TW202302754A - Polymerizable composition, photocurable adhesive agent, cured product manufacturing method, and cured product - Google Patents

Abstract

The present invention addresses the problem of providing a polymerizable composition with which it is possible to manufacture a cured product having excellent resistance to moist heat. The present invention is a polymerizable composition containing a thioether compound (A), a cation-polymerizable compound (B), and a cationic polymerization initiator (C). The thioether compound (A) preferably includes an ester bond in the molecule. The polymerizable composition preferably contains the thioether compound (A) in an amount not less than 0.1 parts by mass but less than 10 parts by mass with respect to 100 parts by mass of the cation-polymerizable compound (B).

Description

Polymerizable composition, photocurable adhesive, method for producing cured product, and cured product

The present invention relates to a polymeric composition and a cured product of the polymeric composition.

The cationically polymerizable composition is used in the fields of ink, paint, various coating agents, adhesives, optical members, and the like.

For example, various cationically polymerizable compositions used as photocurable adhesives are disclosed in the following Patent Documents 1 to 3. prior art literature patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2011-236389 Patent Document 2: Japanese Patent Laid-Open No. 2012-149262 Patent Document 3: International Publication No. 2008/111584

[Problem to be solved by the invention]

However, the heat-and-moisture resistance of the cured products of the polymerizable compositions described in Patent Documents 1 to 3 is not sufficient.

Therefore, an object of the present invention is to provide a polymerizable composition capable of producing a cured product excellent in heat-and-moisture resistance. [Technical means to solve the problem]

The inventors of the present invention have diligently studied to solve the above-mentioned problems, and as a result, have completed the present invention. That is, the present invention provides a polymerizable composition containing a thioether compound (A), a cationic polymerizable compound (B), and a cationic polymerization initiator (C).

Moreover, this invention provides the photocurable adhesive agent containing the said polymeric composition. Furthermore, the present invention provides a method for producing a cured product, which includes the step of irradiating active energy rays or heating the above-mentioned polymerizable composition. Also, the present invention provides a cured product of the above-mentioned polymerizable composition. Furthermore, the present invention provides a use of the above-mentioned polymerizable composition as a photocurable adhesive. [Effect of Invention]

According to the polymerizable composition of this invention, the hardened|cured material excellent in heat-and-moisture resistance can be manufactured.

The polymerizable composition of the present invention will be described in detail below. The polymerizable composition of the present invention contains a thioether compound (A). By containing the thioether compound (A), the heat-and-moisture resistance of the hardened|cured material of a polymeric composition becomes excellent. Furthermore, the heat resistance, adhesiveness, and optical characteristics of this cured product also become excellent.

The thioether compound (A) is a compound having a thioether bond in the molecule. In the present invention, a known thioether compound can be used as the thioether compound (A), without any particular limitation. In the present invention, in the case where the heat and humidity resistance of the cured product of the polymerizable composition becomes better and the heat resistance and adhesiveness of the cured product also become better, it is preferable to use a polymer having an ester bond in the molecule. sulfide compounds.

As a thioether compound having an ester bond in the molecule, for example, a thioether compound having an ester bond in the molecule having a group represented by the following general formula (I) is changed due to the moisture and heat resistance of the cured product of the polymerizable composition. It is better, and the heat resistance and adhesiveness of the cured product also become better, so it is preferable.

[chemical 1]

( ^wherein , R represents an aliphatic hydrocarbon group with 1 to 30 carbon atoms that may have substituents, an aromatic hydrocarbon-containing ring group with 6 to 30 carbon atoms that may have substituents, the above-mentioned aliphatic hydrocarbon group with 1 to 30 carbon atoms One or more methylene groups in the aliphatic hydrocarbon group are substituted with a divalent group selected from the following <Group A>, or one of the above-mentioned aromatic hydrocarbon ring groups with 6 to 30 carbon atoms One or more methylene groups are substituted with divalent groups selected from the following <Group A>, ^Y1 represents a divalent hydrocarbon group with 1 to 30 carbon atoms that may have a substituent or the carbon atom One or more methylene groups in the divalent hydrocarbon groups of 1 to 30 are substituted with divalent groups selected from the following <Group A>, * represents a bond; <Group A>:- O-, -CO-, -COO-, -OCO-, -NR ² -, -NR ³ CO-, or -S- R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms)

The aliphatic hydrocarbon group having ¹ to 30 carbon atoms represented by R in the general formula (I) may, for example, be an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a carbon An alkynyl group having 2 to 30 atoms, a cycloalkyl group having 3 to 30 carbon atoms, and the like.

The alkyl group having 1 to 30 carbon atoms represented by R ¹ may be linear or branched. Examples of linear alkyl groups include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl, Eicosyl, Icodecyl, Eicosyl Dialkyl, tricosyl, tetracosyl, pentadecyl, hexacyl, heptacyl, octadecyl, nonacosyl and triaconyl wait. As the branched alkyl group, one or more of the above-mentioned linear alkyl groups are substituted with an alkyl group having 1 to 9 carbon atoms, specifically, 1,3-dimethylbutyl Base, 1-isopropylpropyl, 1,2-dimethylbutyl, 2-heptyl, 1,4-dimethylpentyl, third heptyl, 2-methyl-1-isopropyl Propyl, 1-ethyl-3-methylbutyl, isooctyl, tertiary octyl, 2-ethylhexyl, 2-methylhexyl, 2-propylhexyl, isononyl, isodecyl, Isoundecyl and isododecyl, etc. The alkyl group having 1 to 9 carbon atoms may, for example, be an alkyl group having 1 to 9 carbon atoms among the alkyl groups having 1 to 30 carbon atoms represented by R ¹ . In the present invention, in the case where the heat resistance of the hardened product of the polymerizable composition becomes better and the heat resistance, adhesiveness and optical properties of the hardened product also become better, the number of carbon atoms of the alkyl group is higher than that of the cured product. Preferably it is 5-23, More preferably, it is 5-20, More preferably, it is 7-17, More preferably, it is 9-15. Also, from the same viewpoint, the alkyl group is preferably linear.

Examples of the alkenyl group having 2 to 30 carbon atoms represented by ^R include vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl Carbenyl, Nonadecenyl, Eicosenyl, Icodecenyl, Dococenyl, Tritricenyl, Tetradecenyl, Pentadecenyl , Hexadecenyl, Heptadecenyl, Hexadecenyl, Hexadecenyl and Triadecenyl, and the corresponding alkadienyl and alkatriene base.

The alkynyl group having 2 to 30 carbon atoms represented by R ¹ may, for example, be ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3- butynyl, 1-octynyl, 1-decynyl, 1-octadecynyl and the like.

Examples of the cycloalkyl group having 3 to 30 carbon atoms represented by ^R include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclooctadecyl. , 2-𦯉 group, 2-iso𦯉 group, 1-adamantyl group, etc.

In the present invention, an aromatic hydrocarbon ring-containing group means a group having an aromatic hydrocarbon ring. The aromatic hydrocarbon-containing ring group having 6 to 30 carbon atoms represented by R ¹ may have a monocyclic structure or a polycyclic structure. The aromatic hydrocarbon-containing ring group of the polycyclic structure may be a condensed ring structure or a structure in which two aromatic hydrocarbon rings are linked. As an aromatic hydrocarbon-containing ring group formed by linking two aromatic hydrocarbon rings, it may be formed by linking two aromatic hydrocarbon rings with a single-ring structure, or it may be an aromatic hydrocarbon ring with a single-ring structure and a condensed ring structure One formed by linking aromatic hydrocarbon rings, or two aromatic hydrocarbon rings of condensed ring structure linked together. As the linking group connecting two aromatic hydrocarbon rings, any aromatic hydrocarbon-containing ring group as a whole may be provided with aromaticity, and examples thereof include a single bond, a thio group (—S—), and a carbonyl group. As an aromatic hydrocarbon ring of a monocyclic structure, benzene, toluene, ethylbenzene, 2,4,6- trimethylbenzene, etc. are mentioned, for example. Examples of the aromatic hydrocarbon ring of the condensed ring structure include naphthalene, anthracene, phenanthrene, pyrene and the like. The aromatic hydrocarbon-containing ring group in which two aromatic hydrocarbon rings are linked may, for example, be a group in which aromatic hydrocarbon rings of a monocyclic structure, such as diphenyl sulfide and benzoylphenyl, are linked. In the present invention, the number of carbon atoms of the aromatic hydrocarbon ring is preferably from 6 to 20 from the viewpoint of better heat-and-moisture resistance of the cured product of the polymerizable composition. The number of carbon atoms in the aromatic hydrocarbon ring is more preferably 6-15 from the viewpoint of improving the heat resistance, adhesiveness, and optical properties of the cured product in addition to the heat-and-moisture resistance.

As the bivalent hydrocarbon group having 1 to 30 carbon atoms represented by ^Y , there may be mentioned an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent represented by ^R , or a carbon atom which may have a substituent A divalent group formed by removing one hydrogen atom from an aromatic hydrocarbon-containing ring group with a number of 6 to 30.

As the hydrocarbon group having 1 to 30 carbon atoms represented by ^R2 and ^R3 in Group A, for example, an aliphatic hydrocarbon group having 1 to 30 carbon atoms and an aromatic hydrocarbon ring group having 6 to 30 carbon atoms . The aliphatic hydrocarbon group having 1 to 30 carbon atoms represented by R ² and R ³ may, for example, be the same as the aliphatic hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ . The aromatic hydrocarbon-containing ring group having 6 to 30 carbon atoms represented by R ² and R ³ may, for example, be the same as the aromatic hydrocarbon ring group having 6 to 30 carbon atoms represented by R ¹ .

As an aliphatic hydrocarbon group having 1 to 30 carbon atoms and an aromatic hydrocarbon ring group having 6 to 30 carbon atoms represented by ^R1 , and a divalent hydrocarbon group having 1 to 30 carbon atoms represented by ^Y1 Examples of substituents include: alkyl groups with 1 to 8 carbon atoms; ethylenically unsaturated groups such as vinyl, allyl, acrylic, and methacrylic groups; halogen atoms such as fluorine, chlorine, bromine, and iodine; Acyl, 2-chloroacetyl, propionyl, octyl, acryl, methacryl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzene Formyl, popentyl, o-hydroxybenzoyl, oxalyl, stearyl, methoxycarbonyl, ethoxycarbonyl, tertiary butoxycarbonyl, n-octadecyloxycarbonyl, Aminoformyl and other acyl groups; Acyloxy, benzoyloxy and other acyloxy groups; Amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2 -Ethylhexylamine, dodecylamine, anilino, chloroanilino, toluidine, methoxyanilino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamine group, methoxycarbonylamine group, phenoxycarbonylamine group, acetamide group, benzamide group, formamide group, pivalylamide group, lauramide group, carbamidamide group, N ,N-Dimethylaminocarbonylamino, N,N-Diethylaminocarbonylamino, Morpholinylcarbonylamino, Methoxycarbonylamino, Ethoxycarbonylamino, Tertiary Butoxycarbonyl Amino group, n-octadecyloxycarbonylamine group, N-methyl-methoxycarbonylamine group, phenoxycarbonylamine group, sulfamoylamine group, N,N-dimethylaminosulfonamide group , methylsulfonamide, butylsulfonamide, phenylsulfonamide and other substituted amino groups; sulfonamide, sulfonyl, carboxyl, cyano, sulfo, hydroxyl, nitro, mercapto, Imino group, carbamoyl group, sulfonamide group, phosphonic acid group, phosphoric acid group, or salts of carboxyl, sulfo group, phosphonic acid group, phosphoric acid group, etc. The alkyl group having 1 to 8 carbon atoms may, for example, be an alkyl group having 1 to 8 carbon atoms among the alkyl groups having 1 to 30 carbon atoms represented by R ¹ .

The number of carbon atoms of a group specified in the present invention includes the number of carbon atoms of a substituent. For example, tolyl is an aromatic hydrocarbon-containing ring group having 7 carbon atoms. Also, the number of carbon atoms in a group in which one or more methylene groups specified in the present invention are substituted with divalent groups selected from <Group A> includes the number of carbon atoms in the divalent group. For example, the number of carbon atoms of a group in which one methylene group in an alkyl group having 10 carbon atoms is substituted with -COO- is assumed to be 10. Also, the number of carbon atoms of a group in which one methylene group in the alkyl group having 10 carbon atoms is replaced by -O- is set to 9. One or more methylene groups are substituted to be selected from the following <Group A1>, <Group B>, <Group C>, <Group D>, <Group E>, <Group F> or <Group G> The same is true for the number of carbon atoms in the base formed by the divalent base.

In the present invention, in the case where the adhesiveness and heat resistance of the cured product of the polymerizable composition become good, R ¹ in the general formula (I) preferably has a substituent having 5 to 20 carbon atoms. aliphatic hydrocarbon group or an aromatic hydrocarbon ring group with 6 to 20 carbon atoms which may have substituents, more preferably an aliphatic hydrocarbon group with 5 to 20 carbon atoms, and more preferably an alkane with 5 to 20 carbon atoms base. From the same viewpoint, the alkyl group having 5 to 20 carbon atoms is preferably linear. Moreover, the alkyl group having 5 to 20 carbon atoms preferably has no substituent from the viewpoint of compatibility.

In the present invention, Y ¹ in the general formula (I) preferably has 1 to 10 carbon atoms which may have a substituent in order to improve the adhesiveness and heat resistance of the cured product of the polymerizable composition. The divalent hydrocarbon group is more preferably an alkylene group having 1 to 10 carbon atoms which may have a substituent or an arylylene group having 1 to 10 carbon atoms which may have a substituent. From the same viewpoint, the alkylene group having 1 to 10 carbon atoms and the arylylene group having 1 to 10 carbon atoms preferably have no substituent. In addition, the number of carbon atoms in the alkylene group is preferably 1-8, more preferably 2-6, from the viewpoint that the cured product of the polymerizable composition has both heat resistance and compatibility. Also, the alkylene group is preferably linear.

In the present invention, when the thioether compound has a group represented by the general formula (I) in the molecule, the number of the groups represented by the general formula (I) in the compound may be 1 or plural. In the case where the adhesiveness and heat resistance of the cured product of the polymerizable composition become good, the thioether compound preferably has a plurality of groups represented by the general formula (I) in the molecule, and more preferably has a group represented by the general formula (I) in the molecule There are 2 to 8 groups represented by the general formula (I) in the molecule, more preferably 2 to 6 groups represented by the general formula (I) in the molecule, and particularly preferably 2 to 4 groups in the molecule The group represented by formula (I).

In the present invention, for example, a compound represented by the following general formula (I-A) can be used as the thioether compound having a group represented by the general formula (I).

[Chem 2]

(wherein, ^R represents an aliphatic hydrocarbon group with 1 to 30 carbon atoms that may have substituents, an aromatic hydrocarbon-containing ring group with 6 to 30 carbon atoms that may have substituents, the above-mentioned aliphatic hydrocarbon group with 1 to 30 carbon atoms One or more methylene groups in the aliphatic hydrocarbon group are substituted with a divalent group selected from the following <Group A>, or one of the above-mentioned aromatic hydrocarbon ring groups with 6 to 30 carbon atoms One or more methylene groups are substituted with divalent groups selected from the following <Group A>, and ^Y1 is a divalent hydrocarbon group with 1 to 30 carbon atoms that may have a substituent or the carbon atom One or more methylene groups in divalent hydrocarbon groups with numbers 1 to 30 are substituted with divalent groups selected from the following <Group A>, n represents an integer of 1 to 6, and D represents n valency group; <Group A>: -O-, -CO-, -COO-, -OCO-, -NR ² -, -NR ³ CO- or -S- R ² and R ³ each independently represent a hydrogen atom or a carbon Hydrocarbon group with 1 to 30 atoms)

The groups represented by R ¹ , R ² , R ³ and Y ¹ in formula (IA) are the same as those in general formula (I).

When n in the formula (I-A) is 1, the monovalent group represented by D includes, for example, an aliphatic hydrocarbon group having 1 to 30 carbon atoms that may have a substituent, and a carbon group that may have a substituent. In the aromatic hydrocarbon ring group having 6 to 30 atoms, one or more methylene groups in the aliphatic hydrocarbon group having 1 to 30 carbon atoms are substituted with divalent groups selected from the following <Group B> or a group in which at least one methylene group in the above-mentioned aromatic hydrocarbon ring group having 6 to 30 carbon atoms is substituted with a divalent group selected from the following <Group B>.

<Group B>: -O-, -CO-, -COO-, -OCO-, -NR ²⁰ -, -NR ³⁰ CO- or -S- R ²⁰ and R ³⁰ each independently represent the number of hydrogen atoms or carbon atoms 1 to 30 hydrocarbon groups.

Examples of the optionally substituted monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms and the optionally substituted monovalent aromatic hydrocarbon ring group having 6 to 30 carbon atoms represented by D include those mentioned above. The optionally substituted aliphatic hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ and the optionally substituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms are the same.

Examples of the hydrocarbon groups having 1 to 30 carbon atoms represented by R ²⁰ and R ³⁰ in <Group B> include the same ones as the hydrocarbon groups having 1 to 30 carbon atoms represented by R ² and R ³ described above.

When n in formula (I-A) is 2, as a divalent group represented by D, the group represented by following formula (1) is mentioned.

[Chem 3]

(wherein, Y ¹⁰ represents a single bond, -CO-, -NR ²⁰⁰ -, -S-, a divalent hydrocarbon group with 1 to 30 carbon atoms which may have a substituent, or the divalent hydrocarbon group with 1 to 30 carbon atoms In which one or more methylene groups are substituted with divalent groups selected from the following <Group C>, R ²⁰⁰ represents a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms, Z ¹ and Z ² Each independently represents a direct bond, -CO-, an optionally substituted divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms, or an optionally substituted divalent aromatic hydrocarbon-containing ring group having 6 to 30 carbon atoms , * represents a bonding bond; <Group C>: -O-, -CO-, -COO-, -OCO-, -NR ²¹ -, -NR ³¹ CO- or -S- R ²¹ and R ³¹ are independently Represents a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms)

As the divalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent represented by ^Y10 in formula (1), the same divalent hydrocarbon group as the above-mentioned divalent hydrocarbon group having 1 to 30 carbon atoms represented by ^Y1 can be exemplified. By.

Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ²⁰⁰ , R ²¹ and R ³¹ in formula (1) include the same hydrocarbon groups as those represented by R ² and R ³ described above. By.

Examples of the divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have substituents represented by ^Z1 and ^Z2 in the formula (1) include carbon atoms which may have substituents represented by ^R1 . A divalent group formed by removing one hydrogen atom from an aliphatic hydrocarbon group of 1 to 30.

Examples of the divalent aromatic hydrocarbon-containing ring group having 6 to 30 carbon atoms that may have substituents represented by ^Z1 and ^Z2 in formula (1) include those represented by ^R1 that may have substituents. A divalent group obtained by removing one hydrogen atom from an aromatic hydrocarbon-containing ring group with 6 to 30 carbon atoms.

When n in formula (I-A) is 3, as a trivalent group represented by D, the group represented by following formula (2) is mentioned.

[chemical 4]

(wherein, ^Y11 represents a trivalent hydrocarbon group having 1 to 30 carbon atoms which may have substituents or one or more methylene groups in the trivalent hydrocarbon group having 1 to 30 carbon atoms are substituted with a group selected from the following A group consisting of divalent groups in <Group D>, Z ¹ , Z ² and Z ³ each independently represent a direct bond, -CO-, a divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent , or a divalent aromatic hydrocarbon-containing ring group with 6 to 30 carbon atoms that may have a substituent, * represents a bond; <Group D>: -O-, -CO-, -COO-, -OCO-, -NR ²² -, -NR ³² CO- or -S- R ²² and R ³² each independently represent a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms)

The trivalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent represented by Y ¹¹ in the formula (2) may be exemplified from the divalent hydrocarbon groups having 1 to 30 carbon atoms represented by Y ¹ above. Then remove one hydrogen atom to form a trivalent group.

The hydrocarbon group having 1 to 30 carbon atoms represented by R ²² and R ³² in the formula (2) may, for example, be the same as the hydrocarbon group having 1 to 30 carbon atoms represented by R ² and R ³ described above.

The optionally substituted divalent aliphatic hydrocarbon groups having 1 to 30 carbon atoms represented by Z ¹ , Z ² and Z ³ in formula (2) may be exemplified by the above-mentioned optionally substituted aliphatic hydrocarbon groups represented by R ¹ . A divalent group formed by removing one hydrogen atom from an aliphatic hydrocarbon group with 1 to 30 carbon atoms in the group.

Examples of divalent aromatic hydrocarbon-containing ring groups having 6 to 30 carbon atoms which may have substituents represented by Z ¹ , Z ² and Z ³ in formula (2) include those represented by R ¹ above. A divalent group obtained by removing one hydrogen atom from an aromatic hydrocarbon-containing ring group having 6 to 30 carbon atoms which may have a substituent.

When n in formula (I-A) is 4, as a tetravalent group represented by D, the group represented by following formula (3) is mentioned.

[chemical 5]

(In the formula, ^Y12 represents a quaternary hydrocarbon group with 1 to 30 carbon atoms that may have a substituent or one or more methylene groups in the 4-valent hydrocarbon group with 1 to 30 carbon atoms are substituted with a group selected from the following A group formed from divalent groups in <Group E>, Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a direct bond, -CO-, and a divalent group with 1 to 30 carbon atoms that may have a substituent An aliphatic hydrocarbon group, or a divalent aromatic hydrocarbon ring group with 6 to 30 carbon atoms which may have a substituent, * indicates a bond; <Group E>: -O-, -CO-, -COO-, - OCO-, -NR ²³ -, -NR ³³ CO- or -S- R ²³ and R ³³ each independently represent a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms)

The tetravalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent represented by ^Y12 in the formula (3) may be exemplified from the divalent hydrocarbon group having 1 to 30 carbon atoms represented by ^Y1 above. Then remove 2 hydrogen atoms to form a 4-valent group.

The hydrocarbon group having 1 to 30 carbon atoms represented by R ²³ and R ³³ in formula (3) may, for example, be the same as the hydrocarbon group having 1 to 30 carbon atoms represented by R ² and R ³ described above.

Examples of divalent aliphatic hydrocarbon groups having 1 to 30 carbon atoms which may have substituents represented by Z ¹ , Z ² , Z ³ and Z ⁴ in formula (3) include those represented by R ¹ above. A divalent group obtained by removing one hydrogen atom from an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.

Examples of divalent aromatic hydrocarbon-containing ring groups having 6 to 30 carbon atoms which may have substituents represented by Z ¹ , Z ² , Z ³ and Z ⁴ in formula (3) include the above-mentioned R ¹ The divalent group obtained by removing one hydrogen atom from the aromatic hydrocarbon-containing ring group having 6 to 30 carbon atoms which may have a substituent.

When n in formula (I-A) is 5, as a pentavalent group represented by D, the group represented by following formula (4) is mentioned.

[chemical 6]

(In the formula, ^Y13 represents a 5-valent hydrocarbon group with 1 to 30 carbon atoms that may have a substituent, or one or more methylene groups in the 5-valent hydrocarbon group with 1 to 30 carbon atoms are substituted with a group selected from the following In <Group F>, a group consisting of a divalent group, Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ each independently represent a direct bond, -CO-, and the number of carbon atoms that may have a substituent is 1 to 30 A divalent aliphatic hydrocarbon group, or a divalent aromatic hydrocarbon ring group with 6 to 30 carbon atoms that may have a substituent, * indicates a bond; <Group F>: -O-, -CO-, -COO -, -OCO-, -NR ²⁴ -, -NR ³⁴ CO- or -S- R ²⁴ and R ³⁴ each independently represent a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms)

The pentavalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent represented by ^Y13 in the formula (4) may, for example, be selected from the divalent hydrocarbon groups having 1 to 30 carbon atoms represented by ^Y1 above. Then remove 3 hydrogen atoms to form a pentadyl group.

The hydrocarbon group having 1 to 30 carbon atoms represented by R ²⁴ and R ³⁴ in formula (4) may, for example, be the same as the hydrocarbon group having 1 to 30 carbon atoms represented by R ² and R ³ described above.

Examples of divalent aliphatic hydrocarbon groups having 1 to 30 carbon atoms which may have substituents represented by Z ¹ , Z ² , Z ³ , Z ^{4 ,} and Z ⁵ in formula (4) include those represented by R ¹ described above. A divalent group obtained by removing one hydrogen atom from an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.

Examples of divalent aromatic hydrocarbon-containing divalent aromatic hydrocarbon ring groups having 6 to 30 carbon atoms which may have substituents represented by Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ in formula (4) include the above-mentioned A divalent group formed by removing one hydrogen atom from the optionally substituent C6-30 aromatic hydrocarbon-containing ring group represented by R ¹ .

When n in formula (I-A) is 6, as a hexavalent group represented by D, the group represented by following formula (5) is mentioned.

[chemical 7]

(wherein, ^Y14 represents a hexavalent hydrocarbon group with 1 to 30 carbon atoms which may have substituents or one or more methylene groups in the hexavalent hydrocarbon group with 1 to 30 carbon atoms are substituted with a group selected from the following <Group G> is a group consisting of divalent groups, Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ each independently represent a direct bond, -CO-, and the number of carbon atoms that may have a substituent A divalent aliphatic hydrocarbon group of 1 to 30, or a divalent aromatic hydrocarbon ring group having 6 to 30 carbon atoms which may have a substituent, * indicates a bond; <Group G>: -O-, -CO- , -COO-, -OCO-, -NR ²⁵ -, -NR ³⁵ CO- or -S- R ²⁵ and R ³⁵ each independently represent a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms)

The hexavalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent represented by ^Y14 in the formula (5) may be exemplified from the divalent hydrocarbon group having 1 to 30 carbon atoms represented by ^Y1 above. Then remove 4 hydrogen atoms to form a hexavalent group.

The hydrocarbon group having 1 to 30 carbon atoms represented by R ²⁵ and R ³⁵ in the formula (5) may, for example, be the same as the hydrocarbon group having 1 to 30 carbon atoms represented by R ² and R ³ described above.

Examples of divalent aliphatic hydrocarbon groups having 1 to 30 carbon atoms that may have substituents represented by Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ in formula (5) include the above-mentioned A divalent group obtained by removing one hydrogen atom from an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent represented by R ¹ .

Examples of divalent aromatic hydrocarbon-containing ring groups having 6 to 30 carbon atoms that may have substituents represented by Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ in formula (5) include A divalent group obtained by removing one hydrogen atom from the above-mentioned optionally substituted carbon atom-containing aromatic hydrocarbon ring group represented by R ¹ and having 6 to 30 carbon atoms.

In the present invention, when the heat-and-moisture resistance of the cured product of the polymerizable composition becomes better and the heat resistance, adhesiveness, and optical properties of the cured product also become better, n in the formula (I-A) Preferably it is 1-6, More preferably, it is 1-5, More preferably, it is 1-4.

When n in the formula (IA) is 1, the moisture and heat resistance of the cured product of the polymerizable composition becomes better, and the heat resistance, adhesiveness and optical properties of the cured product also become better. In other words, the monovalent group represented by D is preferably an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring group having 6 to 30 carbon atoms which may have a substituent. From the same viewpoint, the aromatic hydrocarbon-containing ring group is preferably an aromatic hydrocarbon ring having a monocyclic structure, and is more preferably formed by linking two aromatic hydrocarbon rings having a monocyclic structure. Moreover, when the heat-and-moisture resistance of a polymeric composition becomes more favorable, it is preferable that two aromatic hydrocarbon rings are connected by -S-. In addition, when the heat resistance of the cured product of the polymerizable composition becomes good, it is preferable that the aromatic hydrocarbon-containing ring group has a substituent. Furthermore, the substituent is preferably an alkyl group having 1 to 10 carbon atoms or a hydroxyl group from the viewpoint of compatibility, and is more preferably an aromatic hydrocarbon-containing ring group substituted with an alkyl group or hydroxyl group. The alkyl group is preferably branched. The alkyl group having 1 to 10 carbon atoms may, for example, be an alkyl group having 1 to 10 carbon atoms among the alkyl groups having 1 to 30 carbon atoms represented by R ¹ described above. Also, from the same viewpoint, the number of carbon atoms in the aliphatic hydrocarbon group represented by D is preferably 5-20, more preferably 8-19, and still more preferably 10-15. Also, the aliphatic hydrocarbon group is preferably an alkyl group which may have a substituent, more preferably an alkyl group which does not have a substituent. When the monovalent group represented by D is an aliphatic hydrocarbon which may have a substituent, ^R1 is preferably an aliphatic hydrocarbon group with 5 to 23 carbon atoms which may have a substituent or a carbon atom which may have a substituent A group in which one or more methylene groups in an aliphatic hydrocarbon group of 5 to 23 is substituted with -COO- or -OCO-, more preferably an aliphatic hydrocarbon group of 5 to 23 carbon atoms which may have substituents A group in which one or more methylene groups are substituted with -COO- or -OCO-, and more preferably one or more methylene groups in an alkyl group having 5 to 23 carbon atoms that may have a substituent A group in which the group is substituted with -COO- or -OCO-, and more preferably one methylene group in an unsubstituted alkyl group having 9 to 23 carbon atoms is substituted with -COO- or -OCO- The foundation of becoming. When the number of carbon atoms of the aliphatic hydrocarbon group is within the above-mentioned range, compatibility and heat resistance become more favorable. Also, when R ¹ has -COO- or -OCO- in its structure, heat resistance becomes more favorable. From the viewpoint of moisture and heat resistance, the number of -COO- and -OCO- in the group represented by R ¹ is preferably 1-3, more preferably 1-2.

When n in the formula (IA) is 2, the moisture and heat resistance of the cured product of the polymerizable composition becomes better, and the heat resistance, adhesiveness and optical properties of the cured product also become better. In other words, Y ¹⁰ in formula (1) is preferably -S-. When Y ¹⁰ is -S-, Z ¹ and Z ² are preferably divalent aliphatic hydrocarbon groups with 1 to 30 carbon atoms that may have substituents, or Z ¹ and Z ² may have substituents. A divalent compound containing an aromatic hydrocarbon ring group with 6 to 30 carbon atoms. In the case where the heat-and-moisture resistance of the cured product of the polymerizable composition becomes better and the heat resistance, adhesiveness, and optical properties of the cured product also become better, the number of carbon atoms represented by Z ¹ and Z ² The divalent aliphatic hydrocarbon group of 1 to 30 is preferably an alkylene group having 1 to 30 carbon atoms. From the same viewpoint, the alkylene group is preferably linear. Moreover, it is preferable that this alkylene group does not have a substituent. Furthermore, from the viewpoint of compatibility, the number of carbon atoms in the alkylene group is preferably 1-10, more preferably 1-4. In the case where the heat-and-moisture resistance of the cured product of the polymerizable composition becomes better and the heat resistance, adhesiveness, and optical properties of the cured product also become better, the number of carbon atoms represented by Z ¹ and Z ² The divalent aromatic hydrocarbon-containing ring group of 6 to 30 is preferably an aromatic hydrocarbon ring with a monocyclic structure, more preferably a phenylene group. Also, the aromatic hydrocarbon-containing ring group preferably has a substituent. The substituent is preferably an alkyl group having 1 to 10 carbon atoms. From the viewpoint of compatibility, the alkyl group is preferably branched. The alkyl group having 1 to 10 carbon atoms may, for example, be an alkyl group having 1 to 10 carbon atoms among the alkyl groups having 1 to 30 carbon atoms represented by R ¹ described above.

When n in the formula (IA) is 4, the moisture and heat resistance of the cured product of the polymerizable composition becomes better, and the heat resistance, adhesiveness and optical properties of the cured product also become better. In other words, Y ¹² in formula (3) is preferably a tetravalent aliphatic hydrocarbon group having 1 to 30 carbon atoms, more preferably an alkanetetrayl group having 1 to 30 carbon atoms. The number of carbon atoms of the alkanetetrayl group is preferably 1-10, more preferably 1-7. Z ¹ , Z ² , Z ³ and Z ⁴ in formula (3) are preferably direct bonds.

As the thioether compound (A) of the present invention, when the heat-and-moisture resistance of the cured product of the polymerizable composition becomes better, and the heat resistance and adhesiveness of the cured product also become better, the following general Compounds represented by formula (I-B) are also preferred.

[Chem 7A]

(In the formula, ^R11 represents an aliphatic hydrocarbon group with 1 to 30 carbon atoms that may have substituents, an aromatic hydrocarbon-containing ring group with 6 to 30 carbon atoms that may have substituents, the above-mentioned aliphatic hydrocarbon group with 1 to 30 carbon atoms One or more methylene groups in the aliphatic hydrocarbon group are substituted with a divalent group selected from the following <Group A1>, or one of the above-mentioned aromatic hydrocarbon ring groups having 6 to 30 carbon atoms One or more methylene groups are substituted with divalent groups selected from the following <Group A1>, n1 represents an integer of 1 to 6, and D1 represents an optional substituent having 6 to 30 carbon atoms One or more methylene groups in an aromatic hydrocarbon-containing ring group or an optionally substituted aromatic hydrocarbon-containing ring group having 6 to 30 carbon atoms is substituted with a divalent group selected from the following <Group A1> Formed base; <Group A1>: -O-, -CO-, -COO-, -OCO-, -NR ^2a -, -NR ^3a CO- or -S- R ^2a and R ^3a each independently represent hydrogen atoms or hydrocarbon groups with 1 to 30 carbon atoms)

The aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent and the aromatic hydrocarbon-containing ring group having 6 to 30 carbon atoms which may have a substituent represented by R ¹¹ include the same as those represented by R ¹¹ above. The aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent and the aromatic hydrocarbon-containing ring group having 6 to 30 carbon atoms which may have a substituent are the same.

The aromatic hydrocarbon ring group having 6 to 30 carbon atoms which may have a substituent represented by D1 may, for example, be the same as the aromatic hydrocarbon ring group having 6 to 30 carbon atoms which may have a substituent represented by ^R1 . Those with the same hydrocarbon ring group.

Examples of the hydrocarbon groups having 1 to 30 carbon atoms represented by R ^2a and R ^3a in <Group A1> include the same ones as the hydrocarbon groups having 1 to 30 carbon atoms represented by R ² and R ³ described above.

^R11 in the above general formula (IB) is preferable in the case where the heat-and-moisture resistance of the cured product of the polymerizable composition becomes better and the heat resistance, adhesiveness, and optical properties of the cured product also become better. It is an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. From the same viewpoint, the aliphatic hydrocarbon group is preferably an alkyl group. Also, the number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-10, more preferably 4-8. The aliphatic hydrocarbon group is preferably unsubstituted. In the case where the heat-and-moisture resistance of the cured product of the polymerizable composition becomes better and the heat resistance, adhesiveness, and optical properties of the cured product also become better, n1 in the above general formula (IB) is preferably 1-4, more preferably 2-3. In the case where the heat-and-moisture resistance of the cured product of the polymerizable composition becomes better and the heat resistance, adhesiveness, and optical properties of the cured product also become better, the compound represented by D1 in the above general formula (IB) The aromatic hydrocarbon-containing ring group is preferably an aromatic hydrocarbon ring having a monocyclic structure, more preferably a phenyl group. The number of carbon atoms in the aromatic hydrocarbon-containing ring group is preferably 6-20, more preferably 6-16, and still more preferably 6-110. In addition, when the heat resistance of the cured product of the polymerizable composition becomes good, it is preferable that the aromatic hydrocarbon-containing ring group has a substituent. As the substituent, from the viewpoint of compatibility, it is preferably an alkyl group or hydroxyl group having 1 to 10 carbon atoms, particularly preferably an alkyl group or hydroxyl group having 1 to 4 carbon atoms, and more preferably a group containing The aromatic hydrocarbon ring group is substituted by an alkyl group and a hydroxyl group. The alkyl group having 1 to 10 carbon atoms may, for example, be an alkyl group having 1 to 10 carbon atoms among the alkyl groups having 1 to 30 carbon atoms represented by R ¹ described above.

In this invention, a commercial item can be used for a thioether compound (A). Commercially available thioether compounds (A) include, for example, Adekastab AO-412S, Adekastab AO-503, and Adekastab AO-26 (manufactured by ADEKA Co., Ltd.); and Irganox PS800FL and Irganox PS802FL (manufactured by BASF Corporation). wait.

In the present invention, one of the above-mentioned thioether compounds may be used alone, or two or more of the above-mentioned thioether compounds may be used in combination. When two or more thioether compounds are used in combination, the heat and humidity resistance of the cured product of the polymerizable composition becomes better, and the heat resistance, adhesiveness and optical properties of the cured product also become better Specifically, it is preferable to use the compound represented by n in formula (I-A) being 1 and the compound represented by n in formula (I-A) being 2 in combination.

Regarding the content of the thioether compound (A) in the polymerizable composition of the present invention, when the heat resistance and adhesiveness of the cured product of the polymerizable composition become good, the following cation polymerizable compound ( B) 100 parts by mass, preferably more than 0.1 parts by mass and less than 10 parts by mass of the thioether compound (A), more preferably more than 0.2 parts by mass and less than 5 parts by mass of the thioether compound (A), Furthermore, it is more preferable to contain 0.3 mass part or more and less than 3 mass parts of thioether compounds (A), and it is especially preferable to contain 0.4 mass parts or more and less than 2 mass parts of thioether compounds (A).

Next, the cation polymerizable compound (B) contained in the polymerizable composition of this invention is demonstrated. In the present invention, the cationically polymerizable compound refers to a compound that causes macromolecularization or crosslinking reaction by a cationic polymerization initiator activated by light irradiation or heating.

In the present invention, a known cationically polymerizable compound can be used as the cationically polymerizable compound (B), without any particular limitation. As a cationically polymerizable compound (B), an epoxy compound and an oxetane compound (B4) are mentioned, for example. In the case where the heat-and-moisture resistance of the polymerizable composition becomes better, and the heat resistance and adhesiveness also become better, the cationic polymerizable compound (B) preferably contains an alicyclic epoxy compound (B1) , at least one of the group consisting of an aliphatic epoxy compound (B2) and an aromatic epoxy compound (B3).

In the present invention, the cationically polymerizable compound (B) preferably contains an alicyclic epoxy compound (B1) when the curability of the polymerizable composition becomes favorable. The alicyclic epoxy compound is a compound having an oxidized cycloalkene structure and not having an aromatic ring. The oxidized cycloalkene structure is such as an epoxycyclohexane structure or an epoxycyclopentane structure obtained by epoxidizing a cyclohexene ring-containing compound or a cyclopentene ring-containing compound with an oxidizing agent, and an aliphatic ring and a ring A structure in which the oxygen ring shares part of the ring structure.

In the present invention, the alicyclic epoxy compound (B1) may have one cycloalkene oxide structure in one molecule, or may have two or more cycloalkene oxide structures. The alicyclic epoxy compound (B1) is preferably It has one or two cycloalkene oxide structures in one molecule.

As an alicyclic epoxy compound having one cycloolefin oxide structure, for example, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, di Cyclopentadiene diepoxide, Dioctyl epoxy hexahydrophthalate, Di-2-ethylhexyl epoxy hexahydrophthalate, 1-oxiranyl-3,4-cyclo Oxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, limonene dioxide, etc.

Examples of alicyclic epoxy compounds having two cycloalkene oxide structures include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-cyclohexane Oxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3 ,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3, 4-Epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipic acid Esters, propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, ethylidene bis(3,4- Epoxy cyclohexane carboxylate), etc.

As alicyclic epoxy compound (B1), a commercial item can be used. As a specific example of a commercial item, Celloxide 2021P, Celloxide 2081, Celloxide 2000, Celloxide 3000 (made by Daicel), LDO (made by Symrise), etc. are mentioned, for example.

In the present invention, one of the above-mentioned alicyclic epoxy compounds (B1) may be used alone, or two or more of the above-mentioned alicyclic epoxy compounds (B1) may be used in combination. Regarding the content of the alicyclic epoxy compound (B1) in the cationically polymerizable compound (B), when the heat resistance and adhesiveness of the cured product of the polymerizable composition become good, the content of the alicyclic epoxy compound (B1) in the cationically polymerizable compound ( B) In 100 mass parts, it is preferable to contain 1-20 mass parts of alicyclic epoxy compounds (B1), and it is more preferable to contain 3-10 mass parts of alicyclic epoxy compounds (B1).

In the present invention, the cationically polymerizable compound (B) preferably contains an aliphatic epoxy compound (B2) when the viscosity of the polymerizable composition is low and the handleability is excellent.

The aliphatic epoxy compound (B2) is a compound which has one or more epoxy groups and does not have an aromatic ring and an oxidized cycloolefin structure. As an aliphatic epoxy compound, a monofunctional epoxy compound and a polyfunctional epoxy compound are mentioned, for example. As a monofunctional epoxy compound, the glycidyl ether compound of aliphatic alcohol, the glycidyl ester of alkylcarboxylic acid, etc. are mentioned, for example. As a polyfunctional epoxy compound, the polyglycidyl ether compound of an aliphatic polyhydric alcohol or its alkylene oxide adduct, the polyglycidyl ester of an aliphatic long-chain polybasic acid, etc. are mentioned, for example. In the present invention, the aliphatic epoxy compound (B2) is preferably monofunctional or difunctional because the viscosity of the polymerizable composition is low and the handleability is excellent.

Typical examples of aliphatic epoxy compounds (B2) include: allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol , hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol and other polyhydric alcohol glycidyl ethers. Polyglycidyl etherification of polyether polyol obtained by adding oxane to propylene glycol, trimethylolpropane, glycerin and other aliphatic polyols, diglycidyl ester of aliphatic long-chain dibasic acid. Further examples include: monoglycidyl ether of aliphatic higher alcohol or glycidyl ester of higher fatty acid, epoxidized soybean oil, epoxy octyl stearate, epoxy butyl stearate, epoxidized soybean oil, epoxidized poly butadiene etc.

As aliphatic epoxy compound (B2), a commercial item can be used. As a commercial item of the said aliphatic epoxy compound (B2), for example, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase Chemical Corporation); Epolight M-1230, Epolight 40E, Epolight 100E, Epolight 200E, Epolight 400E, Epolight 70P, Epolight 200P, Epolight 400P, Epolight 1500NP , Epolight 1600, Epolight 80MF, Epolight 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Adeka Glycirol ED-503, Adeka Glycirol ED-503G, Adeka Glycirol ED-506, Adeka Glycirol ED-523T (manufactured by ADEKA), Epogosey 2EH ( Yokkaichi Gosei Manufacturing), etc.

In the present invention, one of the above-mentioned aliphatic epoxy compounds (B2) may be used alone, or two or more of the above-mentioned aliphatic epoxy compounds (B2) may be used in combination. Regarding the content of the aliphatic epoxy compound (B2) in the cationically polymerizable compound (B), when the heat resistance and adhesiveness of the cured product of the polymerizable composition become good, the content of the aliphatic epoxy compound (B2) in the cationically polymerizable compound (B) ) in 100 parts by mass, preferably 20 to 60 parts by mass of the aliphatic epoxy compound (B2), more preferably 30 to 50 parts by mass of the aliphatic epoxy compound (B2).

In the present invention, the cationically polymerizable compound (B) preferably contains an aromatic epoxy compound (B3) when the heat resistance of the cured product of the polymerizable composition becomes good. The aromatic epoxy compound (B3) is a compound having an aromatic ring and at least one epoxy group. The aromatic epoxy compound (B3) may be monofunctional or polyfunctional. In the present invention, the aromatic epoxy compound (B3) preferably contains at least a monofunctional aromatic epoxy compound or a bifunctional aromatic epoxy compound in order to improve the heat resistance of the cured product of the polymerizable composition. epoxy compound.

Examples of monofunctional aromatic epoxy compounds include monovalent phenols having one aromatic ring such as phenol, cresol, and butylphenol, or compounds obtained by adding alkylene oxide to these compounds. Glycerin Ethers. As polyfunctional aromatic epoxy compounds, for example, bisphenol A, bisphenol F, or glycidyl ether compounds of compounds obtained by adding alkylene oxide to these compounds; resorcinol or p-phenylene Glycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups, such as diphenols and catechols; aromatic compounds having two or more alcoholic hydroxyl groups, such as benzenedimethanol, benzenediethyl alcohol, and benzenedibutanol Polyglycidyl ether compounds; glycidyl esters of polyacid aromatic compounds having two or more carboxylic acids, such as phthalic acid, terephthalic acid, trimellitic acid, etc.

As the aromatic epoxy compound (B3), a commercially available item can be used. Specific examples of commercially available aromatic epoxy compounds (B3) include: Denacol EX-121, Denacol EX-141, Denacol EX-142, Denacol EX-145, Denacol EX-146, Denacol EX- 147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, Oncoat EX-1020, Oncoat EX-1030, Oncoat EX-1040, Oncoat EX-1050, Oncoat EX-1051, Oncoat EX- 1010, Oncoat EX-1011, Oncoat 1012 (manufactured by Nagase Chemicals); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (manufactured by Osaka Gas Chemicals); HP4032, HP4032D, HP4700 ( DIC Corporation); ESN-475V (Nippon Steel & Sumikin Chemical Co., Ltd.); Epikote YX8800 (Mitsubishi Chemical Corporation); Marproof G-0105SA, Marproof G-0130SP (Nippon Oil Corporation); Epiclon N-665, Epiclon HP -7200 (manufactured by DIC Corporation); NC-7000L (manufactured by Nippon Kayaku); Adeka Glycirol ED-501, Adeka Glycirol ED-502, Adeka Glycirol ED-509, Adeka Glycirol ED-529, Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP - 4100E, Adeka Resin EP-4901 (manufactured by ADEKA); TECHMORE VG-3101L, EPOX-MKR710, EPOX-MKR151 (manufactured by Printec), YX-4000 (manufactured by Mitsubishi Chemical), and the like.

In the present invention, one of the above-mentioned aromatic epoxy compounds (B3) may be used alone, or two or more of the above-mentioned aromatic epoxy compounds (B3) may be used in combination. With regard to the content of the aromatic epoxy compound (B3) in the cationically polymerizable compound (B), when the heat resistance and adhesiveness of the cured product of the polymerizable composition become good, the content of the aromatic epoxy compound (B3) in the cationically polymerizable compound (B) ) in 100 parts by mass, preferably 30 to 70 parts by mass of the aromatic epoxy compound (B3), more preferably 40 to 60 parts by mass of the aromatic epoxy compound (B3).

In the present invention, the cationically polymerizable compound (B) preferably contains an alicyclic epoxy compound (B1), an aliphatic Epoxy compound (B2) and aromatic epoxy compound (B3).

When the heat-and-moisture resistance of the cured product of the polymerizable composition becomes better, it is preferable that the cationically polymerizable compound (B) contains an oxetane compound (B4). The oxetane compound (B4) is a compound which has at least one oxetanyl group and does not have an epoxy group. In the present invention, it is preferable to use an oxetane compound having one or two oxetanyl groups when the heat-and-moisture resistance of the cured product of the polymerizable composition becomes better.

As an oxetane compound having one oxetanyl group, for example, 3-ethyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-(methoxy oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane Cyclobutane, 3-ethyl-3-(cyclohexyloxymethyl)oxetane, 3-ethyl-3-(4-hydroxybutoxymethyl)oxetane and the like.

As an oxetane compound having two oxetanyl groups, for example: 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,4-bis[( 3-Ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3- Bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3- Ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetane Butylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, 3-ethyl-3-(3-ethyl-3-oxetanylmethoxy (methyl)oxetane, xylylenedioxetane, etc.

As the oxetane compound (B4), a commercially available item can also be used. Examples of commercially available oxetane compounds include: ARONOXETANE OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toagosei), ETERNACOLL OXBP, OXTP (manufactured by Ube Industries), etc.

In the present invention, one of the above-mentioned oxetane compounds (B4) may be used alone, or two or more of the above-mentioned oxetane compounds (B4) may be used in combination. Regarding the content of the oxetane compound (B4) in the cationically polymerizable compound (B), the moisture and heat resistance of the cured product of the polymerizable composition becomes better, and the heat resistance and adhesiveness of the cured product become better. Preferably, the oxetane compound (B4) is preferably contained in 1 to 30 parts by mass, more preferably 5 to 25 parts by mass of oxygen, in 100 parts by mass of the cationically polymerizable compound (B). Heteretane compound (B4).

With regard to the content of the cationic polymerizable compound (B) in the polymerizable composition of the present invention, the heat-and-moisture resistance and heat resistance of the cured product of the polymerizable composition become better, and the adhesiveness and optical properties of the cured product are also improved. When it becomes good, it is preferable to contain 50 mass parts or more and less than 99 mass parts of cationic polymerizable compound (B) in 100 mass parts of solid content of a polymeric composition, and it is more preferable to contain 75 mass parts It is more preferable to contain the cation polymerizable compound (B) of 85 mass parts or more and less than 99 mass parts of cation polymerizable compounds (B), and it is more preferable to contain 85 mass parts or more and less than 99 mass parts of cation polymerizable compounds (B). The above-mentioned solid content represents what removed the solvent mentioned later from a polymeric composition.

Next, the cationic polymerization initiator (C) contained in the polymerizable composition of this invention is demonstrated. In the present invention, the cationic polymerization initiator (C) refers to a compound that releases a substance that initiates cationic polymerization by irradiation with light or heating. In the present invention, a photocationic polymerization initiator or a thermal cationic polymerization initiator can be used as the cationic polymerization initiator (C). In the present invention, it is preferable to use a photocationic polymerization initiator as the cationic polymerization initiator (C) when curing shrinkage is small and adhesiveness is excellent.

As the photocationic polymerization initiator, as long as it is a compound that releases a substance that initiates cationic polymerization by irradiation with light, it is preferably a double salt of an onium salt that releases a Lewis acid by irradiation with light. , or its derivatives.

As a double salt of an onium salt or its derivative(s), the salt of the cation and anion represented by following general formula (i) is mentioned, for example. [A] ^{m +} [B] ^m (i)

Here, the cation [A] ^m+ is onium, and its structure can be represented by the following general formula, for example. [(R ¹¹⁰ ) _x Q] ^m+ (ii) In the above general formula (ii), R ¹¹⁰ represents an organic group having 1 to 60 carbon atoms and may contain some atoms other than carbon atoms. x represents an integer of 1-5. The x R ^110s are independent, and may be the same or different. At least one of the x R ¹¹⁰ represents the aforementioned organic group having an aromatic ring. Q represents an atom or an atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F and N=N. Also, when the atomic valence of Q in the cation [A] ^m+ is q, it is necessary that the relation m=x−q be established. Among them, N=N is regarded as the atomic valence is 0.

Also, the anion [B] ^m- is preferably a halide complex, and its structure can be represented by, for example, the following general formula (iii). [LX _y ] ^m- (iii) In the above general formula (iii), L represents a metal or semimetal (Metalloid) as the central atom of a halide complex, and is B, P, As, Sb, Fe, Sn , Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn or Co. X represents a halogen atom. y represents an integer of 3-7. Also, when the valence of L in the anion [B] ^m- is p, the relationship m=y−p needs to be established.

Specific examples of the anion [LX _y ] ^m- of the above general formula (iii) include: tetrakis(pentafluorophenyl) borate [(C ₆ F ₅ ) ₄ B] ^- , tetrafluoroborate (BF ₄ ) ^- , hexafluorophosphate (PF ₆ ) ^- , hexafluoroantimonate (SbF ₆ ) ^- , hexafluoroarsenate (AsF ₆ ) ^- , hexachloroantimonate (SbCl ₆ ) ^- , three (five Fluoromethyl) trifluorophosphate ion (FAP anion), etc.

In addition, the anion [B] ^m- may have a structure represented by the following general formula (iv). [LX _y-1 (OH)] ^m- (iv) Here, L, X and b are the same as above. Further, other anions include perchlorate ion (ClO ₄ ) ^- , trifluoromethylsulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonate ion (FSO ₃ ) ^- , toluenesulfonate anion , trinitrobenzenesulfonate anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctylsulfonate, tetraaryl borate, tetrakis(pentafluorophenyl)borate, etc.

In the present invention, in the case where the curability of the polymerizable composition becomes good and the adhesiveness of the cured product of the polymerizable composition becomes good, among such onium salts, the following group I Or a columium salt of a columium cation such as triphenylcobaltium cation represented by group II and anion such as hexafluorophosphate, hexafluoroantimonate or tetrakis(pentafluorophenyl)borate.

[Chem.8] <Group I>

[Chemical 9] ＜Group II＞

A commercial item can also be used for a photocationic polymerization initiator. As commercial products of photocationic polymerization initiators, for example, "Kayarad (registered trademark) PCI-220" and "Kayarad (registered trademark) PCI-620" manufactured by Nippon Kayaku Co., Ltd.; "UVI-6990" manufactured by the company; "Adeka Arkles (registered trademark) SP-150", "Adeka Optomer (registered trademark) SP-170", "Adeka Optomer (registered trademark) SP-500" manufactured by ADEKA Co., Ltd. ; "CI-5102", "CIT-1370", "CIT-1682", "CIP-1866S", "CIP-2048S", "CIP-2064S" manufactured by Nippon Soda Co., Ltd.; Nippon Green Chemical Co., Ltd. "DPI-101", "DPI-102", "DPI-103", "DPI-105", "MPI-103", "MPI-105", "BBI-101", "BBI-102", "BBI-103", "BBI-105", "TPS-101", "TPS-102", "TPS-103", "TPS-105", "MDS-103", "MDS-105", "DTS -102", "DTS-103"; "PI-2074" manufactured by Rhodia; and CPI-100P manufactured by San-Apro, etc.

Regarding the content of the photocationic polymerization initiator in the polymerizable composition of the present invention, in terms of the adhesiveness of the cured product of the polymerizable composition becomes good and the curability of the polymerizable composition becomes good, it is relatively For 100 parts by mass of the cationic polymerizable compound, it is preferable to contain 0.1 to 15 parts by mass of the photocationic polymerization initiator (C), more preferably to contain 1 to 13 parts by mass of the photocationic polymerization initiator (C), and even more Preferably, it contains 3-13 mass parts of photocationic polymerization initiators (C).

In the present invention, a compound that generates a cationic species or a Lewis acid by heating can be used as a thermal cationic polymerization initiator without particular limitation. Specifically, salts such as cerium salts, thiophenium salts, tetrahydrothiophenium salts, benzyl ammonium salts, pyridinium salts, and thiophene salts; diethylenetriamine, triethylenetriamine, tetrakis Polyalkylpolyamines such as ethylpentamine; 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine and other esters Cyclic polyamines; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; by utilizing conventional methods to make the above polyamines and phenyl glycidyl ether, Butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether and other glycidyl ethers or glycidyl esters of carboxylic acids and other epoxy resins are produced by reacting polyepoxy resins. A modified product; an amidated modified product produced by reacting the above-mentioned organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid, and dimer acid by a conventional method; Manny produced by reacting the above-mentioned polyamines with aldehydes such as formaldehyde and phenols having at least one hydroformylation reactive site in the nucleus such as phenol, cresol, xylenol, tert-butylphenol, and resorcinol Helium modified products; polycarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylglutaric acid, 2-methylsuberic acid, 3,8-dimethylsebacic acid , 3,7-dimethyl sebacic acid, hydrogenated dimer acid, dimer acid and other aliphatic dicarboxylic acids; phthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid and other aromatic dicarboxylic acids Carboxylic acids; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; tricarboxylic acids such as trimellitic acid, 1,3,5-benzenetricarboxylic acid, and trimers of castor oil fatty acids; pyromellitic acid and other tetracarboxylic acids Anhydrides of carboxylic acids, etc.); dicyandiamide, imidazoles, carboxylates, sulfonates, amidoimides, etc.

When the curability of the polymerizable composition becomes good, the content of the thermal cationic polymerization initiator in the polymerizable composition of the present invention is preferably 100 parts by mass of the cationic polymerizable compound (B). It is 0.001-10 mass parts, More preferably, it is 0.1-8 mass parts.

As a thermal cationic polymerization initiator, a commercial item can also be used. Examples of commercially available thermal cationic polymerization initiators include Adekaopton CP-77, Adekaopton CP-66 (manufactured by ADEKA), CI-2639, CI-2624 (Nippon Soda), San-Aid SI-60, San-Aid SI-80 and San-Aid SI-100 (manufactured by Sanshin Chemical Industry) and the like.

The polymerizable composition of the present invention may also contain a solvent capable of dissolving or dispersing the thioether compound (A), the cationically polymerizable compound (B) and the cationic polymerization initiator (C). The solvent is a compound that is not classified as the above-mentioned components and is liquid at 25° C. and 1 atmosphere. Examples of solvents include methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc. Ketones; ether solvents such as diethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, etc.; acetic acid Methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, Texanol (2,2,4-trimethyl- 1,3-pentanediol monoisobutyrate) and other ester solvents; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and other cellosolve solvents; methanol, ethanol, iso-or n-propanol, iso-or n-propanol Alcohol solvents such as butanol and pentanol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol mono Ether ester solvents such as methyl ether acetate, 3-methoxybutyl acetate, and ethoxyethyl propionate; BTX (Benzene-Toluene-Xylene, benzene-toluene-xylene) such as benzene, toluene, and xylene solvents; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine, D-limonene, and pinene; mineral spirits, Swazol#310 (Cosmo Songshan Petroleum ( Stock)), Solvesso#100 (Exon Chemical Co., Ltd) and other paraffin solvents; carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane and other halogenated aliphatic hydrocarbon solvents ; chlorobenzene and other halogenated aromatic hydrocarbon solvents; propylene carbonate, carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N -Dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, water, etc.; these solvents can also be used in the form of a mixed solvent of two or more.

The polymerizable composition of the present invention may add other monomers, other polymerization initiators, inorganic fillers, organic fillers, pigments, dyes and other colorants, photosensitizers, defoamers, tackifiers, surfactants, leveling agents, etc. additives, flame retardants, thixotropic agents, diluents, plasticizers, stabilizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flow regulators, adhesion promoters and other resin additives.

The total amount of optional components other than the thioether compound (A), cationic polymerizable compound (B) and cationic polymerization initiator (C) in the polymerizable composition of the present invention also depends on the use of the present invention, etc., but From the viewpoint of further enhancing the effect of the present invention, it is preferably at most 20 parts by mass, particularly preferably at most 10 parts by mass, based on 100 parts by mass of the cationically polymerizable compound (A).

The polymerizable composition of the present invention is a combination of a thioether compound (A), a cationic polymerizable compound (B) and a cationic polymerization initiator (C). Even if a thioether compound (A) is combined with a radical polymerizable composition and a radical polymerization initiator, the effect of this invention which obtains the hardened|cured material favorable in heat-and-moisture resistance is not exhibited. Furthermore, the adhesiveness of the hardened|cured material of the polymerizable composition containing a radical polymerizable composition and a radical polymerization initiator is poor. Therefore, the polymerizable composition of the present invention preferably does not contain a radical polymerizable composition and a radical polymerization initiator.

The radically polymerizable composition is a compound capable of radically polymerizing. As a radically polymerizable compound, the compound which has ethylenically unsaturated groups, such as an acryl group, a methacryl group, a vinyl group, is mentioned, for example. Specifically, the radical polymerizable compound described in International Publication No. 2018/012383, the radical polymerizable organic substance described in International Publication No. 2014/021023, etc. are mentioned.

系化合物及肟酯系化合物、作為熱自由基聚合起始劑之偶氮系化合物、過氧化物及過硫酸鹽等、以及日本專利特開2016-210849號公報所記載之光自由基聚合起始劑等。Radical polymerization initiators are compounds that generate free radicals that can initiate polymerization by exposure or heating to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays. Specifically, for example, acetophenone-based compounds, benzoyl-based compounds, benzophenone-based compounds, 9- Oxygen sulfur 𠮿

Oxime-based compounds and oxime ester-based compounds, azo-based compounds, peroxides, and persulfates as thermal radical polymerization initiators, and photoradical polymerization initiators described in Japanese Patent Application Laid-Open No. 2016-210849 agent etc.

Specific applications of the polymerizable composition of the present invention include optical materials represented by eyeglasses and photographic lenses, paints, coating agents, lining agents, inks, resists, liquid resists, adhesives, etc. Agent, printing plate, insulating varnish, insulating sheet, laminate, printed circuit board, semiconductor device, LED (Light Emitting Diode, light emitting diode) package, liquid crystal injection port, organic EL (Electroluminescence, electroluminescence) , sealants for optical elements, electrical insulation, electronic parts, separation films, etc., molding materials, putty, glass fiber impregnating agents, caulking agents, passivation films for semiconductors, solar cells, etc., interlayer insulating films, Protective film, lens part of lens sheets such as lens sheets such as Fresnel lens sheets and lenticular lens sheets used in backlight devices of liquid crystal display devices, Fresnel lens sheets used in projection TV screens, or backlight devices using such sheets, etc. Optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, casting agents for optical molding, etc., as substrates that can be used as coating agents, for example, metals, wood, rubber, plastics, glass, ceramics products, etc. By using the thioether compound (A) in combination with the cationic polymerizable compound (B) and the cationic polymerization initiator (C), the cured product of the polymerizable composition of the present invention has excellent heat and humidity resistance. In addition, by using these components in combination, the heat resistance, adhesiveness, and optical properties of the polymerizable composition of the present invention also become excellent. Therefore, the polymerizable composition of the present invention is suitable as an adhesive, especially a photocurable adhesive.

Next, the photocurable adhesive agent of this invention is demonstrated. The photocurable adhesive agent of this invention contains the polymerizable composition of this invention. Since the photocurable adhesive agent of this invention contains the polymeric composition of this invention, it becomes excellent in heat-and-moisture resistance. In addition, the photocurable adhesive of the present invention is also excellent in heat resistance, adhesiveness, and optical properties.

Next, the cured product of the present invention will be described. The cured product of the present invention is a cured product of the polymerizable composition of the present invention, and can be produced by irradiating the polymerizable composition with active energy rays or heating the polymerizable composition. The irradiation conditions and heating conditions are not limited to active energy rays, and known conditions can be employed.

Next, the use of the present invention as a photocurable adhesive of a polymerizable composition will be described. In this invention, the said polymeric composition is used as a photocurable adhesive agent for bonding two members by irradiation of light. There are no particular limitations on the amount of the polymerizable composition used, the method of applying it to the member, the wavelength or amount of irradiated light, and known methods and conditions can be appropriately adopted. Moreover, according to this invention, the method of bonding two members with the said polymeric composition is also provided. Specifically, after disposing the above-mentioned polymerizable composition between two members, the polymerizable composition is irradiated with light to harden the polymerizable composition, and the two members are bonded together. Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[Example and Comparative Example] Each component was fully mixed with the composition shown in the following Tables 1-3, and the polymeric composition 1-21 of Examples 1-21, and the polymeric composition of Comparative Examples 1 and 2 were prepared. The symbols in the table mean the following components. In addition, the numerical value in a table shows a mass part.

A-1: A compound represented by the following formula (A-1) A-2: A compound represented by the following formula (A-2) A-3: A compound represented by the following formula (A-3) A-4: A compound represented by the following formula (A-4) A-5: A compound represented by the following formula (A-5) A-6: A compound represented by the following formula (A-6) A-7: A compound represented by the following formula (A-7) A'-1: a compound represented by the following formula (A'-1)

[chemical 10]

[chemical 11]

[chemical 12]

[chemical 13]

[chemical 13A]

[chemical 13B]

[chemical 13C]

[chemical 14]

B1-1: A compound represented by the following formula (B1-1) B1-2: A compound represented by the following formula (B1-2) B2-1: A compound represented by the following formula (B2-1) B2-2: A compound represented by the following formula (B2-2) B3-1: A compound represented by the following formula (B3-1) B3-2: A compound represented by the following formula (B3-2) B3-3: A compound represented by the following formula (B3-3) B3-4: A compound represented by the following formula (B3-4) B4-1: A compound represented by the following formula (B4-1) B4-2: A compound represented by the following formula (B4-2)

[chemical 15]

[chemical 16]

[chemical 17]

[chemical 18]

[chemical 19]

[chemical 20]

[chem 21]

[chem 22]

[chem 23]

[chem 24]

C-1: 50% by mass solution of propylene carbonate of the compound represented by the following formula (C1-2) C-2: 50% by mass solution of propylene carbonate of the compound represented by the following formula (C2)

[chem 25]

[chem 26]

The heat-and-moisture resistance, heat resistance, adhesiveness, and optical properties of cured products of the polymerizable compositions prepared in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Tables 1-3.

<Adhesion test> The compositions prepared in Examples and Comparative Examples were coated on TAC (triacetyl cellulose, cellulose triacetate) films (manufactured by Fujifilm Co., Ltd.) so that the film thickness after curing became 3 μm. Fujitac TD80), forming a coating film. Then, a COP (cycloolefin polymer; manufactured by Japan Zeon Co., Ltd.: product number ZeonorFilm 14-060) film subjected to corona discharge treatment was bonded to the surface of the TAC film on which the coating film was formed by using a laminating machine to obtain laminated body. Next, the laminate was irradiated with light equivalent to 1000 mJ/cm ² through the COP film using an electrodeless ultraviolet lamp, followed by bonding to manufacture a test piece. The obtained test pieces were preserved under conditions of 30° C., 50% RH, and atmospheric pressure for 12 hours from the exposure. Then, a 2.0 cm width was cut out from the test piece to obtain a sample for evaluation. A 90-degree peel test was performed on the obtained samples, and the adhesiveness of the evaluation samples was evaluated according to the following criteria. The 90-degree peel test is carried out at 30°C, 50%RH, and atmospheric pressure. The larger the value of N/2 cm, the better the adhesiveness. A: More than 2.5 N/2 cm or the base material is broken B: More than 1.5 N/2 cm and less than 2.5 N/2 cm C: More than 0.5 N/2 cm and less than 1.5 N/2 cm D: Less than 0.5 N /2 cm.

＜Moisture resistance test＞ Test pieces were obtained in the same manner as in the adhesion test. The obtained test pieces were kept in an environment of 85° C. and 85% RH for 500 hours. Thereafter, after the test piece was lowered to room temperature, a 90-degree peel test was performed on the test piece in the same manner as in the adhesion test, and the heat and humidity resistance of the evaluation sample was evaluated in accordance with the following criteria. The larger the value of N/2 cm is, the more excellent the heat-and-moisture resistance is. A: 1.5 N/2 cm or more B: More than 1.0 N/2 cm and less than 1.5 N/2 cm C: More than 0.5 N/2 cm and less than 1.0 N/2 cm D: Less than 0.5 N/2 cm

<Optical characteristic test> The polymerizable compositions prepared in Examples and Comparative Examples were applied to glass plates so that the film thickness after curing became 50 μm, and then other glass plates were bonded to the glass plates. There is a coated surface. A high-pressure Hg lamp was used to irradiate the bonded glass plate with energy of 1000 mJ/cm ² , and then the glass plate was heated at 150° C. for 1 hour to obtain a test piece. The b* of the obtained test piece was measured using the ultraviolet-visible-near-infrared spectrophotometer V-670 (manufactured by JASCO Corporation), and the optical characteristics of the test piece were evaluated on the basis of the following criteria. The smaller the value of b* is, the more excellent the optical properties are. A: The b* of the hardened product is less than 5 B: The b* of the hardened product is 5 or more and less than 10 C: The b* of the hardened product is 10 or more

＜Heat Resistance Test＞ A test piece was obtained in the same manner as in the optical characteristic test. b* of the obtained test piece was measured using the ultraviolet-visible-near-infrared spectrophotometer V-670 (manufactured by JASCO Corporation). Next, after maintaining the test piece in an environment of 85°C and 85%RH for 500 hours, b* of the test piece was measured. Next, the heat resistance of the test piece was evaluated according to the following criteria. The smaller Δb* is, the more excellent the heat resistance is. A: Δb*<3 B: 3≦Δb*<5 C: 5≦Δb*<8 D: 8≦Δb*

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 A component A-1 0.3 0.5 A-2 0.5 1 4 1 1 1 A-3 0.7 1.4 A-4 0.3 0.6 A'-1 B component B1-1 5 5 5 5 5 6.5 8 7 5 B1-2 4 B2-1 25 25 25 25 25 0 43 30 25 25 B2-2 10 10 10 10 10 13 16 13 10 10 B3-1 40 40 40 40 40 54.5 0 50 40 B3-2 20 B3-3 twenty three B3-4 B4-1 20 20 20 20 20 26 33 0 20 20 B4-2 C component C-1 10 10 10 10 10 10 10 10 10 10 C-2 Moisture resistance B B A A B B B B A B heat resistance B B B A B A B A A B Continuity B B B B B B B B B A optical properties A A A A A A A A A A

[Table 2] Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Comparative example 1 Comparative example 2 A component A-1 A-2 0.5 1 1 1 1 1 1 A-3 0.7 A-4 0.3 A'-1 0.5 1 1 1 1 1 1 1 1 B component B1-1 5 5 5 B1-2 4 4 4 0 10 10 4 B2-1 25 25 25 25 30 0 38 25 25 25 B2-2 10 10 10 10 10 0 12 10 10 10 B3-1 40 40 25 B3-2 20 25 25 25 37 0 25 B3-3 twenty three B3-4 18 18 18 18 0 18 B4-1 20 20 20 20 20 35 40 10 20 20 B4-2 10 C component C-1 10 10 10 10 10 10 10 10 10 C-2 10 Moisture resistance B A A A B B B A C C heat resistance B A A A A A B A C D. Continuity A A A A B B B A B B optical properties A A A A A A A A A C

[table 3] Example 19 Example 20 Example 21 A-5 0.5 A-6 0.5 A-7 0.5 B component B1-1 5 5 5 B2-1 25 25 25 B2-2 10 10 10 B3-1 40 40 40 B4-1 20 20 20 C component C-1 10 10 10 Moisture resistance A A A heat resistance B B B Continuity B B B optical properties A A A

As is clear from Tables 1 to 3, the cured products of the polymerizable compositions of Examples 1 to 21 have good heat and humidity resistance. Furthermore, these cured products are also excellent in heat resistance, adhesiveness and optical properties. On the other hand, the cured product of the polymerizable composition of Comparative Example 1 that did not contain the thioether compound (A) was not good in heat resistance as well as in moist heat resistance. Also, the cured product of the polymerizable composition of Comparative Example 2 containing another component (A'-1) instead of the thioether compound (A) was not good in heat resistance and optical properties in addition to poor heat and humidity resistance.

Claims (15)

A polymerizable composition containing a thioether compound (A), a cationic polymerizable compound (B), and a cationic polymerization initiator (C). The polymerizable composition according to claim 1, wherein the thioether compound (A) has an ester bond in the molecule. The polymerizable composition according to claim 1, wherein the thioether compound (A) has a group represented by the following general formula (I), [Chem. 1]

( ^wherein , R represents an aliphatic hydrocarbon group with 1 to 30 carbon atoms that may have substituents, an aromatic hydrocarbon-containing ring group with 6 to 30 carbon atoms that may have substituents, the above-mentioned aliphatic hydrocarbon group with 1 to 30 carbon atoms One or more methylene groups in the aliphatic hydrocarbon group are substituted with a divalent group selected from the following <Group A>, or one of the above-mentioned aromatic hydrocarbon ring groups with 6 to 30 carbon atoms One or more methylene groups are substituted with divalent groups selected from the following <Group A>, ^Y1 represents a divalent hydrocarbon group with 1 to 30 carbon atoms that may have a substituent or the carbon atom One or more methylene groups in the divalent hydrocarbon groups of 1 to 30 are substituted with divalent groups selected from the following <Group A>, * represents a bond; <Group A>:- O-, -CO-, -COO-, -OCO-, -NR ² -, -NR ³ CO- or -S-, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms ). Such as the polymerizable composition of claim 3, wherein ^R in the general formula (I) is an aliphatic hydrocarbon group with 5 to 20 carbon atoms that may have substituents or an aliphatic hydrocarbon group with 6 to 20 carbon atoms that may have substituents. Aromatic hydrocarbon ring group. The polymerizable composition according to claim 3, wherein Y ¹ in the general formula (I) is a divalent hydrocarbon group with 1 to 10 carbon atoms which may have a substituent. The polymerizable composition according to claim 3, wherein the thioether compound (A) has a plurality of groups represented by the general formula (I) in the molecule. The polymeric composition according to claim 1, wherein the thioether compound (A) is a compound represented by the following general formula (IB), [Chem. 2]

(wherein, R ¹¹ represents an aliphatic hydrocarbon group with 1 to 30 carbon atoms that may have substituents, an aromatic hydrocarbon-containing ring group with 6 to 30 carbon atoms that may have substituents, the above-mentioned aliphatic hydrocarbon group with 1 to 30 carbon atoms One or more methylene groups in the aliphatic hydrocarbon group are substituted with a divalent group selected from the following <Group A1>, or one of the above-mentioned aromatic hydrocarbon ring groups having 6 to 30 carbon atoms One or more methylene groups are substituted with divalent groups selected from the following <Group A1>, n1 represents an integer of 1 to 6, D1 represents an optional substituent having 6 to 30 carbon atoms An aromatic hydrocarbon ring group or an aromatic hydrocarbon ring group with 6 to 30 carbon atoms which may have a substituent; <Group A1>: -O-, -CO-, -COO-, -OCO-, -NR ^2a -, -NR ^3a CO- or -S- R ^2a and R ^3a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms). The polymerizable composition according to claim 7, wherein D1 in the above general formula (I-B) has an aromatic hydrocarbon ring with a monocyclic structure. The polymerizable composition according to claim 7, wherein R ¹¹ in the general formula (IB) is an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have substituents. The polymerizable composition of Claim 1 which contains 0.1 mass part or more and less than 10 mass parts of thioether compounds (A) with respect to 100 mass parts of cationic polymerizable compounds (B). The polymeric composition according to claim 1, wherein the cationic polymerizable compound (B) contains an alicyclic epoxy compound (B1), an aliphatic epoxy compound (B2) and an aromatic epoxy compound (B3) At least one of the group. A photocurable adhesive containing the polymerizable composition according to claim 1. A method for producing a cured product, comprising the step of irradiating active energy rays or heating the polymerizable composition according to claim 1. A cured product of the polymeric composition as claimed in claim 1. A use of the polymerizable composition as claimed in claim 1 as a photocurable adhesive.