s may be bonded to each other to form a ring, and the ring is unsubstituted or has a substituent.
  • R 121 , R 122 and R 123 are each independently a hydrogen atom, an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms, and an unsubstituted or unsubstituted group having 6 to 20 carbon atoms.
  • An aliphatic hydrocarbon group having the above substituent, an aromatic hydrocarbon ring-containing group having the above substituent, a heterocyclic ring-containing group having the above substituent, and a plurality of R 41s are mutually exclusive.
  • the substituent that replaces one or more of the hydrogen atoms in the ring formed by bonding is an atom or group selected from the following group II-2. a1 is an integer from 0 to 5, a2 is an integer from 0 to 4, b1 is an integer from 0 to 4, b2 is an integer from 0 to 3 and c1 is an integer from 0 to 4, c2 is an integer from 0 to 1 and * Represents the joint location.
  • 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 "-.
  • R'and R independently represent hydrogen atoms or unsubstituted aliphatic hydrocarbon groups, and when a plurality of R'or R'are present, they may be the same or different.
  • the R'or R'used in groups I-2, II-2 of the general formulas (Ara1), (Arb1), (Arc1) is the same group as that used in groups I-1, II-1 and the like. Can be used.
  • Examples of the ring formed by bonding a plurality of R 41s to each other include a benzene ring condensed with a benzene ring located on the left side of Arb1, and the structure of the formula Arb1 in which the ring is formed is the following formula (Arb1 ⁇ ). , (Arb1 ⁇ ) or (Arb1 ⁇ ).
  • R 43 is an atom or group selected from the group II-2, b3 is a number of 0 ⁇ 4, b1 'is a number of 0 ⁇ 2 .Y 2 , Y 3, R 42, b2, except that it is the same as equation (Arb1) .R 41 'is a plurality of R 41' are not bonded to each other to form a ring, the same as R 41.)
  • the aromatic ring group Ar is preferably a group represented by the above general formula (Ara1) or formula (Arb1), and particularly preferably a group represented by the formula (Ara1). This is because compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the above composition is more excellent in storage stability and low temperature adhesiveness.
  • R 31 and R 32 in the general formula (Ara1) are independently a nitro group, an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 10 carbon atoms, and 3 to 10 carbon atoms.
  • a -COR 121 and R 121 is unsubstituted or unsubstituted or aryl group has a substituent, or 3 to 10 carbon atoms of 6 to 10 carbon atoms It is preferably a heterocyclic-containing group having a substituent. This is because compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the above composition is more excellent in storage stability and low temperature adhesiveness.
  • 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 preferably 0. Most preferred. This is because compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the above composition is more excellent in storage stability and low temperature adhesiveness.
  • 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. This is because compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the above composition is more excellent in storage stability and low temperature adhesiveness.
  • Formula (ARA1) bonding site in, i.e., -CO-CR 1 R 2 A + B - the position of the bonding site of A may be a bondable position of the aromatic ring, relative to Y 1, It is preferably in the para position. This is because compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the above composition is more excellent in storage stability and low temperature adhesiveness. Therefore, when Y 1 is a sulfur atom, it is preferable that the compound 1 is a compound represented by the following general formula (11).
  • Y 1 is preferably a sulfur atom, CO, SO, NR 102 , and particularly preferably a sulfur atom. This is because the compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the composition is more excellent in storage stability and low temperature adhesiveness. Also, it is easy to synthesize. For the above reasons, among the compounds 1, the compound represented by the following formula (11) is preferable.
  • R 41 and R 42 in the general formula (Arb1) are independently a nitro group, an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 10 carbon atoms, and 3 to 10 carbon atoms.
  • a -COR 121 and R 121 is unsubstituted or unsubstituted or aryl group has a substituent, or 3 to 10 carbon atoms of 6 to 10 carbon atoms It is preferable that it is a heterocyclic-containing group having a substituent, or that R 41 are bonded to each other and have a group represented by the above (Arb1 ⁇ ) to (Arb1 ⁇ ). This is because compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the above composition is more excellent in storage stability and low temperature adhesiveness.
  • b1 in the general formula (Arb1) is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and 0 to 2. It is particularly preferable that it is an integer of 1. This is because compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the above composition is more excellent in storage stability and low temperature adhesiveness.
  • R 41 are bonded to each other to form a ring and are represented by any of the formulas (Arb1 ⁇ ) to (Arb1 ⁇ ), b1'is preferably 0 and b3 is preferably an integer of 0 to 1. This is because compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the above composition is more excellent in storage stability and low temperature adhesiveness.
  • B2 in the general formula (Arb1) or the like is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, and most preferably 0. This is because compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the above composition is more excellent in storage stability and low temperature adhesiveness.
  • Formula (ARB1) bonding site such as, i.e., -CO-CR 1 R 2 A + B - the position of the bonding site of A, may be a bondable position of the aromatic ring, relative to Y 3, It is preferably in the meta or para position. This is because compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the above composition is more excellent in storage stability and low temperature adhesiveness.
  • Y 2 is preferably a single bond, and Y 3 is preferably CR 102 2 or NR 101 . This is because the compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the composition is more excellent in storage stability and low temperature adhesiveness. Also, it is easy to synthesize.
  • one or more of an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms or a methylene group in the aliphatic hydrocarbon group is selected from the above group I-2. It is preferably a group substituted with a divalent group, and particularly preferably an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 10 carbon atoms.
  • one or more of an aliphatic hydrocarbon group having a hydrogen atom or an unsubstituted or substituent having 1 to 20 carbon atoms or a methylene group in the aliphatic hydrocarbon group is from the above group I-2. It is preferably a group substituted with a selected divalent group, and particularly preferably an aliphatic hydrocarbon group having a hydrogen atom or an unsubstituted or substituent having 1 to 8 carbon atoms. This is because the compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the composition is more excellent in storage stability and low temperature adhesiveness.
  • the compound represented by the following formula (12) is particularly preferable.
  • B in the general formula (1) the monovalent anion represented by, for example, halide ions, inorganic halide anions, sulfonate anions, phosphorus-containing anions, imide ion, a borate anion ( "borate anion” (Sometimes called), carboxylic acid anion, dithiocarbamide anion, organic sulfonylmethide ion, thiocyanate anion, dithiocarbamate anion and the like.
  • halide ion examples include chlorine anion, bromine anion, iodine anion, and fluorine anion.
  • inorganic halogenated anion examples include perchlorate anion, chlorate anion, thiocyanate anion, hexafluorophosphate anion, hexafluoride antimony anion, arsenic hexafluoride anion, boron tetrafluoride anion and the like.
  • sulfonic acid anion examples include methanesulfonic acid ion, fluorosulfonic acid ion, benzenesulfonic acid anion, toluenesulfonic acid anion, 1-naphthylsulfonic acid anion, 2-naphthylsulfonic acid anion, trifluoromethanesulfonic acid anion, and pentafluoroethanesulfone.
  • examples of the phosphorus-containing anion include phosphate ester anions such as octyl phosphate anion, dodecyl phosphate anion, octadecyl phosphate anion, phenyl phosphate anion, and nonylphenyl phosphate anion, and 2,2'-methylenebis.
  • Phosphonate ester anion such as (4,6-di-t-butylphenyl) phosphonate anion, organic group substituted phosphinic acid anion such as phenyl (2,4,6-trimethylbenzoyl) phosphinate, dialkylphosphinate, diphenylphosphinate And so on.
  • imide ion examples include bis (trifluoromethanesulfone) imide ion, bis (pentafluoroethanesulfone) imide ion, phthalimide ion, o-sulfobenzimide, bis (heptafluoropropanesulfone) imide ion, bis (nonafluorobutane sulfone) imide ion, and bis ( Undecafluoropentane sulfone) imide ion, bis (pentadecafluoroheptane sulfone) imide ion, bis (tridecafluorohexane sulfone) imide ion, bis (heptadecafluorooctane sulfone imide) ion, (trifluoromethane sulfone) (nonafluorobutane sulfone)
  • imide ion examples include imide i
  • borate anion examples include an organic anion in which an alkyl group and / or an aryl group is bonded to any of the bonds of the boron atom.
  • specific examples of the borate anion include tetraaryl borates such as tetrakis (pentafluorophenyl) borate anion, tetrakis (4-fluorophenyl) borate anion, tetraphenyl borate anion, and borate anion described in JP-A-2007-112854. Anions and triarylalkylboran anions are added.
  • the borate anion described in JP-A-6-184170, the borate anion described in JP-A-2002-526391, and the like can also be mentioned.
  • carboxylic acid anion examples include benzoic acid anion, trifluoroacetic acid anion, 2-oxo-2-phenylacetic acid anion and the like.
  • Examples of the methide ion include organic sulfonyl methide ions such as tris (trifluoromethanesulfonyl) methide and tris (methanesulfonyl) methide.
  • Examples of the dithiocarbamide anion include N, N-diethyldithiocarbamide anion.
  • alkyl sulfonic acid ions fluoro-substituted alkyl sulfonic acid ions
  • alkyl sulfonimides fluoro-substituted alkyl sulfonimides substituted with acryloyloxy groups and methacryloyloxy groups
  • aliphatic cyclic alkyls such as norbornyl groups and adamantyl groups. Examples include those substituted with a group.
  • a quencher anion having a function of deexciting (quenching) an active molecule in an excited state a ferrocene having an anionic group such as a carboxy group, a phosphonic acid group, a sulfonic acid group, etc. in a cyclopentadienyl ring, luteosen, etc.
  • the metallocene compound anion of the above can also be used as needed.
  • B - Among the monovalent anion represented by the low temperature adhesion properties, storage stability, in terms of a balance of the raw material availability, etc., borate anions, thiocyanate anions, phthalimide anion, halide anions, sulfo benzimidamide Anions, tetrafluoroboron anions, hexafluorinated phosphorus anions, trifluoromethanesulfonic acid anions, and phosphorus-containing anions are more preferable, among which borate anions and phosphorus-containing anions are particularly preferable, and borate anions are particularly preferable, and the following general formula (I) ) Is most preferable.
  • R 301 to R 304 is an aryl group having an unsubstituted or substituent having 6 to 10 carbon atoms is preferable. This is because compound 1 is more excellent in storage stability and polymerization catalytic ability, and as a result, the above composition is more excellent in storage stability and low temperature adhesiveness.
  • R 301 , R 302 , R 303 and R 304 are each an alkyl group having an unsubstituted or substituent having 1 to 20 carbon atoms and an unsubstituted or substituent having 6 to 20 carbon atoms, respectively.
  • the above-mentioned substituent is an atom or group selected from the following group II-5.
  • R'independently represents a hydrogen atom or an unsubstituted aliphatic hydrocarbon group, and when a plurality of R'are present, they may be the same or different.
  • R'used in group II-5 of the general formula (I) the same groups as those used in group II-1 can be used.
  • the method for producing the compound represented by the general formula (I) is not particularly limited, but for example, it can be produced by the following method according to the following reaction formula 1. That is, the compound 1 which is a Br salt is obtained by reacting a ketone body in which bromine is bound to the ⁇ -position of the carbonyl group with quinuclidine or a derivative thereof.
  • A is represented by the general formula (A1), R 11 to R 19 are hydrogen atoms, and X 11 and X 12 are ⁇ CH 2 ⁇ , but other compounds 1 are also used. It can be produced by changing the quinuclidine derivative.
  • Compound 1 other than Br salt can be obtained by reacting a target anion B ⁇ with a cation M + such as an alkali metal cation (reaction formula 2 below).
  • a cation M + such as an alkali metal cation
  • Examples of the cation M + include sodium cations and the like.
  • the content of compound 1 is preferably 1 part by mass or more and 20 parts by mass or less in a total of 100 parts by mass of the cyclic ether component, the thiol component and compound 1.
  • 3 It is preferably 5 parts by mass or more and 15 parts by mass or less, and preferably 5 parts by mass or more and 10 parts by mass or less. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the content of compound 1 is preferably 5 parts by mass or more and 30 parts by mass or less, and 7 parts by mass or more and 25 parts by mass or less, based on 100 parts by mass of the total of the thiol component and compound 1. It is more preferably 10 parts by mass or less and 20 parts by mass or less. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the content of the compound 1 may be any as long as it can obtain desired storage stability and low temperature adhesiveness, but 0.2 mass by mass in 100 parts by mass of the solid content of the composition. It is preferably 5 parts by mass or more and 30 parts by mass or less, particularly preferably 0.5 parts by mass or more and 20 parts by mass or less, particularly preferably 2 parts by mass or more and 15 parts by mass or less, and 3 parts by mass or more and 10 parts by mass or less. Is preferable. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the solid content refers to the total mass of all components other than the solvent.
  • the content of the compound 1 may be any as long as it can obtain desired storage stability and low temperature adhesiveness, but is 0.2 parts by mass or more and 30 parts by mass in 100 parts by mass of the composition. It is preferably 0.5 parts by mass or more and 20 parts by mass or less, particularly preferably 2 parts by mass or more and 15 parts by mass or less, and 3 parts by mass or more and 10 parts by mass or less. Is preferable. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the content of the compound 1 may be any as long as it can obtain the desired storage stability and low-temperature adhesiveness, but the composition contains radicals in addition to the cyclic ether component and the thiol component as curable components.
  • a polymerizable component is contained, it is preferably 0.2 parts by mass or more and 30 parts by mass or less with respect to a total of 100 parts by mass of the cyclic ether component, the thiol component and the radically polymerizable component, and in particular, 0. It is preferably 5.5 parts by mass or more and 20 parts by mass or less, particularly preferably 1 part by mass or more and 15 parts by mass or less, and particularly preferably 3 parts by mass or more and 10 parts by mass or less. This is because the above composition has an excellent balance between storage stability and curability.
  • the thiol component refers to a component that is one or more of a compound having a thiol group (hereinafter, may be referred to as a thiol compound).
  • the thiol compound is contained in the composition as a component other than the above-mentioned compound 1, and a compound having both a thiol group and a cyclic ether group also corresponds to the thiol compound.
  • thiol component only one kind of thiol compound may be used, or two or more kinds may be combined.
  • a composition having particularly excellent curability can be obtained by combining the above compound 1 with a thiol component.
  • the type of the thiol group in the above thiol compound a primary thiol group, a secondary thiol group, a tertiary thiol group and the like can be used.
  • the type of the thiol group is preferably a primary thiol group or a secondary thiol group, and among them, 1 It is preferably a primary thiol group.
  • the number of thiol groups contained in one molecule is preferably 2 or more, and more preferably 3 or more, from the viewpoint of further enhancing the effect that the thiol compound is excellent in storage stability and low-temperature adhesiveness.
  • the number of thiol groups is preferably 10 or less, more preferably 8 or less, further preferably 7 or less, preferably 6 or less, preferably 5 or less, and preferably 4 or less from the viewpoint of improving storage stability.
  • it is a primary thiol compound having the above number of thiol groups, that is, the thiol compound is preferably a compound having 2 or more primary thiol groups, and is a compound having 2 or more and 10 or less primary thiol groups.
  • the compound has a primary thiol group of 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, and particularly 3 or more and 4 or less. ..
  • the thiol compound as an example of a compound having 2 or more and 10 or less thiol groups, it is preferable to use a compound represented by the following formula (A) (hereinafter, may be referred to as compound A). .. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness. Further, it is preferable in terms of availability, storage stability of the composition, and a balance of curability.
  • X 1 is an aliphatic hydrocarbon group having the same number of valences as n1 and having an unsubstituted or substituent having 1 to 40 carbon atoms, an unsubstituted or unsubstituted group having 6 to 40 carbon atoms.
  • n1 represents an integer of 2 or more and 10 or less.
  • Group III -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 "'-, -S A group selected from -S- or -SO 2-.
  • R''' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and when there are a plurality of R''', they may be the same or different.
  • X 1 is used as a linking group to which n1 —SH groups are bonded.
  • the heterocyclic groups in the above are aliphatic hydrocarbon groups having 1 to 40 monovalent carbon atoms, aromatic hydrocarbon ring-containing groups having 6 to 40 monovalent carbon atoms, and monovalent carbon atoms, respectively. It is a group having a structure in which (n1-1) hydrogen atoms are removed from 2 to 20 heterocyclic-containing groups.
  • the aliphatic hydrocarbon group having 1 to 40 carbon atoms having the same number of valences as n 1 may have 1 to 30 carbon atoms. More preferably, it may be 1 to 20.
  • each of the aliphatic hydrocarbon group having 1 to 20 carbon atoms used in the R 1 or the like as described above an aromatic 6 to 20 carbon atoms used in the R 1 or the like hydrocarbon ring-containing group and R 1 A group similar to the heterocyclic-containing group having 2 to 20 carbon atoms used in the above can be used.
  • the alkyl group having 1 to 8 carbon atoms used for R'' in the above group III among the alkyl groups having 1 to 20 carbon atoms used for R 1 and the like, those having a predetermined carbon atom number are used. Can be used.
  • the alkyl group may be unsubstituted or substituted with a substituent described later.
  • divalent groups shall not be adjacent to each other.
  • the plurality of divalent groups may be the same or different from each other.
  • Substituted aliphatic hydrocarbon groups represented by X 1 aromatic hydrocarbon ring-containing group, one of the hydrogen atoms of such groups and heterocyclic ring-containing group it is replaced with a group selected from the group III or two or more
  • the substituent for substituting one or two or more of the hydrogen atoms in the substituent and the alkyl group having 1 to 8 carbon atoms used for the substituent and R''' the group or atom selected from the above-mentioned group II-1 is used. Of these, it can be other than a thiol group.
  • a preferable group represented by X 1 will be further described from the viewpoint of the balance between the storage stability and the low temperature adhesiveness of the composition.
  • the aliphatic hydrocarbon group having an unsubstituted or substituent having a divalent carbon atom number of 1 to 40 represented by X 1 include an alkylene group such as methylene, ethylene, propylene, butylene and butyldiyl.
  • a group in which the methylene group thereof is replaced with a group selected from the above group III and a group in which these groups are substituted with the above-mentioned substituents are preferably used. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • Examples of the aliphatic hydrocarbon group having an unsubstituted or substituent having a trivalent carbon atom number of 1 to 40 represented by X 1 include alcoholidine such as propyridine and 1,1,3-butylidine and the like. Preferred are groups in which one or more of the methylene groups are replaced with a group selected from Group III and one or two of the hydrogen atoms in these groups are substituted with the above-mentioned substituents. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • An aliphatic hydrocarbon group having an unsubstituted or substituent having a tetravalent carbon atom number of 1 to 40 represented by X 1 or a methylene group in the aliphatic hydrocarbon group was selected from Group III.
  • Preferred examples of a group substituted with a group include a group containing a residue of a polyol (for example, a group represented by the general formula (X3) described later) and a group in which these groups are substituted with the above-mentioned substituent. Can be mentioned.
  • An aliphatic hydrocarbon group having an unsubstituted or substituent having a hexavalent carbon atom number of 1 to 40 represented by X 1 or a methylene group in the aliphatic hydrocarbon group was selected from Group III.
  • Preferred examples of a group substituted with a group include a group containing a residue of a polyol (for example, a group represented by the general formula (X4) described later) and a group in which these groups are substituted with the above-mentioned substituent. Can be mentioned.
  • the aromatic hydrocarbon ring-containing group having an unsubstituted or substituent having 6 to 40 divalent carbon atoms represented by X 1 or the methylene group thereof was replaced with a group selected from Group III.
  • Preferred examples of the group are, for example, arylene groups such as phenylene and naphthylene, residues of bifunctional phenols such as catechol, bisphenol and their alkylene oxide adducts; 2,4,8,10-tetraoxaspiro [5, 5] Examples include undecane and the like and groups in which these groups are substituted with the above-mentioned substituents.
  • Examples of the aromatic hydrocarbon ring-containing group having an unsubstituted or substituent having a trivalent carbon atom number of 6 to 40 represented by X 1 include phenyl-1,3,5-trimethylene and these. Examples thereof include a group in which the group of is substituted with the above-mentioned substituent.
  • Examples of the heterocyclic ring-containing group having an unsubstituted or substituent having a divalent carbon atom number of 2 to 20 represented by X 1 include a pyridine ring, a pyrimidine ring, a piperidine ring, a piperazine ring and a triazine ring. , A group having a heterocycle such as a furan ring, a thiophene ring, an indole ring, and a group in which one or more of the hydrogen atoms of these groups are substituted with the above-mentioned substituents.
  • heterocyclic-containing group having an unsubstituted or substituent having a trivalent carbon atom number of 2 to 20 represented by X 1 include a group having an isocyanul ring or a triazine ring and a hydrogen atom of these groups. Examples thereof include groups in which one or more are substituted with the above-mentioned substituents.
  • heterocyclic-containing group having an unsubstituted or substituent having a tetravalent carbon atom number of 2 to 20 represented by X 1 the group having a glycoluril group and the hydrogen atom of this group are substituted above. Examples include groups substituted with groups.
  • X 1 is one of an aliphatic hydrocarbon group, an aromatic hydrocarbon ring-containing group and a methylene group in the heterocyclic ring-containing group.
  • two or more are preferably replaced with a group selected from Group III, among which one or more of the methylene groups are replaced with -O-CO- or -CO-O-.
  • n1 methylene groups are replaced with —O—CO— or —CO—O—.
  • n1 is preferably 2 to 8, particularly preferably 2 to 6, and particularly preferably 3 to 4. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the X 1 has a structure represented by any of the following X1 to X6 in terms of the balance between the storage stability and the low temperature adhesiveness of the composition, and particularly any of X2 to X6. It is preferable to have a structure represented by X2, X3 or X5 in terms of the balance between storage stability and curability of the composition, and it is particularly preferable to have a structure represented by X2, X3 or X5. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • a11 is an integer from 1 to 20. * Represents the joint location.
  • the compound represented by the above formula (A) is particularly a compound represented by any of the following formulas (A1) to (A6), that is, the storage stability of the composition and the low temperature adhesion. It is preferable in terms of the balance of sex, more preferably represented by any of (A2) to (A6), and particularly preferably represented by any of (A2), (A3) or (A5). This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness. (In the formula, L 11 , L 12 , L 21 , L 22 , L 23 , L 31 , L 32 , L 33 , L 34 , L 41 , L 42 , L 43 , L 44 , L 45 , L 46 , L.
  • L 11 to L 64 are independently linear or branched with 1 to 10 carbon atoms. Represents an alkylene group.
  • R 64 , R 65 and R 66 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
  • A21 represents an integer of 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 in which one hydrogen atom is removed from an alkyl group having 1 to 10 carbon atoms.
  • the alkyl group having 1 to 10 carbon atoms for example, among the alkyl groups having 1 to 20 carbon atoms in R 1 or the like, those having a predetermined carbon atom number can be used.
  • the aliphatic hydrocarbon group having 1 to 20 carbon atoms used in R 64 , R 65 and R 66 shall be the same as the aliphatic hydrocarbon group having 1 to 20 carbon atoms in R 1 and the like. Can be done.
  • the alkylene group having 1 to 10 carbon atoms represented by L 11 to L 64 and the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R 64 , R 65 and R 66 are 1 of these groups. or more hydrogen atoms is the or unsubstituted are substituted, the substituents when substituted, one or more hydrogen atoms of the aliphatic hydrocarbon group represented by X 1 It can have the same contents as the substituent that replaces.
  • the above L 11 to L 64 are preferably alkylene groups having 1 to 5 carbon atoms, and among them, linear carbon atoms 1 to 3 are preferable. It is preferably an alkylene group or a branched 3 to 5 alkylene group, and particularly preferably a linear alkylene group having 1 to 3 carbon atoms. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • linear alkylene group having 1 to 3 carbon atoms represented by L 11 to L 64 include methylene, ethylene (ethane-1,2-diyl), and propylene (propane-1,1). 3-Gile) and the like.
  • branched 3 to 5 alkylene groups represented by L 11 to L 64 include propane-1,1-diyl, propane-1,2-diyl, and butane-1,1-diyl.
  • L 11 and L 12 in (A1) may be the same group or different groups, but from the viewpoint of easy synthesis, they are preferably the same group. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness. This means L 21 to L 23 in (A2), L 31 to L 34 in (A3), L 41 to L 46 in (A4), L 51 to L 53 in (A5), and L 61 to (A6). The same applies to L 64.
  • the R 64 is preferably an alkyl group having 1 to 20 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably 1 to 3 carbon atoms. It is preferably an alkyl group of. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the thiol compound preferably has a molecular weight of 100 or more and 1,000 or less, more preferably 300 or more and 900 or less, and 350 or more and 800 or less, from the viewpoint of the balance between storage stability and curability of the composition. Is particularly preferred. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the thiol group equivalent of the thiol compound is preferably 500 or less, and more than 100. It is preferably 400 or less, and particularly preferably 120 or more and 300 or less. This is because when the thiol group equivalent of the thiol compound is in the above range, the composition has an excellent balance between storage stability and curability. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • thiol compound a commercially available product may be used.
  • examples of commercially available thiol compounds include, for example, dodecanethiol (monofunctional thiol compound), Karenz MT (registered trademark) BD (trade name, bifunctional thiol compound, 1,4-bis (3-mercaptobutyryloxy)).
  • the content of the thiol component is preferably 1 part by mass or more and 80 parts by mass or less, more preferably 10 parts by mass or more and 70 parts by mass or less, and 20 parts by mass or more and 50 parts by mass or less in 100 parts by mass of the composition.
  • the amount is more preferably 25 parts by mass or more, and particularly preferably 45 parts by mass or less. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the content of the thiol component is more preferably 10 parts by mass or more and 70 parts by mass or less, further preferably 20 parts by mass or more and 50 parts by mass or less, and 25 parts by mass, based on 100 parts by mass of the solid content of the composition. It is particularly preferable that the amount is 45 parts by mass or less. This is because the above composition has an excellent balance between storage stability and low-temperature adhesiveness.
  • the content of the thiol component is more preferably 10 parts by mass or more and 70 parts by mass or less, and more preferably 20 parts by mass or more and 60 parts by mass or less, based on 100 parts by mass of the total of compound 1, the thiol component and the cyclic ether component. It is more preferably 25 parts by mass or more and 50 parts by mass or less. This is because the above composition has an excellent balance between storage stability and low-temperature adhesiveness.
  • the total number of thiol groups (unit: mol) in the thiol component is preferably 80 or more and 150 or less, preferably 90 or more, when the total number of cyclic ether groups in the cyclic ether component in the composition is 100. It is preferably 120 or less, and preferably 95 or more and 110 or less. This is because the above composition has excellent adhesive strength.
  • the cyclic ether component refers to a component that is one or more of a compound having a cyclic ether group (hereinafter, may be referred to as a cyclic ether compound).
  • the cyclic ether compound is contained in the composition as a component other than the above-mentioned compound 1 and the thiol compound, and the compound having both a thiol group and a cyclic ether group does not correspond to the cyclic ether compound and is a thiol component. It is applicable.
  • the cyclic ether group may be any one having at least one ether bond in the ring structure, and examples thereof include an epoxy group and an oxetanyl group.
  • examples of the cyclic ether compound include an epoxy compound having an epoxy group and an oxetane compound having an oxetanyl group.
  • the cyclic ether compound it is preferable to use a compound having no base generating ability in terms of storage stability.
  • a compound having a hydroxyl group such as an ethylenically unsaturated group, a carboxy group, an acid anhydride structure and a phenol group also falls under the category of the cyclic ether compound.
  • examples of the ethylenically unsaturated group include an acryloyl group, a methacryloyl group, and a vinyl group.
  • the compound having an alkoxysilyl group together with the cyclic ether group is usually classified as a silane coupling agent, and does not correspond to the above cyclic ether compound.
  • a silane coupling agent compounds having an alkoxysilyl group together with an epoxy group such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane are usually used.
  • the content of the cyclic ether group in the cyclic ether compound can be appropriately set according to the desired curability and the like.
  • the content of the cyclic ether group may be 1 or more per molecule of the cyclic ether compound, but may be 2 or more and 10 or less, and more preferably 2 or more and 8 or less. This is because a composition using such a cyclic ether compound has an excellent balance between storage stability and curability. Further, when it is used as an adhesive, it exhibits excellent adhesiveness and adhesiveness.
  • the cyclic ether group equivalent in the cyclic ether compound may be one that can obtain desired storage stability and low temperature adhesiveness, but is preferably 100 or more and 1,500 or less, and more preferably 130 or more and 500 or less. It is preferably present, and in particular, it is preferably 150 or more and 400 or less. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • composition of the present disclosure it is preferable to contain an epoxy compound as a cyclic ether component. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • Epoxy compound The epoxy compound includes all cyclic ether compounds having an epoxy group as the cyclic ether group.
  • a compound containing an epoxy group and another cyclic ether group such as an oxetanyl group in one molecule shall be included in the epoxy compound.
  • examples of such an epoxy compound include aromatic epoxy compounds, aliphatic epoxy compounds and alicyclic epoxy compounds.
  • (1-1) Aromatic Epoxy Compound The aromatic epoxy compound has an aromatic ring and an epoxy group, and does not have a cycloalkene oxide structure. As such an aromatic epoxy compound, a compound having at least one aromatic hydrocarbon ring can also be used.
  • the aromatic epoxy compound examples include polyvalent phenol having at least one aromatic ring such as bisphenol A and bisphenol F, or a polyglycidyl etherified product of an alkylene oxide adduct thereof; an epoxy novolak resin (phenol novolak type epoxy compound); Polyglycidyl etherified product of an aromatic compound having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, and catechol; poly of an aromatic compound having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol, and phenyldibutanol.
  • polyvalent phenol having at least one aromatic ring such as bisphenol A and bisphenol F, or a polyglycidyl etherified product of an alkylene oxide adduct thereof
  • an epoxy novolak resin phenol novolak type epoxy compound
  • Polyglycidyl etherified product of an aromatic compound having two or more phenolic hydroxyl groups such as resorcinol,
  • Examples thereof include glycidyl etherified products; polyglycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid, and trimellitic acid; and diepyloxidized products of divinylbenzene. Further, two or more glycidyl ether groups are added to the main chain skeleton containing a rubber component and a group capable of reacting with an epoxy group to form a covalent bond (hereinafter, also referred to as "epoxy group reactive group"). The compound obtained by reacting the aromatic epoxy compound having is also mentioned.
  • the epoxy equivalent of the aromatic epoxy compound may be one that can obtain desired storage stability and low-temperature adhesiveness, but is preferably 100 or more and 500 or less, and more preferably 130 or more and 400 or less. It is preferable, and in particular, it is preferably 150 or more and 350 or less. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • 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, ON.
  • the aromatic epoxy compound preferably contains a polyhydric phenol having at least one aromatic ring or a polyglycidyl etherified product of an alkylene oxide adduct thereof, and is particularly represented by the following general formula (14). It is preferable to contain the compound to be used. This is because, by containing the above compound, the above composition is excellent in the balance of storage stability and low temperature adhesiveness, and also in the balance of ease of preparation and coatability of the composition.
  • X 11 includes an aromatic hydrocarbon ring-containing group having 6 to 40 carbon atoms.
  • One or more of the methylene groups in the aromatic hydrocarbon ring-containing group having 6 to 40 carbon atoms may be substituted with —O—, and the aromatic hydrocarbon ring having 6 to 40 carbon atoms may be substituted.
  • One or more hydrogen atoms in the contained group may be substituted with a hydroxyl group.
  • n11 represents an integer of 1 to 10.
  • aromatic hydrocarbon ring-containing group having 6 to 40 carbon atoms a group obtained by removing "n11-1" of a hydrogen atom from the aromatic hydrocarbon ring-containing group having 6 to 40 monovalent carbon atoms shall be used. Can be done.
  • the aromatic hydrocarbon ring-containing group having a monovalent carbon atom number of 6 to 40 represented by X 11 may be a hydrocarbon group containing an aromatic hydrocarbon ring and not containing a heterocycle, and may be, for example, the above. Examples thereof include groups similar to the aromatic hydrocarbon ring-containing group having 6 to 40 carbon atoms used in X 1 and the like. More specifically, examples of the aromatic hydrocarbon ring-containing group represented by X 11 include a group in which an aryl group and a linear or branched alkyl group are combined. For example, one or more hydrogen atoms in a linear or branched alkyl group may be substituted with an aryl group, or one or more methylene groups in a linear or branched alkyl group.
  • a group substituted with a group obtained by removing one hydrogen atom from an aryl group, a group in which one or more of the hydrogen atoms of the aryl group are substituted with a linear or branched alkyl group, residues of phenol novolac, etc. Can be mentioned.
  • the contents of the aryl group and the alkyl group the same group as the aryl group and the alkyl group used for R 1 and the like can be used.
  • N11 is preferably an integer of 1 to 7, particularly preferably an integer of 2 to 3, and particularly preferably 2. This is because the above composition is excellent in the balance of storage stability and low-temperature adhesiveness, and is also excellent in the balance of ease of preparation and coatability of the composition.
  • the aromatic hydrocarbon ring-containing group having a monovalent 6 to 40 carbon atoms represented by X 11 includes one or two methylene groups in a linear or branched alkyl group having 6 to 20 carbon atoms.
  • the above is preferably a group substituted with a group obtained by removing one hydrogen atom from the aryl group, and among them, one or more of the methylene groups in the linear or branched alkyl group are from the aryl group. It is preferably a group having 13 to 18 carbon atoms substituted with a group excluding one hydrogen atom.
  • 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 independently represent numbers from 0 to 5, respectively. R 61-1 represents a divalent aromatic ring-containing group represented by the following general formula (7). * Represents a bond. )
  • 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 independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, and the hydrogen atom in the alkylene group may be substituted with a methyl group or a halogen atom.
  • t represents an integer from 0 to 5 and represents u represents an integer from 0 to 30 * Represents the joint location.
  • Examples of the alkyl group having 1 to 4 carbon atoms represented by R 62-1 and R 63-1 of the general formula (6-1) include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. Examples thereof include an isobutyl group, a second butyl group, and a third butyl group.
  • Examples of the alkylene group having 1 to 4 carbon atoms represented by Z 3 and Z 4 of the general formula (7) include a methylene group, a methylidene group, an ethylene group, an ethylidene group, an n-propylene group, a propyridene group and an isopropi.
  • Examples thereof include a lidene group, a methylethylene group, an n-butylene group, a butylidene group, an isobutylidene group, a sec-butylidene group, a 1,2-dimethylethylene group, a 1-methylpropylene group and a 2-methylpropylene group.
  • Examples of the halogen atom that replaces the hydrogen atom in the alkylene group having 1 to 4 carbon atoms represented by Z 3 and Z 4 of the general formula (7) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Can be mentioned.
  • r1 and s1 are each independently preferably an integer of 0 to 3, particularly preferably an integer of 0 to 2, and particularly an integer of 0 to 1. It is preferably present, and particularly preferably 0. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • 85 , R 86 and R 87 are a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, that is, a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • Z 3 and Z 4 are independently alkylene groups having 1 to 4 carbon atoms, and in particular, Z 3 and Z 4 are alkylene groups having 2 to 4 carbon atoms. It is preferably an alkylene group having 2 to 3 carbon atoms.
  • the alkylene group used for Z 3 and Z 4 is an alkylidene group such as a methylene group, an ethylidene group, a propylene group, a propyridene group or an isopropylidene group, that is, the aromatic epoxy compound has a bisphenol A type structure. It is preferable that the compound has a bisphenol structure such as a bisphenol E type structure and a bisphenol F type structure. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • t is preferably 0 to 3, and more preferably 0 to 1.
  • u is preferably 0 to 10, particularly preferably 0 to 5, particularly preferably 0 to 2, and particularly preferably 0. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the aliphatic epoxy compound has an epoxy group and does not contain a cycloalkene oxide structure and an aromatic ring.
  • Specific examples of such an aliphatic epoxy compound include a glycidyl etherified product of an aliphatic alcohol, a polyglycidyl etherified product of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof.
  • 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, glycerin.
  • Triglycidyl ether Triglycidyl ether, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, diglycidyl ether of neopentyl glycol, etc.
  • examples thereof include monoglycidyl ether of alcohol and epoxidized polybutadiene.
  • two or more glycidyl ether groups are added to the main chain skeleton containing a rubber component and a group capable of reacting with an epoxy group to form a covalent bond (hereinafter, also referred to as "epoxide group reactive group").
  • Examples thereof include a compound obtained by reacting an aliphatic type glycidyl ether type epoxy compound having the same.
  • a hydrogenated additive of an aromatic epoxy compound such as hydrogenated bisphenol A diglycidyl ether can also be used.
  • the aliphatic epoxy compound include cycloalkyl derived from an epoxycycloalkyl ring such as 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol.
  • a compound having a structure in which an oxylanyl group is directly bonded to the ring by a single bond as a constituent unit and a structure in which the epoxy groups of the epoxycycloalkyl ring are polymerized as a main chain structure can also be used.
  • the aliphatic epoxy compound any of an aliphatic ring-containing epoxy compound having an aliphatic ring such as an aliphatic hydrocarbon ring and an aliphatic heterocycle, and a chain aliphatic epoxy compound having no aliphatic ring can be used.
  • the aliphatic epoxy compound contains an aliphatic ring-containing epoxy compound having an aliphatic hydrocarbon ring and a chain aliphatic epoxy compound. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the content of the epoxy group in the above-mentioned aliphatic epoxy compound may be one that can obtain desired storage stability and low-temperature adhesiveness, and may be 1 or more per molecule of the aliphatic epoxy compound, but 1 or more. It is preferably 6 or less, preferably 1 or more and 4 or less, preferably 1 or more and 3 or less, and preferably 1 or 2. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the epoxy equivalent of the aliphatic epoxy compound may be one that can obtain desired storage stability and low-temperature adhesiveness, but is preferably 100 or more and 500 or less, and more preferably 130 or more and 400 or less. It is preferable, and in particular, it is preferably 150 or more and 350 or less. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • aliphatic epoxy compound a commercially available product can be used, for example, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-221, 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 Corporation); Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P,
  • (1-3) Alicyclic Epoxy Compound As a specific example of the alicyclic epoxy compound, a polyglycidyl etherified compound or cyclohexene of a polyvalent alcohol having at least one alicyclic ring and having a hydroxyl group directly bonded to the alicyclic ring. Examples thereof include cycloalkene oxide structure-containing compounds such as cyclohexene oxide and cyclopentene oxide obtained by epoxidizing a cyclopentene ring-containing compound with an oxidizing agent.
  • the epoxy equivalent of the alicyclic epoxy compound may be one that can obtain desired storage stability and low-temperature adhesiveness, but is preferably 80 or more and 500 or less, and above all, 100 or more and 300 or less. Is preferable, and in particular, it is preferably 120 or more and 250 or less. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate.
  • Examples of commercially available products that can be suitably used as the alicyclic epoxy compound include those described in Japanese Patent No. 6103653.
  • the molecular weight of the cyclic ether compound is not particularly limited as long as it can obtain desired curability and the like, and is, for example, 50 or more and 20. It can be 000 or less. From the viewpoint of the balance of storage stability and low-temperature adhesiveness of the composition, as well as the ease of coating and adhesion of the composition, it is more preferably 100 or more and 2,000 or less, and further preferably 200 or more and 1,500 or less. Is preferable.
  • the molecular weight indicates the weight average molecular weight (Mw) when the compound is a polymer. Further, the weight average molecular weight can be obtained as a standard polystyrene-equivalent value by gel permeation chromatography (GPC).
  • the weight average molecular weight for example, GPC (LC-2000plus series) manufactured by JASCO Corporation is used, the elution solvent is tetrahydrofuran, and the polystyrene standard for calibration curve is 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 Toso Co., Ltd.), and the measurement column is KF. It can be measured and obtained as -804, KF-803, KF-802 (manufactured by Showa Denko Corporation). Further, the measurement temperature can be 40 ° C. and the flow rate can be 1.0 mL / min.
  • the cyclic ether component contains, as the epoxy compound, a glycidyl ether type epoxy compound having a glycidyl ether group. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness. Further, since the glycidyl ether type epoxy compound has excellent curability, the composition exhibits excellent curability.
  • the cyclic ether component preferably contains at least one of an aromatic epoxy compound and an aliphatic epoxy compound as the epoxy compound, and more preferably contains an aromatic epoxy compound. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness. Further, it is preferable from the viewpoint of providing an excellent balance between storage stability and curability.
  • the cyclic ether component preferably contains a glycidyl ether type compound from the viewpoint of the balance between the storage stability and the low temperature adhesiveness of the composition, and the content thereof is particularly the composition.
  • the proportion of the glycidyl ether type epoxy compound in 100 parts by mass is preferably 30 parts by mass or more, and more preferably 80 parts by mass or more. In particular, it is preferably 90 parts by mass or more.
  • the proportion of the aromatic epoxy compound in 100 parts by mass of the cyclic ether component is preferably 30 parts by mass or more, particularly preferably 80 parts by mass or more, and particularly 90 parts by mass or more. Is preferable. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the content of the compound represented by the above general formula (14) is preferably 30 parts by mass or more, and more than 40 parts by mass in 100 parts by mass of the cyclic ether component. It is preferably 50 parts by mass or more, and particularly preferably 60 parts by mass or more.
  • the compound in which X 11 of the formula (14) is a group represented by the general formula (6-1) is preferably 30 parts by mass or more in 100 parts by mass of the cyclic ether component, and 40 parts by mass in particular.
  • the above is preferable, and in particular, it is preferably 50 parts by mass or more, and particularly preferably 60 parts by mass or more. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the content of the aliphatic epoxy compound is 1 part by mass or more and 30 parts by mass or less in 100 parts by mass of the cyclic ether component. It is preferably 5 parts by mass or more and 20 parts by mass or less. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the content of the alicyclic epoxy compound is 0.1 part by mass or more and 30 parts by mass in 100 parts by mass of the cyclic ether component. It is preferably 0.2 parts by mass or more, preferably 20 parts by mass or less, and preferably 0.3 parts by mass or more and 10 parts by mass or less. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the content of the cyclic ether component is preferably 20 parts by mass or more and 80 parts by mass or less, and 40 parts by mass or more and 75 parts by mass or more, in a total of 100 parts by mass of the cyclic ether component and the thiol component. It is more preferably less than parts by mass. This is because the above composition is excellent in the balance between storage stability and low temperature adhesiveness.
  • the content of the cyclic ether component is preferably 10 parts by mass or more and 90 parts by mass or less, preferably 15 parts by mass, out of 100 parts by mass of the composition of the present disclosure. It is more preferably 20 parts by mass or more and 75 parts by mass or less, further preferably 30 parts by mass or more and 70 parts by mass or less, and particularly preferably 70 parts by mass or less.
  • the content of the cyclic ether component is preferably 10 parts by mass or more and 90 parts by mass or less in 100 parts by mass of the solid content of the composition of the present disclosure. , 15 parts by mass or more and 80 parts by mass or less, further preferably 20 parts by mass or more and 75 parts by mass or less, and particularly preferably 30 parts by mass or more and 70 parts by mass or less.
  • the composition may contain a radically polymerizable component as a curable component as well as a cyclic ether component and a thiol component.
  • the radically polymerizable component refers to one or more of compounds having a radically polymerizable group (hereinafter, also referred to as “radical polymerizable compound”). Since the radically polymerizable compound has an excellent curing rate as compared with the cyclic ether component or the like, it may be easy to set the bonding conditions according to the application by curing the radically polymerizable compounds with each other.
  • compound 1 can generate radicals when generating bases
  • radically polymerizable compounds can be polymerized with each other without adding a separate radical polymerization initiator or by adding a smaller amount of radical polymerization initiator than usual.
  • a compound having an ethylenically unsaturated group and a thiol compound, which are typical examples of radically polymerizable compounds are cured by a Michael addition reaction with a base generated by a base generator. Therefore, it becomes easy to adjust the curing speed, the durability of the cured product, and the like.
  • a compound having an ethylenically unsaturated group such as an acryloyl group, a methacryloyl group, and a vinyl group can be used.
  • 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.
  • the radically polymerizable compound is a compound having no cyclic ether group or thiol group.
  • radically polymerizable compounds examples include polyethylene glycol diacrylate, polypropylene glycol diacrylate, propoxylated ethoxylated bisphenol A diacrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, and the like.
  • Tricyclodecanedimethanol diacrylate 1,10-decanediol diacrylate, 1,9-nonanediol diacrylate, tripropylene glycol diacrylate, polytetramethylene glycol # 650 diacrylate, ethoxylated isocyanuric acid triacrylate, ⁇ - Caprolactone-modified tris- (2-acryloxyethyl) isocyanurate, pentaerythritol triacrylate, trimethylolpropanetriacrylate, ditrimethylolpropanetetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc.
  • radically polymerizable compound a compound described as a radically polymerizable compound in International Publication No. 2016/136752, JP-A-2016-210849, JP-A-2016-17609 and the like can also be used.
  • the number of functional groups such as ethylenically unsaturated groups of the radically polymerizable compound is preferably 2 or more and 8 or less from the viewpoint that the curing rate can be improved, and in particular, 3 It is preferably 7 or more, and more preferably 3 or more and 6 or less.
  • a compound represented by the following general formula (15) can be preferably used. This is because the above-mentioned composition easily enhances the low-temperature adhesiveness by being such a compound.
  • R 1501 represents a hydrogen atom or a methyl group.
  • X 15 is an aliphatic hydrocarbon group having the same number of valences as n15 and having an unsubstituted or substituent having 1 to 40 carbon atoms; and having the same number of valences as n15 and having 6 to 6 carbon atoms.
  • n15 represents an integer of 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 "-)
  • X 15 having a same number of valence and n15, unsubstituted or substituted group is an aliphatic hydrocarbon radical having; n15 have the same number of valence and, having unsubstituted or substituted group Aromatic hydrocarbon ring-containing groups; and heterocyclic or substituent-containing heterocyclic groups having the same number of valences as n15 are represented by X 1 in the above general formula (A).
  • Examples thereof include an aromatic hydrocarbon ring-containing group or a group similar to a heterocyclic ring-containing group having an unsubstituted or substituent having 2 to 20 carbon atoms.
  • R'or R'used in group IV of the general formula (15) the same groups as those used in groups I-1, II-1 and the like can be used.
  • N15 is preferably in the same range as the preferable number of functional groups such as ethylenically unsaturated groups of the radically polymerizable compound.
  • the radically polymerizable component is a compound containing no aromatic ring or heterocyclic ring
  • the radically polymerizable component is represented by the above formula (15)
  • X 15 is an aliphatic hydrocarbon group or an aliphatic hydrocarbon. Examples thereof include compounds in which one or more of the methylene groups of the group are replaced by a group selected from Group IV under non-adjacent conditions, for example X 15 is an aliphatic hydrocarbon group or an aliphatic group.
  • Compounds in which one or more of the methylene groups of the hydrocarbon radical are replaced with —O— are preferred. This is because the radically polymerizable component is easily available and the curing rate of the composition is easily increased.
  • X 15 is a compound in which one or more of the aliphatic hydrocarbon group or the methylene group of the aliphatic hydrocarbon group is replaced with a group selected from Group IV.
  • a compound represented by the formula (15), wherein X 15 is a branched alkyl group having 5 to 16 carbon atoms or a group in which the methylene group of the alkyl group is replaced with —O— is preferable.
  • a compound represented by the above formula (15) and X 15 is the group exemplified above as X 11 of the above formula (14) can be used.
  • X 15 may be a group represented by the above formula (6-1).
  • the content of the radically polymerizable component may be, for example, 0 part by mass in 100 parts by mass of the total amount of the radically polymerizable component and the cyclic ether component, but when it is contained, it is 1 part by mass or more and 70 parts by mass. It is preferably 5 parts by mass or more and 40 parts by mass or less, and particularly preferably 8 parts by mass or more and 30 parts by mass or less. When the content is within such a range, the above composition may easily enhance low-temperature adhesiveness.
  • the content of the radically polymerizable component may be, for example, 0 part by mass in 100 parts by mass of the total amount of the radically polymerizable component, the cyclic ether component and the thiol component, but if it is contained, it is 1 part by mass or more. It is preferably 50 parts by mass or less, more preferably 5 parts by mass or more and 30 parts by mass or less, and particularly preferably 10 parts by mass or more and 20 parts by mass or less. When the content is within the range, it may be easy to improve the low temperature adhesiveness.
  • resin components other than the cyclic ether component, the radically polymerizable component and the thiol component may be contained.
  • other resin components include photosensitive resins, specific examples thereof include resins having an anionic polymerizable functional group as catalysts, and resins whose curing temperature is lowered by using a base as a catalyst, and specific examples thereof include energy such as ultraviolet rays.
  • photosensitive resins specific examples thereof include resins having an anionic polymerizable functional group as catalysts, and resins whose curing temperature is lowered by using a base as a catalyst, and specific examples thereof include energy such as ultraviolet rays.
  • Examples thereof include a photosensitive resin that polymerizes and cures by irradiating with a line, or a cured resin that lowers the curing temperature.
  • the suitable amount thereof is preferably 50 parts by mass or less, preferably 30 parts by mass or less, based on 100 parts by mass of the total amount of the radically polymerizable compound and the cyclic ether compound. More preferably, it is less than or equal to a part. This is because it is easy to improve the storage stability and low temperature adhesiveness of the composition by setting the amount of the thiol component and the cyclic ether component to a certain amount or more.
  • the above composition can contain a radical polymerization initiator together with a radically polymerizable component.
  • the radical polymerization initiator include photoradical polymerization initiators for acetophenone-based compounds, benzyl-based compounds, benzophenone-based compounds, thioxanthone-based compounds and oxime ester-based compounds, and azo-based compounds described in International Publication No. 2018/012383.
  • Thermal radical polymerization initiators such as compounds, peroxides and persulfates, and photoradical polymerization initiators described in JP-A-2016-210849 can be used.
  • solvent is liquid at room temperature (25 ° C.) at atmospheric pressure and can disperse or dissolve each component in the composition. Therefore, the compound 1, the cyclic ether component, the thiol component, and the radically polymerizable component are not contained in the solvent even if it is liquid at room temperature (25 ° C.) atm.
  • the solvent either water or an organic solvent can be used. In the present disclosure, it is preferable that the solvent is an organic solvent. This is because the compound 1, the cyclic ether component and the thiol component can be easily dissolved or dispersed.
  • organic solvent examples include carbonates such as propylene carbonate and diethyl carbonate; ketones such as acetone and 2-heptanone; monomethyl ethers of ethylene glycol, propylene glycol, propylene glycol monoacetate, dipropylene glycol and dipropylene glycol monoacetate.
  • Polyhydric alcohols such as monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; esters such as ethyl formate, 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene; Examples thereof include lactones such as ⁇ -caprolactone and ⁇ -caprolactone.
  • the content of the solvent is preferably 1 part by mass or more and 70 parts by mass or less, and 2 parts by mass or more and 50 parts by mass or less in 100 parts by mass of the composition for ease of handling and coatability of the composition. It is more preferable in terms of the like.
  • the composition contains compound 1, a thiol component, and a cyclic ether component, and may contain a radically polymerizable component and a solvent, if necessary, but may further contain an additive if necessary. ..
  • an additive those described as additives in International Publication 2019/111762 can be used, and for example, an inorganic compound, a coloring material, a latent epoxy curing agent, a chain transfer agent, a sensitizer, and a surfactant.
  • the total content of the additives (excluding the inorganic compound and the coloring material) is appropriately selected depending on the purpose of use thereof and is not particularly limited, but is preferably a total of 100 of the compound 1, the cyclic ether component and the thiol component. It can be 50 parts by mass or less with respect to the mass part. This is because the above composition tends to be excellent in storage stability and low temperature adhesiveness.
  • compositions of the present disclosure have high storage stability and can form a film having a uniform film thickness, and also have high curability and are not metal corrosive. From these points, the compositions of the present disclosure can be particularly suitably used for adhesives or wiring protection. It can also be used for wiring protection and as a protective material that comes into direct contact with metal wiring.
  • Applications other than adhesives or wiring protection include photocurable paints or varnishes; metal coatings; printed circuit boards; color filters in color display liquid crystal display elements such as color televisions, PC monitors, mobile information terminals, and digital cameras.
  • Color filter for CCD image sensor Electrode material for plasma display panel; Powder coating; Printing ink; Printing plate; Adhesive; Dental composition; Gel coat; Photo resist for electronic engineering; Electro-plated resist; Etching resist; Dry Films; solder resists; resists for manufacturing color filters for various display applications or for forming their structures in the manufacturing process of plasma display panels, electroluminescent displays, and LCDs; encapsulation of electrical and electronic components.
  • compositions for Materials for manufacturing objects Holography recording materials; Image recording materials; Microelectronic circuits; Decolorizing materials; Decolorizing materials for image recording materials; Decolorizing materials for image recording materials using microcapsules; For printed wiring boards
  • the cured product of the present disclosure is a cured product of the above-mentioned composition. According to the cured product of the present disclosure, since it is formed by using the above-mentioned composition, it is sufficiently adhered at a desired place without causing deterioration of peripheral members.
  • the cured product may contain a high molecular weight substance obtained by polymerizing the cyclic ether components with each other, the cyclic ether component and the thiol component.
  • the plan view shape of the cured product can be appropriately set according to the intended use of the cured product, and may be, for example, a pattern shape such as a dot shape or a line shape.
  • the uses and the like of the cured product can be the same as those described in the section of "A. Composition" above.
  • the method for producing the cured product is not particularly limited as long as it can form the cured product of the composition into a desired shape.
  • a manufacturing method for example, the manufacturing method described in the section "C. Manufacturing method of cured product" described later can be used.
  • the method for producing a cured product of the present disclosure includes a curing step of curing the above-mentioned composition. According to the present disclosure, since it is formed by using the above-mentioned composition, it is possible to obtain a sufficiently adhered cured product at a desired place without causing deterioration of peripheral members. Hereinafter, each step of the manufacturing method of the present disclosure will be described in detail.
  • the curing step is a step of curing the above composition.
  • the method for curing the composition may be any method as long as it is a method for obtaining a high molecular weight body by polymerizing the cyclic ether components in the composition, the cyclic ether component and the thiol component.
  • a polymerization method a method in which the above composition is subjected to light irradiation treatment to generate a base and a radical from compound 1 can be used.
  • the light irradiated to the composition may include light having a wavelength of 300 nm to 450 nm.
  • the light source for the light irradiation examples include ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc and the like.
  • Laser light may be used as the light to be irradiated.
  • a light having a wavelength of 340 to 430 nm can be used.
  • a light source in the visible to infrared region such as an argon ion laser, a helium neon laser, a YAG laser, and a semiconductor laser can also be used.
  • the composition can contain a sensitizing dye that absorbs the region from visible to infrared.
  • the coating film may or may not be heated after irradiation with the above energy rays for curing the composition of the present disclosure.
  • heating at about 40 to 150 ° C. is preferable in terms of the curing rate, but in the present disclosure, it can be a low temperature of 100 ° C. or lower, further a low temperature of 80 ° C. or lower.
  • the heating time is usually 1 minute to 120 minutes.
  • the method for producing a cured product may include, if necessary, other steps in addition to the curing step.
  • Other steps include a development step of removing unpolymerized portions in the coating film of the composition to obtain a patterned cured product after the curing step, and a post-baking step of heat-treating the cured product after the curing step. Examples thereof include a prebaking step of heat-treating the composition to remove the solvent in the composition before the curing step, a step of forming a coating film of the composition before the curing step, and the like.
  • a method for removing the unpolymerized portion in the development step for example, a method of applying an alkaline developer to the unpolymerized portion can be mentioned.
  • an alkaline developer a tetramethylammonium hydroxide (TMAH) aqueous solution, a potassium hydroxide aqueous solution, or the like, which is generally used as an alkaline developer, can be used.
  • the timing of carrying out the development step may be after the curing step.
  • the heating conditions in the post-baking step may be any as long as they can improve the strength of the cured product obtained in the curing step, and can be, for example, 20 to 90 minutes at 200 ° C. or higher and 250 ° C. or lower.
  • the heating conditions in the prebaking step may be any one that can remove the solvent in the composition, and can be, for example, 70 ° C. or higher and 150 ° C. or lower for 30 seconds to 300 seconds.
  • a method for applying the composition in the step of forming the coating film known methods such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, and dipping can be used.
  • the coating film can be formed on a substrate.
  • the base material can be appropriately set according to the intended use of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, wiring substrates, metals, paper, plastics, and the like. Further, the cured product may be formed on a base material and then peeled off from the base material and used, or may be transferred from the base material to another adherend and used.
  • the present disclosure is not limited to the above embodiment.
  • the above embodiment is an example, and any one having substantially the same structure as the technical idea described in the claims of the present disclosure and having the same effect and effect is the present invention. Included in the technical scope of the disclosure.
  • compositions were prepared according to the formulations shown in Tables 3 to 6 below.
  • the numerical values in the table represent parts by mass.
  • the reference numerals of the respective components in the table represent the following components.
  • the structure of some of the following components is shown below.
  • 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, aliphatic ring-containing epoxy compound having an aliphatic hydrocarbon ring, hydrogenated bisphenol A type epoxy compound)
  • A5 Compound represented by the following formula (A-5) (alicyclic epoxy compound, Daicel, Celoxide 2021P)
  • A6 Compound represented by the following formula (A-6) (aliphatic epoxy compound, glycid)
  • B1 Compound represented by the following formula (B-1) (PEMP, molecular weight 488.64, functional group 4, SC Organic Chemistry Co., Ltd.)
  • B2 Compound represented by the following formula (B-2) (TEMPIC, molecular weight 525.6, functional group 3, SC Organic Chemistry Co., Ltd.)
  • B3 Compound represented by the following formula (B-3) (TMMP, molecular weight 398.5, functional group 3, SC Organic Chemistry Co., Ltd.)
  • C1 Compound represented by the following formula (C-1) (DPHA, Nippon Kayaku Co., Ltd.)
  • C2 Compound represented by the following formula (C-2) (Viscort # 295, Osaka Organic Chemical Industry Co., Ltd.)
  • C3 Compound represented by the following formula (C-3) (ABE300, Shin Nakamura Chemical Industry Co., Ltd.)
  • C4 Compound represented by the following formula (C-4) (4-HBA, Mitsubishi Chemical Corporation)
  • Adhesiveness 1 The compositions obtained in Examples and Comparative Examples were applied to a SUS substrate as a first substrate with a dispenser so that the thickness after curing (thickness of the adhesive layer) was 100 ⁇ m, and the composition was applied with a high-pressure mercury lamp. Irradiation was performed at 3,000 mJ / cm 2 (integrated light intensity in the wavelength range of 315 nm to 400 nm). Next, a SUS base material was placed on the coating film as a second base material, and then heat treatment was performed at 60 ° C. for 60 minutes to obtain an evaluation sample. The peel strength was measured using this evaluation sample.
  • the bonding of the first base material and the second base material was adjusted so that the contact area between the cured product of the composition and the first base material and the second base material had 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, and the compression shear adhesive force (MPa) was measured under the conditions of a measurement temperature of 25 ° C. and a compression speed of 15 mm / min. From the measurement results, the adhesive strength was evaluated according to the following criteria. The results are shown in Tables 3 to 6 below. ++: Material destruction or 5 MPa or more +: Less than 5 MPa but cured.
  • Adhesive strength 2 The same as "3. Adhesive strength 1" above, except that a SUS substrate was placed as a second substrate on the coating film after light irradiation and then allowed to stand at 25 ° C. for 24 hours to obtain an evaluation sample. The adhesive strength was evaluated by the method of. The results are shown in Tables 3 to 6 below.
  • compositions of the present disclosure are excellent in curability when maintained from room temperature to low temperature after light irradiation and stability of adhesiveness after exposure. It has high adhesiveness when the members are bonded to each other, and has excellent low-temperature adhesiveness.
  • composition was prepared with the formulations shown in Tables 9 to 13 below.
  • the numerical values in the table represent parts by mass.
  • the reference numerals of the respective components in the table represent the following components.
  • the structure of some of the following components is shown below.
  • A10 Compound represented by the following formula (A-10) (aliphatic epoxy compound, glycidyl ether type, ED-523T manufactured by ADEKA Corporation).
  • A11 Compound represented by the following formula (A-11) (aliphatic epoxy compound, glycidyl ether type, Epogosei 2EH manufactured by Yokkaichi Chemical Co., Ltd.)
  • A12 A compound represented by the following formula (A-12) (aliphatic epoxy compound, ED-505 manufactured by ADEKA Corporation).
  • A13 Compound represented by the following formula (A-13) (aliphatic epoxy compound, glycidyl ether type, DY-022 manufactured by Nagase ChemteX Corporation)
  • (Radical polymerizable component) C5 Compound represented by the following formula (C-5) (KAYARAD DPCA-60 manufactured by Nippon Kayaku Co., Ltd.)
  • compositions shown in Tables 9 to 13 were evaluated in 1 to 5 above. The results are shown in Tables 9 to 13. The diagonal line indicates that the evaluation has not been carried out.

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
WO2023058605A1 (ja) * 2021-10-06 2023-04-13 株式会社ダイセル 硬化性樹脂組成物及びその硬化物
WO2025131912A1 (en) 2023-12-22 2025-06-26 Essilor International Latent borate-ammonium or iminium salts as photo-activatable catalysts for polythiourethane based substrates

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001513765A (ja) * 1997-02-26 2001-09-04 チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド α−アンモニウムケトン、イミニウムケトンまたはアミジニウムケトンおよびアリールボラートに基づく、光による活性化が可能な窒素含有塩基
CN105924571A (zh) * 2016-05-19 2016-09-07 深圳长朗三维科技有限公司 连续光固化三维打印材料
WO2019017418A1 (ja) * 2017-07-21 2019-01-24 株式会社Adeka 組成物、これを含む接着剤、組成物の硬化物およびその製造方法
JP2020139136A (ja) * 2018-11-30 2020-09-03 株式会社Adeka 組成物、硬化物及び硬化物の製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7691555B2 (en) * 2003-08-06 2010-04-06 Mitsubishi Gas Chemical Company, Inc. Photocurable composition and coating composition
JP4843955B2 (ja) * 2004-02-16 2011-12-21 三菱瓦斯化学株式会社 光塩基発生剤
JP5682311B2 (ja) 2008-12-02 2015-03-11 和光純薬工業株式会社 光塩基発生剤
JP5516417B2 (ja) 2008-12-02 2014-06-11 和光純薬工業株式会社 光塩基発生剤
WO2021261497A1 (ja) * 2020-06-26 2021-12-30 株式会社Adeka 化合物、開始剤、組成物、硬化物及び硬化物の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001513765A (ja) * 1997-02-26 2001-09-04 チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド α−アンモニウムケトン、イミニウムケトンまたはアミジニウムケトンおよびアリールボラートに基づく、光による活性化が可能な窒素含有塩基
CN105924571A (zh) * 2016-05-19 2016-09-07 深圳长朗三维科技有限公司 连续光固化三维打印材料
WO2019017418A1 (ja) * 2017-07-21 2019-01-24 株式会社Adeka 組成物、これを含む接着剤、組成物の硬化物およびその製造方法
JP2020139136A (ja) * 2018-11-30 2020-09-03 株式会社Adeka 組成物、硬化物及び硬化物の製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023058605A1 (ja) * 2021-10-06 2023-04-13 株式会社ダイセル 硬化性樹脂組成物及びその硬化物
JP2023055437A (ja) * 2021-10-06 2023-04-18 株式会社ダイセル 硬化性樹脂組成物及びその硬化物
WO2025131912A1 (en) 2023-12-22 2025-06-26 Essilor International Latent borate-ammonium or iminium salts as photo-activatable catalysts for polythiourethane based substrates

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