KR20230163354A - Polymerizable composition, photocurable adhesive, manufacturing method and cured product - Google Patents

Abstract

The object of the present invention is to provide a polymerizable composition capable of producing a cured product excellent in heat and moisture resistance. The present invention is a polymerizable composition containing a thioether compound (A), a cationic polymerizable compound (B), and a cationic polymerization initiator (C). The thioether compound (A) preferably has an ester bond within the molecule. The polymerizable composition preferably contains 0.1 parts by mass or more and less than 10 parts by mass of the thioether compound (A) relative to 100 parts by mass of the cationically polymerizable compound (B).

Description

Polymerizable composition, photocurable adhesive, manufacturing method and cured product

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

Cationic curable compositions are used in fields such as inks, paints, various coating agents, adhesives, and optical members.

For example, the following Patent Documents 1 to 3 disclose cationically polymerizable compositions used as various photocurable adhesives.

Japanese Patent Publication No. 2011-236389 Japanese Patent Publication No. 2012-149262 International Publication WO2008/111584

However, the cured product of the polymerizable composition described in Patent Documents 1 to 3 did not have sufficient heat-and-moisture resistance.

Therefore, the object of the present invention is to provide a polymerizable composition that can produce a cured product excellent in heat and moisture resistance.

The inventors of the present invention conducted intensive studies to solve the above problems and, as a result, 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).

Additionally, the present invention provides a photocurable adhesive containing the above polymerizable composition.

Additionally, the present invention provides a method for producing a cured product including a step of irradiating active energy rays to the polymerizable composition or a step of heating the polymerizable composition.

Additionally, the present invention provides a cured product of the polymerizable composition.

Additionally, the present invention provides use of the polymerizable composition as a photocurable adhesive.

According to the polymerizable composition of the present invention, a cured product excellent in heat and moisture resistance can be produced.

Hereinafter, the polymerizable composition of the present invention will be described in detail.

The polymerizable composition of the present invention contains a thioether compound (A). By containing the thioether compound (A), the cured product of the polymerizable composition becomes excellent in heat-and-moisture resistance. Additionally, this cured product has excellent heat resistance, adhesiveness, and optical properties.

A thioether compound (A) is a compound that has a thioether bond in the molecule. In the present invention, known thioether compounds can be used as the thioether compound (A) without particular restrictions. In the present invention, it is preferable to use a thioether compound having an ester bond in the molecule because the heat resistance and heat resistance of the cured product of the polymerizable composition are further improved, and the heat resistance and adhesiveness of the cured product are also improved.

As a thioether compound having an ester bond in the molecule, for example, those having a group represented by the following general formula (I) have better heat-and-moisture resistance of the cured product of the polymerizable composition, and the heat resistance and adhesiveness of the cured product are also good. It is desirable because it is worn out.

(Wherein, R ¹ is an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent, or an aliphatic group having 1 to 30 carbon atoms) A group in which at least one methylene group among the hydrocarbon groups is substituted by a divalent group selected from <Group A> below, or at least one methylene group among the aromatic hydrocarbon ring-containing groups having 6 to 30 carbon atoms described above is < Represents a group substituted by a divalent group selected from group A>,

Y ¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms, which may have a substituent, or a divalent hydrocarbon group in which at least one methylene group of the above divalent hydrocarbon groups having 1 to 30 carbon atoms is selected from <Group A> below. Represents a group substituted by a group,

* represents the number of combinations.

<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 having 1 to 30 carbon atoms.)

In general formula (I), the aliphatic hydrocarbon group with 1 to 30 carbon atoms represented by R ¹ includes an alkyl group with 1 to 30 carbon atoms, an alkenyl group with 2 to 30 carbon atoms, and an alkynyl group with 2 to 30 carbon atoms. , cycloalkyl groups having 3 to 30 carbon atoms, etc.

The alkyl group having 1 to 30 carbon atoms represented by R ¹ may be linear or branched. Examples of straight-chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, and tetradecyl. , pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, Octacosyl group, nonacosyl group, and triacontyl group can be mentioned. Branched alkyl groups include groups in which one or two or more of the above-described straight-chain alkyl groups are replaced with alkyl groups having 1 to 9 carbon atoms, specifically, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, 2-heptyl group, 1,4-dimethylpentyl group, tert-heptyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, isooctyl group, Examples include tert-octyl group, 2-ethylhexyl group, 2-methylhexyl group, 2-propylhexyl group, isononyl group, isodecyl group, isoundecyl group, and isododecyl group. Examples of the alkyl group having 1 to 9 carbon atoms include those having 1 to 9 carbon atoms among the alkyl groups having 1 to 30 carbon atoms represented by R ¹ .

In the present invention, as the heat-and-moisture resistance of the cured product of the polymerizable composition becomes further improved, the heat resistance, adhesiveness, and optical properties of the cured product also improve, so the number of carbon atoms in the alkyl group is preferably 5 to 23, and 5 to 20. It is more preferable that it is 7-17, and it is still more preferable that it is 9-15. Also, from the same viewpoint, it is preferable that the alkyl group is linear.

Alkenyl groups having 2 to 30 carbon atoms represented by R ¹ include, for example, ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, and undecyl group. Cenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icosenyl group, henicosenyl group , dococenyl group, tricocenyl group, tetracosenyl group, pentacocenyl group, hexacocenyl group, heptacocenyl group, octacocenyl group, nonacosenyl group and triacontenyl group, and alkadiene corresponding to these groups. Nyl group and alkatrienyl group can be mentioned.

Alkynyl groups having 2 to 30 carbon atoms represented by R ¹ include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-octinyl group, 1 -Decinyl group, 1-octadecynyl group, etc. are mentioned.

Cycloalkyl groups having 3 to 30 carbon atoms represented by R ¹ include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group, 2-bornyl group, 2-isobornyl group, 1-adamantyl group, etc. are mentioned.

In the present invention, an aromatic hydrocarbon ring-containing group means a group having an aromatic hydrocarbon ring.

The aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms represented by R ¹ may have a monocyclic structure or a polycyclic structure. The aromatic hydrocarbon ring-containing group of the polycyclic structure may have a condensed ring structure or may be one in which two aromatic hydrocarbon rings are connected.

The aromatic hydrocarbon ring-containing group in which two aromatic hydrocarbon rings are connected may be one in which two aromatic hydrocarbon rings in a monocyclic structure are connected, or an aromatic hydrocarbon ring in a monocyclic structure and an aromatic hydrocarbon ring in a condensed ring structure may be connected, or an aromatic hydrocarbon ring in a two-condensed ring structure may be connected. The hydrocarbon ring may be connected.

The linking group that connects two aromatic hydrocarbon rings may be any group that can have aromaticity as a whole of the aromatic hydrocarbon ring-containing group, and includes a single bond, a sulfide group (-S-), and a carbonyl group.

Examples of aromatic hydrocarbon rings with a monocyclic structure include benzene, toluene, ethylbenzene, and 2,4,6-trimethylbenzene.

Examples of aromatic hydrocarbon rings with a condensed ring structure include naphthalene, anthracene, phenanthrene, and pyrene.

Examples of aromatic hydrocarbon ring-containing groups in which two aromatic hydrocarbon rings are linked include groups in which monocyclic aromatic hydrocarbon rings, such as diphenyl sulfide and benzoylphenyl, are linked.

From the viewpoint of further improving the heat-and-moisture resistance of the cured product of the polymerizable composition, in the present invention, the number of carbon atoms in the aromatic hydrocarbon ring is preferably 6 to 20. From the viewpoint of improving the heat resistance, adhesiveness, and optical properties of the cured product in addition to the heat-and-moisture resistance, it is more preferable that the number of carbon atoms in the aromatic hydrocarbon ring is 6 to 15.

The divalent hydrocarbon group having 1 to 30 carbon atoms represented by Y ¹ is an aliphatic hydrocarbon group having 1 to 30 carbon atoms that may have a substituent represented by R ¹ or the number of carbon atoms that may have 6 to 30 carbon atoms. A divalent group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring-containing group can be mentioned.

Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ² and R ³ in Group A include an aliphatic hydrocarbon group having 1 to 30 carbon atoms and an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms. there is.

Examples of the aliphatic hydrocarbon group having 1 to 30 carbon atoms represented by R ² and R ³ include those similar to the aliphatic hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ .

Examples of the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms represented by R ² and R ³ include those similar to the aromatic hydrocarbon ring containing group having 6 to 30 carbon atoms represented by R ¹ .

The substituents for the aliphatic hydrocarbon group with 1 to 30 carbon atoms represented by R ¹ and the aromatic hydrocarbon ring-containing group with 6 to 30 carbon atoms, and the divalent hydrocarbon group with 1 to 30 carbon atoms represented by Y ¹ Alkyl group having 1 to 8 carbon atoms; Ethylenically unsaturated groups such as vinyl, allyl, acrylic, and methacryl; Halogen atoms such as fluorine, chlorine, bromine, and iodine; Acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, jade Acyl groups such as saloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl, and carbamoyl; Acyloxy groups such as acetyloxy and benzoyloxy; Amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, Diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino , N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n -Octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N,N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenyl Substituted amino groups such as sulfonylamino; Sulfonamide group, sulfonyl group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imide group, carbamoyl group, sulfonamide group, phosphonic acid group, phosphoric acid group or carboxyl group, sulfo group, phosphonic acid group, Salts of phosphoric acid groups, etc. can be mentioned. Examples of the alkyl group having 1 to 8 carbon atoms include those 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 the group specified in the present invention includes the number of carbon atoms of the substituent. For example, the methylphenyl group is an aromatic hydrocarbon ring-containing group having 7 carbon atoms.

In addition, the number of carbon atoms of the group in which one or more of the methylene groups defined in the present invention is substituted by a divalent group selected from <Group A> includes the number of carbon atoms of the divalent group. For example, the number of carbon atoms of an alkyl group with 10 carbon atoms in which one methylene group is substituted with -COO- is set to 10. In addition, the number of carbon atoms of an alkyl group having 10 carbon atoms in which one methylene group is substituted with -O- is set to 9. One or more of the methylene groups are selected from <Group A1>, <Group B>, <Group C>, <Group D>, <Group E>, <Group F>, or <Group G>, which will be described later. The same applies to the number of carbon atoms in the substituted group.

In the present invention, because the adhesiveness and heat resistance of the cured product of the polymerizable composition are improved, R ¹ in the general formula (I) is an aliphatic hydrocarbon group with 5 to 20 carbon atoms that may have a substituent, or a carbon atom that may have a substituent. It is preferable that it is an aromatic hydrocarbon ring-containing group with 6 to 20 carbon atoms, more preferably an aliphatic hydrocarbon group with 5 to 20 carbon atoms, and even more preferably an alkyl group with 5 to 20 carbon atoms. From the same viewpoint, it is preferable that the alkyl group having 5 to 20 carbon atoms is linear. Additionally, it is preferable that the alkyl group having 5 to 20 carbon atoms does not have a substituent from the viewpoint of compatibility.

In the present invention, since the adhesion and heat resistance of the cured product of the polymerizable composition are improved, it is preferable that Y ¹ in the general formula (I) is a divalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and has a substituent. An alkylene group optionally having 1 to 10 carbon atoms or an arylene group having 1 to 10 carbon atoms optionally having a substituent is more preferable. From the same viewpoint, it is preferable that the alkylene group having 1 to 10 carbon atoms and the arylene group having 1 to 10 carbon atoms do not have a substituent. In addition, the number of carbon atoms of the alkylene group is preferably 1 to 8, more preferably 2 to 6, from the viewpoint of heat resistance and compatibility with the cured product of the polymerizable composition. Additionally, the alkylene group is preferably linear.

In the present invention, when a thioether compound has a group represented by general formula (I) in the molecule, the number of groups represented by general formula (I) in the compound may be one or more. The adhesiveness and heat resistance of the cured product of the polymerizable composition are improved. The thioether compound preferably has a plurality of groups represented by general formula (I) in the molecule, more preferably 2 to 8, and 2 to 6. It is more preferable to have 2 to 4 pieces, and it is especially preferable to have 2 to 4 pieces.

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

(Wherein, R ¹ is an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent, or an aliphatic group having 1 to 30 carbon atoms) A group in which at least one methylene group among the hydrocarbon groups is substituted by a divalent group selected from <Group A> below, or at least one methylene group among the aromatic hydrocarbon ring-containing groups having 6 to 30 carbon atoms described above is < Represents a group substituted by a divalent group selected from group A>,

Y ¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms, which may have a substituent, or a divalent hydrocarbon group in which at least one methylene group of the above divalent hydrocarbon groups having 1 to 30 carbon atoms is selected from <Group A> below. It is a group substituted by a group,

n represents an integer from 1 to 6,

D represents an n-valent 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 hydrocarbon group having 1 to 30 carbon 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 formula (I-A) is 1, the monovalent group represented by D is an aliphatic hydrocarbon group having 1 to 30 carbon atoms that may have a substituent, or an aromatic hydrocarbon ring having 6 to 30 carbon atoms that may have a substituent. A containing group, a group in which at least one methylene group of the aliphatic hydrocarbon group having 1 to 30 carbon atoms is substituted with a divalent group selected from <Group B> below, or an aromatic hydrocarbon ring having 6 to 30 carbon atoms Among the containing groups, groups in which one or more methylene groups are substituted by a divalent group selected from <Group B> below can be mentioned.

<Group B>: -O-, -CO-, -COO-, -OCO-, -NR ²⁰ -, -NR ³⁰ CO- or -S-

R ²⁰ and R ³⁰ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.

The monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms, which may have a substituent represented by D, and the monovalent aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms, which may have a substituent, are represented by R ¹ described above. Examples of the same include aliphatic hydrocarbon groups having 1 to 30 carbon atoms which may have a substituent, and aromatic hydrocarbon ring-containing groups having 6 to 30 carbon atoms which may have a substituent.

Among <Group B>, the hydrocarbon groups having 1 to 30 carbon atoms represented by R ²⁰ and R ³⁰ include those similar to the hydrocarbon groups having 1 to 30 carbon atoms represented by R ² and R ³ described above.

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

(In the formula, Y ¹⁰ is a single bond, -CO-, -NR ²⁰⁰ -, -S-, a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, or a divalent hydrocarbon group having 1 to 30 carbon atoms above) Represents a group in which at least one methylene group among the hydrocarbon groups is substituted by a divalent group selected from <Group C> below,

R ²⁰⁰ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms,

Z ¹ and Z ² are each independently a direct bond, -CO-, a divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, or a divalent aromatic group having 6 to 30 carbon atoms which may have a substituent. Represents a hydrocarbon ring-containing group,

* represents the number of bonds.

<Group C>: -O-, -CO-, -COO-, -OCO-, -NR ²¹ -, -NR ³¹ CO- or -S-

R ²¹ and R ³¹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.)

In formula (1), the divalent hydrocarbon group having 1 to 30 carbon atoms that may have a substituent represented by Y ¹⁰ includes the same divalent hydrocarbon group having 1 to 30 carbon atoms represented by Y ¹ described above. there is.

In formula (1), the hydrocarbon group having 1 to 30 carbon atoms represented by R ²⁰⁰ , R ²¹ and R ³¹ may be the same as the hydrocarbon group having 1 to 30 carbon atoms represented by R ² and R ³ described above. there is.

In formula (1), the divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms that may have a substituent represented by Z ¹ and Z ² includes an aliphatic group having 1 to 30 carbon atoms that may have a substituent represented by R ¹ A divalent group obtained by removing one hydrogen atom from a hydrocarbon group can be mentioned.

In formula (1), the divalent aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms that may have a substituent represented by Z ¹ and Z ² includes 6 to 30 carbon atoms that may have a substituent represented by R ¹ A divalent group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring-containing group can be mentioned.

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

(In the formula, Y ¹¹ is a trivalent hydrocarbon group having 1 to 30 carbon atoms, which may have a substituent, or at least one methylene group among the above trivalent hydrocarbon groups having 1 to 30 carbon atoms in <Group D> below. Represents a group substituted by a selected divalent group,

Z ¹ , Z ² and Z ³ are each independently a direct bond, -CO-, a divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, or a divalent aliphatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent. Represents a divalent aromatic hydrocarbon ring-containing group,

* represents the number of bonds.

<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 having 1 to 30 carbon atoms.)

In formula (2), the trivalent hydrocarbon group having 1 to 30 carbon atoms that may have a substituent represented by Y ¹¹ includes hydrogen in addition to the divalent hydrocarbon group having 1 to 30 carbon atoms represented by Y ¹ described above. A trivalent group with one atom removed can be mentioned.

In formula (2), examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ²² and R ³² include those similar to the hydrocarbon groups having 1 to 30 carbon atoms represented by R ² and R ³ described above.

In formula (2), the divalent aliphatic hydrocarbon group having a carbon atom number of 1 to 30 that may have a substituent represented by Z ¹ , Z ² and Z ³ is the number of carbon atoms that may have a substituent represented by R ¹ described above. A divalent group obtained by removing one hydrogen atom from an aliphatic hydrocarbon group numbered 1 to 30 can be mentioned.

In formula (2), the divalent aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms that may have a substituent represented by Z ¹ , Z ² and Z ³ includes carbon that may have a substituent represented by R ¹ described above. A divalent group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring-containing group having 6 to 30 atoms can be mentioned.

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

(In the formula, Y ¹² is a tetravalent hydrocarbon group having 1 to 30 carbon atoms, which may have a substituent, or at least one methylene group among the tetravalent hydrocarbon groups having 1 to 30 carbon atoms in <Group E> below. Represents a group substituted by a selected divalent group,

Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a direct bond, -CO-, a divalent aliphatic hydrocarbon group with 1 to 30 carbon atoms which may have a substituent, or 6 carbon atoms which may have a substituent. Represents ~30 divalent aromatic hydrocarbon ring-containing groups,

* represents the number of bonds.

<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 having 1 to 30 carbon atoms.)

In formula (3), the tetravalent hydrocarbon group having 1 to 30 carbon atoms that may have a substituent represented by Y ¹² includes hydrogen in addition to the divalent hydrocarbon group having 1 to 30 carbon atoms represented by Y ¹ described above. A tetravalent group with two atoms removed can be mentioned.

In formula (3), examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ²³ and R ³³ include those similar to the hydrocarbon groups having 1 to 30 carbon atoms represented by R ² and R ³ described above.

In formula (3), the divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent represented by Z ¹ , Z ² , Z ³ and Z ⁴ includes the above-mentioned divalent aliphatic hydrocarbon group which may have a substituent represented by R ¹ A divalent group obtained by removing one hydrogen atom from an aliphatic hydrocarbon group having 1 to 30 carbon atoms can be mentioned.

In formula (3), the divalent aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent represented by Z ¹ , Z ² , Z ³ and Z ⁴ has a substituent represented by R ¹ described above. A divalent group obtained by removing one hydrogen atom from an optional aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms can be mentioned.

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

(In the formula, Y ¹³ is a pentavalent hydrocarbon group having 1 to 30 carbon atoms, which may have a substituent, or at least one methylene group among the pentavalent hydrocarbon groups having 1 to 30 carbon atoms in <Group F> below. Represents a group substituted by a selected divalent group,

Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are each independently a direct bond, -CO-, a divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, or carbon which may have a substituent Represents a divalent aromatic hydrocarbon ring-containing group with 6 to 30 atoms,

* represents the number of bonds.

<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 having 1 to 30 carbon atoms.)

In formula (4), the pentavalent hydrocarbon group having 1 to 30 carbon atoms that may have a substituent represented by Y ¹³ includes hydrogen in addition to the divalent hydrocarbon group having 1 to 30 carbon atoms represented by Y ¹ described above. A pentavalent group in which three atoms have been removed can be mentioned.

In formula (4), the hydrocarbon group having 1 to 30 carbon atoms represented by R ²⁴ and R ³⁴ includes the same hydrocarbon group having 1 to 30 carbon atoms represented by R ² and R ³ described above.

In formula (4), the divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms that may have substituents represented by Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ includes the substituent 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 can be mentioned.

In formula (4), the divalent aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms that may have substituents represented by Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ is represented by R ¹ described above. A divalent group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms, which may have a substituent, can be mentioned.

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

(In the formula, Y ¹⁴ is a hexavalent hydrocarbon group having 1 to 30 carbon atoms, which may have a substituent, or one or more methylene groups among the above-mentioned hexavalent hydrocarbon groups having 1 to 30 carbon atoms in <Group G> below. Represents a group substituted by a selected divalent group,

Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ are each independently a direct bond, -CO-, a divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, or a substituent. Represents a divalent aromatic hydrocarbon ring-containing group optionally having 6 to 30 carbon atoms,

* represents the number of bonds.

<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 having 1 to 30 carbon atoms.)

In formula (5), the hexavalent hydrocarbon group having 1 to 30 carbon atoms that may have a substituent represented by Y ¹⁴ includes hydrogen in addition to the divalent hydrocarbon group having 1 to 30 carbon atoms represented by Y ¹ described above. A hexavalent group with four atoms removed can be mentioned.

In formula (5), examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ²⁵ and R ³⁵ include those similar to the hydrocarbon groups having 1 to 30 carbon atoms represented by R ² and R ³ described above.

In formula (5), the divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have substituents represented by Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ is 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 any substituent, can be mentioned.

In formula (5), the divalent aromatic hydrocarbon ring-containing group 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 includes the above-mentioned R ¹ A divalent group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring-containing group with 6 to 30 carbon atoms that may have a substituent represented by .

In the present invention, as the heat-and-moisture resistance of the cured product of the polymerizable composition becomes further improved, the heat resistance, adhesiveness, and optical properties of the cured product also improve, so that n in the formula (I-A) is preferably 1 to 6, and 1 to 6. It is more preferable that it is 5, and it is more preferable that it is 1-4.

When n in the formula (IA) is 1, the heat-and-moisture resistance of the cured product of the polymerizable composition becomes even better, and the heat resistance, adhesiveness, and optical properties of the cured product also improve, so the monovalent group represented by D is a substituent. It is preferable that it is an aliphatic hydrocarbon group having 1 to 30 carbon atoms, which may have a substituent, or an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms, which may have a substituent. From the same viewpoint, the aromatic hydrocarbon ring-containing group preferably has a monocyclic aromatic hydrocarbon ring, and more preferably has two monocyclic aromatic hydrocarbon rings connected. Moreover, since the heat-and-moisture resistance of the polymerizable composition becomes even better, it is preferable that two aromatic hydrocarbon rings are connected by -S-. In addition, the aromatic hydrocarbon ring-containing group preferably has a substituent because the heat resistance of the cured product of the polymerizable composition improves. Furthermore, from the viewpoint of compatibility, the substituent is preferably an alkyl group or hydroxyl group having 1 to 10 carbon atoms, and more preferably the aromatic hydrocarbon ring-containing group is substituted with an alkyl group or a hydroxyl group. The alkyl group is preferably branched. Examples of the alkyl group having 1 to 10 carbon atoms include those 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 of the aliphatic hydrocarbon group represented by D is preferably 5 to 20, more preferably 8 to 19, and even more preferably 10 to 15. Additionally, the aliphatic hydrocarbon group is preferably an alkyl group that may have a substituent, and more preferably is an alkyl group that does not have a substituent. When the monovalent group represented by D is an aliphatic hydrocarbon group that may have a substituent, R ¹ is an aliphatic hydrocarbon group with 5 to 23 carbon atoms that may have a substituent or an aliphatic hydrocarbon group with 5 to 23 carbon atoms that may have a substituent. It is preferable that at least one methylene group in the group is a group substituted with -COO- or -OCO-, and among aliphatic hydrocarbon groups with 5 to 23 carbon atoms that may have a substituent, at least one methylene group is -COO- Or, it is more preferable that it is a group substituted with -OCO-, and it is more preferable that at least one methylene group among alkyl groups of 5 to 23 carbon atoms that may have a substituent is substituted with -COO- or -OCO-, Among the unsubstituted alkyl groups having 9 to 23 carbon atoms, it is further preferable that one of the methylene groups is a group substituted with -COO- or -OCO-. By keeping the number of carbon atoms of the aliphatic hydrocarbon group within the above-mentioned range, compatibility and heat resistance become even better. In addition, heat resistance becomes even better when R ¹ has -COO- or -OCO- in its structure. From the viewpoint of moist heat resistance, the number of -COO- and -OCO- in the group represented by R ¹ is preferably 1 to 3, and more preferably 1 to 2.

When n in the formula (IA) is 2, the heat-and-moisture resistance of the cured product of the polymerizable composition becomes even better, and the heat resistance, adhesiveness, and optical properties of the cured product also improve, so that Y ¹⁰ in the formula (1) is - It is preferable that it is S-. When Y ¹⁰ is -S-, Z ¹ and Z ² are divalent aliphatic hydrocarbon groups with 1 to 30 carbon atoms which may have a substituent, or Z ¹ and Z ² have 6 carbon atoms which may have a substituent. Compounds containing ~30 divalent aromatic hydrocarbon ring groups are preferred.

The divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms represented by Z ¹ and Z ² improves the heat-and-moisture resistance of the cured product of the polymerizable composition, and the heat resistance, adhesiveness, and optical properties of the cured product also improve. It is preferable that it is an alkylene group having 1 to 30 carbon atoms. From the same viewpoint, it is preferable that the alkylene group is linear. Additionally, it is preferable that the alkylene group does not have a substituent. In addition, the number of carbon atoms of the alkylene group is preferably 1 to 10, and more preferably 1 to 4 from the viewpoint of compatibility.

The divalent aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms represented by Z ¹ and Z ² improves the heat-and-moisture resistance of the cured product of the polymerizable composition, and also improves the heat resistance, adhesiveness, and optical properties of the cured product. Therefore, it is preferable that it is an aromatic hydrocarbon ring with a monocyclic structure, and it is more preferable that it is a phenylene group. Additionally, the aromatic hydrocarbon ring-containing group preferably has a substituent. The substituent is preferably an alkyl group having 1 to 10 carbon atoms. The alkyl group is preferably branched from the viewpoint of compatibility. Examples of the alkyl group having 1 to 10 carbon atoms include those 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 heat-and-moisture resistance of the cured product of the polymerizable composition becomes even better, and the heat resistance, adhesiveness, and optical properties of the cured product also improve, so Y ¹² in the formula (3) is carbon It is preferable that it is a tetravalent aliphatic hydrocarbon group with 1 to 30 atoms, and it is more preferable that it is an alkanetetrayl group with 1 to 30 carbon atoms. The number of carbon atoms in the alkane tetral group is preferably 1 to 10, and more preferably 1 to 7.

In formula (3), Z ¹ , Z ² , Z ³ and Z ⁴ are preferably a direct bond.

As the thioether compound (A) of the present invention, a compound represented by the following general formula (I-B) is also preferable because the heat-and-moisture resistance of the cured product of the polymerizable composition is further improved and the heat resistance and adhesiveness of the cured product are also improved. .

(Wherein, R ¹¹ is an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent, or an aliphatic group having 1 to 30 carbon atoms. A group in which at least one methylene group among the hydrocarbon groups is substituted by a divalent group selected from <Group A1> below, or at least one methylene group among the aromatic hydrocarbon ring-containing groups having 6 to 30 carbon atoms described above is < Represents a group substituted by a divalent group selected from group A1>,

n1 represents an integer from 1 to 6,

D1 is an aromatic hydrocarbon ring-containing group with 6 to 30 carbon atoms that may have a substituent, or one or more methylene groups among the aromatic hydrocarbon ring-containing groups with 6 to 30 carbon atoms that may have a substituent. <Group A1> It represents a group substituted by a divalent group selected from .

<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 aliphatic hydrocarbon group having 1 to 30 carbon atoms that may have a substituent represented by R ¹¹ and the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms that may have a substituent include the substituent represented by R ¹ described above. Examples include the same aliphatic hydrocarbon group, which may have 1 to 30 carbon atoms, and an aromatic hydrocarbon ring-containing group, which may have 6 to 30 carbon atoms, which may have a substituent.

Examples of the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms that may have a substituent represented by D 1 include the same aromatic hydrocarbon ring-containing groups having 6 to 30 carbon atoms that may have a substituent represented by R ¹ described above. You can.

Among <Group A1>, the hydrocarbon groups having 1 to 30 carbon atoms represented by R ^2a and R ^3a include the same hydrocarbon groups having 1 to 30 carbon atoms represented by R ² and R ³ described above.

As the heat-and-moisture resistance of the cured product of the polymerizable composition becomes further improved, the heat resistance, adhesiveness, and optical properties of the cured product also improve. Therefore, in the general formula (IB), R ¹¹ may have a substituent, and the number of carbon atoms is 1 to 1. It is preferable that it is an aliphatic hydrocarbon group of 30, and from the same viewpoint, it is preferable that the aliphatic hydrocarbon group is an alkyl group. Additionally, the number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 10, and more preferably 4 to 8. It is preferable that the aliphatic hydrocarbon group is unsubstituted.

As the heat-and-moisture resistance of the cured product of the polymerizable composition becomes better, the heat resistance, adhesiveness, and optical properties of the cured product also improve, so n1 in the general formula (I-B) is preferably 1 to 4, and 2 to 3. It is more preferable to be

As the heat-and-moisture resistance of the cured product of the polymerizable composition becomes further improved, the heat resistance, adhesiveness, and optical properties of the cured product also improve, so the aromatic hydrocarbon ring-containing group represented by D1 in the general formula (IB) is an aromatic monocyclic structure. It is preferable that it has a hydrocarbon ring, and it is more preferable that it is a phenyl group. The number of carbon atoms in the aromatic hydrocarbon ring-containing group is preferably 6 to 20, more preferably 6 to 16, and still more preferably 6 to 110. In addition, the aromatic hydrocarbon ring-containing group preferably has a substituent because the heat resistance of the cured product of the polymerizable composition improves. From the viewpoint of compatibility, the substituent is preferably an alkyl group or hydroxyl group having 1 to 10 carbon atoms, especially 1 to 4 carbon atoms, and more preferably the aromatic hydrocarbon ring-containing group is substituted with an alkyl group or a hydroxyl group. Examples of the alkyl group having 1 to 10 carbon atoms include those having 1 to 10 carbon atoms among the alkyl groups having 1 to 30 carbon atoms represented by R ¹ described above.

In the present invention, a commercial product may be used as the thioether compound (A). Commercially available products of the thioether compound (A) include, for example, Adekastab AO-412S, Adekastab AO-503, and Adekastab AO-26 (manufactured by ADEKA Corporation); and Irganox PS800FL and Irganox PS802FL (product of BASF).

In the present invention, one type of the above-mentioned thioether compound may be used individually, or two or more types may be used in combination. When two or more thioether compounds are used in combination, the heat-and-moisture resistance of the cured product of the polymerizable composition becomes even better, and the heat resistance, adhesiveness, and optical properties of the cured product also improve, so that n in Formula (I-A) It is preferable to use a combination of a compound represented by 1 and a compound where n in formula (I-A) is represented by 2.

Since the content of the thioether compound (A) in the polymerizable composition of the present invention improves the heat resistance and adhesiveness of the cured product of the polymerizable composition, the thioether compound ( It is preferred to contain 0.1 parts by mass or more and less than 10 parts by mass of A), more preferably 0.2 parts by mass or more and less than 5 parts by mass, more preferably 0.3 parts by mass or more and less than 3 parts by mass, and more preferably 0.4 parts by mass. It is particularly preferable to contain less than 2 parts by mass.

Next, the cationically polymerizable compound (B) contained in the polymerizable composition of the present invention will be described.

In the present invention, a cationic polymerizable compound refers to a compound that undergoes polymerization or crosslinking reaction by a cationic polymerization initiator activated by light irradiation or heating.

In the present invention, known cationically polymerizable compounds can be used as the cationically polymerizable compound (B) without particular restrictions. Examples of the cationically polymerizable compound (B) include an epoxy compound and an oxetane compound (B4). The cationic polymerizable compound (B) further improves the heat-and-moisture resistance of the polymerizable composition and improves heat resistance and adhesiveness, so it can be used as an alicyclic epoxy compound (B1), an aliphatic epoxy compound (B2), and an aromatic epoxy compound (B3). It is preferable to contain at least one type selected from the group consisting of.

In the present invention, the cationically polymerizable compound (B) preferably contains an alicyclic epoxy compound (B1) because the curability of the polymerizable composition improves. An alicyclic epoxy compound is a compound that has a cycloalkene oxide structure and does not have an aromatic ring.

The cycloalkene oxide structure is a structure in which the aliphatic ring and the epoxy ring share part of the ring structure, such as the cyclohexene oxide structure or cyclopentene oxide structure obtained by epoxidizing a cyclohexene ring-containing compound or a cyclopentene ring-containing compound with an oxidizing agent.

In the present invention, the alicyclic epoxy compound (B1) may have one or two or more cycloalkene oxide structures in one molecule. As the heat resistance of the cured product of the polymerizable composition becomes better, the heat resistance, adhesiveness, and optical properties of the cured product also improve, so the alicyclic epoxy compound (B1) contains one or two cycloalkene oxide structures per molecule. It is desirable to have.

Examples of alicyclic epoxy compounds having one cycloalkene oxide structure include 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentadiene diepoxide, and epoxy. Examples include dioctyl hexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, and limonene dioxide. .

Examples of alicyclic epoxy compounds having two cycloalkene oxide structures include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-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)adipate, propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, ethylenebis( 3,4-epoxycyclohexanecarboxylate) and the like.

A commercial product can be used as the alicyclic epoxy compound (B1). Specific examples of commercial products include Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxide 3000 (Daicel product), LDO (Symrise product), etc.

In the present invention, one type of the above-mentioned alicyclic epoxy compound (B1) may be used individually or two or more types may be used in combination.

Since the content of the alicyclic epoxy compound (B1) in the cationically polymerizable compound (B) improves the heat resistance and adhesiveness of the cured product of the polymerizable composition, the alicyclic epoxy compound ( It is preferable to contain 1 to 20 parts by mass of B1), and it is more preferable to contain 3 to 10 parts by mass.

In the present invention, the cationically polymerizable compound (B) preferably contains an aliphatic epoxy compound (B2) because the polymerizable composition has low viscosity and excellent handling properties.

The aliphatic epoxy compound (B2) is a compound that has one or more epoxy groups and does not have an aromatic ring or cycloalkene oxide structure. Examples of aliphatic epoxy compounds include monofunctional epoxy compounds and polyfunctional epoxy compounds. Examples of monofunctional epoxy compounds include glycidyl ethers of aliphatic alcohols and glycidyl esters of alkyl carboxylic acids. Examples of polyfunctional epoxy compounds include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts, and polyglycidyl esters of aliphatic long-chain polybasic acids. In the present invention, the aliphatic epoxy compound (B2) is preferably monofunctional or difunctional because the polymerizable composition has low viscosity and excellent handling properties.

Representative compounds of aliphatic epoxy compounds (B2) include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, and 1,4-butanediol diglycy. Dyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, Glycidyl ethers of polyhydric alcohols such as diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, and glycerin, and one or two or more types of alkyl Examples include polyglycidyl etherification of polyether polyol obtained by adding lene oxide, and diglycidyl ester of aliphatic long-chain dibasic acid. Further examples include monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxystearate, butyl epoxystearate, epoxidized soybean oil, and epoxidized polybutadiene.

A commercial product can be used as the aliphatic epoxy compound (B2). Commercially available products of the aliphatic epoxy compound (B2) include, for example, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, and 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 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 Chemtech Co., Ltd.); Eporite M-1230, Eporite 40E, Eporite 100E, Eporite 200E, Eporite 400E, Eporite 70P, Eporite 200P, Eporite 400P, Eporite 1500NP, Eporite 1600, Eporite 80MF, Eporite 100MF ( (manufactured by Kyoeisha Kagaku Co., Ltd.), Adecaglycirol ED-503, Adecaglycirol ED-503G, Adecaglycirol ED-506, Adecaglycirol ED-523T (produced by ADEKA Co., Ltd.), Examples include Pogose 2EH (Yokaichi Kose product).

In the present invention, one type of the above-mentioned aliphatic epoxy compound (B2) may be used individually or two or more types may be used in combination.

Since the content of the aliphatic epoxy compound (B2) in the cationically polymerizable compound (B) improves the heat resistance and adhesiveness of the cured product of the polymerizable composition, the aliphatic epoxy compound (B2) is added to 100 parts by mass of the cationically polymerizable compound (B). It is preferable to contain 20 to 60 parts by mass, and it is more preferable to contain 30 to 50 parts by mass.

In the present invention, the cationically polymerizable compound (B) preferably contains an aromatic epoxy compound (B3) because the heat resistance of the cured product of the polymerizable composition is improved.

An 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, since the heat resistance of the cured product of the polymerizable composition becomes good, it is preferable that the aromatic epoxy compound (B3) contains at least a monofunctional aromatic epoxy compound or a bifunctional aromatic epoxy compound.

Examples of monofunctional aromatic epoxy compounds include monohydric phenols with one aromatic ring, such as phenol, cresol, and butylphenol, or glycidyl etherified products of compounds obtained by adding alkylene oxide to these compounds. .

Examples of polyfunctional aromatic epoxy compounds include bisphenol A, bisphenol F, and glycidyl ether products of compounds obtained by adding alkylene oxide to these compounds; Glycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups, such as resorcinol, hydroquinone, and catechol; Polyglycidyl etherified products of aromatic compounds having two or more alcoholic hydroxyl groups such as benzenedimethanol, benzenediethanol, and benzenedibutanol; and glycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid, and trimellitic acid.

As the aromatic epoxy compound (B3), a commercially available product 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, and Denacol EX. -147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, Oncote EX-1020, Oncote EX-1030, Oncote EX-1040, Oncote EX-1050 , Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, Oncoat 1012 (manufactured by Nagase Chemtech Co., Ltd.); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (manufactured by Osaka Gas Chemicals); HP4032, HP4032D, HP4700 (DIC company products); ESN-475V (produced by Shin-Ni-Tetsu Sumikin Kagaku Corporation); Epicoat YX8800 (manufactured by Mitsubishi Chemical Corporation); Maproof G-0105SA, Maproof G-0130SP (Nichiyu); Epiclon N-665, Epiclon HP-7200 (manufactured by DIC); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, ); Adecaglycirol ED-501, Adecaglycirol ED-502, Adecaglycirol ED-509, Adecaglycirol ED-529, AdekaResin EP-4000, AdekaResin EP-4005, Adeka Resin EP-4100E, Adeka Resin EP-4901 (made by ADEKA); TECHMORE VG-3101L, EPOX-MKR710, EPOX-MKR151 (manufactured by Printech), YX-4000 (manufactured by Mitsubishi Chemical), etc.

In the present invention, one type of the aromatic epoxy compound (B3) described above may be used individually or two or more types may be used in combination.

Since the content of the aromatic epoxy compound (B3) in the cationically polymerizable compound (B) improves the heat resistance and adhesiveness of the cured product of the polymerizable composition, the aromatic epoxy compound (B3) is added to 100 parts by mass of the cationically polymerizable compound (B). It is preferable to contain 30 to 70 parts by mass, and it is more preferable to contain 40 to 60 parts by mass.

In the present invention, because the heat resistance and adhesiveness of the cured product of the polymerizable composition are improved, the cationic polymerizable compound (B) contains an alicyclic epoxy compound (B1), an aliphatic epoxy compound (B2), and an aromatic epoxy compound (B3). It is desirable.

The cationically polymerizable compound (B) preferably contains an oxetane compound (B4) because the heat-and-moisture resistance of the cured product of the polymerizable composition becomes even better.

The oxetane compound (B4) is a compound that has at least one oxetanyl group and no epoxy group. In the present invention, it is preferable to use an oxetane compound having one or two oxetanyl groups because the heat-and-moisture resistance of the cured product of the polymerizable composition becomes even better.

Examples of oxetane compounds having one oxetanyl group include 3-ethyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-(methoxymethyl)oxetane, and 3-ethyl-3- (hexyloxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(cyclohexyloxymethyl)oxetane, 3-ethyl-3-(4-hyde Roxybutyloxymethyl)oxetane, etc. can be mentioned.

Oxetane compounds having two oxetanyl groups include, for example, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,4-bis[(3-ethyl-3-oxeta) Nylmethoxy)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-oxetanyl) Methyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, 3-ethyl-3-(3 -Ethyl-3-oxetanylmethyloxymethyl)oxetane, xylylenebisoxetane, etc. are mentioned.

A commercial product can also be used as the oxetane compound (B4). Commercially available oxetane compounds include, for example, aronoxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (made by Toagosei), and etanacol OXBP and OXTP. (Ube Kosan product), etc. can be mentioned.

In the present invention, one type of the above-mentioned oxetane compound (B4) may be used individually or two or more types may be used in combination.

The content of the oxetane compound (B4) in the cationically polymerizable compound (B) improves the heat-and-moisture resistance of the cured product of the polymerizable composition, and the heat resistance and adhesion of the cured product improves, so the cationically polymerizable compound ( B) It is preferable to contain 1 to 30 parts by mass of the oxetane compound (B4) in 100 parts by mass, and it is more preferable to contain 5 to 25 parts by mass.

The content of the cationically polymerizable compound (B) in the polymerizable composition of the present invention improves the heat-and-moisture resistance and heat resistance of the cured product of the polymerizable composition, and the adhesiveness and optical properties of the cured product improve. It is preferable to contain 50 parts by mass but less than 99 parts by mass of the cationically polymerizable compound (B) in 100 parts by mass of solid content of the composition, more preferably 75 parts by mass to less than 99 parts by mass, and more preferably 85 parts by mass to 99 parts by mass. It is more preferable to contain less than one part. The solid content refers to the solvent to be described later removed from the polymerizable composition.

Next, the cationic polymerization initiator (C) contained in the polymerizable composition of the present invention will be described.

In the present invention, the cationic polymerization initiator (C) is a compound that can release a substance that initiates cationic polymerization by irradiation of light or heating.

In the present invention, a photo cationic 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 photo cationic polymerization initiator (C) as the cationic polymerization initiator (C) because curing shrinkage is small and adhesiveness is excellent.

The photo cationic polymerization initiator may be any compound that can release a substance that initiates cationic polymerization upon irradiation of light, but a double salt or a derivative thereof, which is an onium salt that releases a Lewis acid upon irradiation of light, is preferred.

Examples of the double salt, which is an onium salt, or its derivative, include a salt of a cation and anion represented by the following general formula (i).

[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 general formula (ii), R ¹¹⁰ represents an organic group having a number of carbon atoms of 1 to 60 and which may contain several atoms other than carbon atoms.

x represents an integer from 1 to 5.

Each of x R ¹¹⁰ is independent and may be the same or different.

At least one of x R ¹¹⁰ represents the organic group having an aromatic ring.

Q represents an atom or atom group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F and N=N. Additionally, when the valence of Q among cations [A] ^m+ is set to q, it is necessary that the relationship m=xq be established. However, N=N is treated as valence 0.

Additionally, the anion [B] ^m- is preferably a halide complex, and its structure can be represented, for example, by the following general formula (iii).

[LX _y ] ^m- (iii)

In the general formula (iii), L represents a metal or semimetal (Metalloid) which is the central atom of the halide complex, and 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 from 3 to 7. Additionally, when the valence of L among the anions [B] ^m- is set to p, it is necessary that the relationship m=yp be established.

^Specific _{examples of the} ^anion _{[ L} ^_ Hexafluorophosphate (PF ₆ ) ^- , Hexafluoroantimonate (SbF ₆ ) ^- , Hexafluoroarsenate (AsF ₆ ) - , Hexachloroantimonate (SbCl ₆ ^{) -} , Tris (pentafluoro) and methyl)trifluorophosphate ion (FAP anion).

Additionally, the anion [B] ^m- may have a structure represented by the following general formula (iv).

[LXy _-1 (OH)] ^m- (iv)

Here, L, X and b are the same as above.

In addition, other anions include perchlorate ion (ClO ₄ ) ^- , trifluoromethylsulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonic acid ion (FSO ₃ ) ^- , toluenesulfonic acid anion, trinitrobenzenesulfonic acid anion, and camphor sulfo. nate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraaryl borate, tetrakis(pentafluorophenyl)borate, etc.

In the present invention, among such onium salts, sulfonium cations such as triphenylsulfonium cations represented by group I or group II below are used because the curability of the polymerizable composition improves and the adhesiveness of the cured product of the polymerizable composition improves. Sulfonium salts with anions such as hexafluorophosphate, hexafluoroantimonate, and tetrakis(pentafluorophenyl)borate are preferred.

A commercial product can also be used as a photocationic polymerization initiator. Commercially available photocationic polymerization initiators include, for example, “Kayarad (registered trademark) PCI-220” and “Kayarad (registered trademark) PCI-620” manufactured by Nippon Kayaku Co., Ltd.; “UVI-6990” from Dow Chemical Company; “Adeka Acles (registered trademark) SP-150”, “Adeka Optomer (registered trademark) SP-170” and “Adeka Optomer (registered trademark) SP-500” manufactured by ADEKA Co., Ltd.; “CI-5102”, “CIT-1370”, “CIT-1682”, “CIP-1866S”, “CIP-2048S”, “CIP-2064S” from Nippon Soda Co., Ltd.; "DPI-101", "DPI-102", "DPI-103", "DPI-105", "MPI-103", "MPI-105", "BBI-101", manufactured by Midori Kagaku Co., Ltd. "BBI-102", "BBI-103", "BBI-105", "TPS-101", "TPS-102", "TPS-103", "TPS-105", "MDS-103", "MDS -105", "DTS-102", "DTS-103"; “PI-2074” from Rhodia; and CPI-100P of San-Apro products.

The content of the photo cationic polymerization initiator in the polymerizable composition of the present invention improves the adhesion of the cured product of the polymerizable composition and improves the curability of the polymerizable composition, so that the photo cation polymerization initiator is adjusted to 100 parts by mass of the cationically polymerizable compound. It is preferable to contain 0.1 to 15 parts by mass of the initiator (C), more preferably to contain 1 to 13 parts by mass, and even more preferably to contain 3 to 13 parts by mass.

In the present invention, a compound that generates cationic species or Lewis acid by heating can be used as a thermal cationic polymerization initiator without particular limitation. Specifically, salts such as sulfonium salt, thiophenium salt, thioranium salt, benzyl ammonium salt, pyridinium salt, and hydrazinium salt; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; Alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, and isophorone diamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; The above polyamines, glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, and bisphenol F-diglycidyl ether, or glycidyl esters of carboxylic acids Polyepoxy addition-modified products manufactured by reacting various epoxy resins such as Ryu according to a conventional method; Amide-modified products prepared by reacting the above organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid, and dimer acid according to a conventional method; Mannichase prepared by reacting the above polyamines with aldehydes such as formaldehyde and phenols having at least one aldehyde reactive site in the nucleus such as phenol, cresol, xylenol, tertiary butylphenol, and resorcin according to a conventional method. denaturant; Polyhydric carboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanoic acid, 2-methylsuccinic acid, 2-methyladipic acid, Aliphatic dicarboxylic acids such as 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, dimer acid, etc. Leboxylic acids; Aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid; Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; Trimellitic acid, trimesic acid, castor oil fatty acid acid anhydrides of (tricarboxylic acids such as trimers; tetracarboxylic acids such as pyromellitic acid, etc.); Dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, amine imides, etc. can be used.

The content of the thermal cationic polymerization initiator in the polymerizable composition of the present invention is preferably 0.001 to 10 parts by mass, and 0.1 to 8 parts by mass, per 100 parts by mass of the cationically polymerizable compound (B) because the curability of the polymerizable composition is improved. It is more preferable to deny it.

A commercial product can also be used as a thermal cationic polymerization initiator. Commercially available thermal cationic polymerization initiators include, for example, Adeka Optone CP-77, Adeka Optone CP-66 (made by ADEKA), CI-2639, CI-2624 (Nippon Soda), San Aid SI-60, and San Aid. SI-80 and San-Aid SI-100 (manufactured by Sanshin Kagaku Kogyo), etc. can be mentioned.

The polymerizable composition of the present invention may contain a solvent capable of dissolving or dispersing the thioether compound (A), the cationic polymerizable compound (B), and the cationic polymerization initiator (C). A solvent is a compound that is liquid at 25°C and 1 atmosphere of pressure and is not classified into the above-mentioned components. Examples of solvents include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; Ether-based solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; Ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and Texanol; Cellosolve-based solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol-based solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; Ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, etc. ether ester solvent; BTX-based solvents such as benzene, toluene, and xylene; Aliphatic hydrocarbon-based solvents such as hexane, heptane, octane, and cyclohexane; Terpene hydrocarbon oils such as turpentine, D-limonene, and pinene; Paraffin-based solvents such as mineral spirits, Swasol #310 (Cosmo Matsuyama Sekiyu Co., Ltd.), and Solvetso #100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichlorethylene, methylene chloride, and 1,2-dichloroethane; Halogenated aromatic hydrocarbon-based solvents such as chlorobenzene; Propylene carbonate, carbitol-based solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, Water and the like can be mentioned, and these solvents can also be used as a mixed solvent of two or more types.

The polymerizable composition of the present invention may optionally contain other monomers, other polymerization initiators, inorganic fillers, organic fillers, colorants such as pigments and dyes, light sensitizers, anti-foaming agents, thickeners, surfactants, leveling agents, flame retardants, thixotropic agents, and diluents. , various resin additives such as plasticizers, stabilizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flow regulators, and adhesion promoters can be added.

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 varies depending on the purpose of the present invention, etc., but can further enhance the effect of the present invention. From the viewpoint of further height, it is preferable to set it to 20 parts by mass or less, especially 10 parts by mass or less, per 100 parts by mass of the cationically polymerizable compound (A).

The polymerizable composition of the present invention combines a thioether compound (A), a cationic polymerizable compound (B), and a cationic polymerization initiator (C). Even if a thioether compound (A), a radical polymerizable composition, and a radical polymerization initiator are combined, the effect of the present invention of obtaining a cured product with good heat-and-moisture resistance is not exhibited. Additionally, the cured product of the radical polymerizable composition and the polymerizable composition containing a radical polymerization initiator has poor adhesiveness. Therefore, it is preferable that the polymerizable composition of the present invention does not contain a radical polymerizable composition and a radical polymerization initiator.

A radically polymerizable composition is a compound capable of radical polymerization. Examples of radically polymerizable compounds include compounds having an ethylenically unsaturated group such as an acrylic group, methacryl group, or vinyl group. Specifically, radically polymerizable compounds described in International Publication WO2018/012383, radically polymerizable organic substances described in International Publication WO2014/021023, etc. are included.

A radical polymerization initiator is a compound that generates radicals that can initiate polymerization by exposure to or heating of radiation such as visible light, ultraviolet rays, deep ultraviolet rays, electron beams, or X-rays. Specifically, for example, photo radical polymerization initiators, azo compounds, peroxides, and A thermal radical polymerization initiator such as persulfate, a photo radical polymerization initiator described in Japanese Patent Application Laid-Open No. 2016-210849, etc. can be mentioned.

Specific uses of the polymerizable composition of the present invention include optical materials such as glasses and imaging lenses, paints, coatings, linings, inks, resists, liquid resists, adhesives, printing plates, insulating varnishes, insulating sheets, laminates, and print bases. , encapsulants, molding materials, putties, glass fiber impregnation agents for semiconductor devices, LED packages, liquid crystal inlets, organic EL, optical devices, electrical insulation, electronic components, separators, etc. , fillers, passivation films for semiconductors and solar cells, interlayer insulating films, protective films, prism lens sheets used in the backlight of liquid crystal displays, and lens sheets such as Fresnel lens sheets and lenticular lens sheets used in screens such as projection TVs. Lens parts or backlights using such sheets, optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, optical molding agents, etc., and for example, substrates that can be applied as coating agents. Materials include metal, wood, rubber, plastic, glass, and ceramic products.

The polymerizable composition of the present invention uses a combination of a thioether compound (A), a cationic polymerizable compound (B), and a cationic polymerization initiator (C), so that the cured product has excellent heat-and-moisture resistance. In addition, the polymerizable composition of the present invention has excellent heat resistance, adhesiveness, and optical properties by using these components in combination. Accordingly, the polymerizable composition of the present invention is particularly useful as an adhesive, especially a photocurable adhesive.

Next, the photocurable adhesive of the present invention will be described.

The photocurable adhesive of the present invention contains the polymerizable composition of the present invention. Since the photocurable adhesive of the present invention contains the polymerizable composition of the present invention, it has excellent heat and moisture resistance. In addition, the photocurable adhesive of the present invention has excellent 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. There are no restrictions on the irradiation conditions and heating conditions of active energy rays, and known conditions can be adopted.

Next, the use of the polymerizable composition of the present invention as a photocurable adhesive will be explained.

In the present invention, the polymerizable composition described above is used as a photocurable adhesive for bonding two members together by irradiation of light. There are no particular restrictions on the amount of the polymerizable composition used, the method of application to the member, the wavelength or amount of light to be irradiated, and known methods and conditions can be appropriately adopted. In addition, according to the present invention, a method of bonding two members using the above-described polymerizable composition is also provided. Specifically, after the above-described polymerizable composition is placed between two members, light is irradiated to the polymerizable composition to cure the polymerizable composition, thereby bonding the two members.

Example

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

[Examples and Comparative Examples]

Each component was sufficiently mixed in the formulation shown in Tables 1 to 3 below to prepare polymerizable compositions 1 to 21 of Examples 1 to 21 and polymerizable compositions of Comparative Examples 1 and 2. The symbols in the table indicate the following components. In addition, the numbers in the table represent parts by mass.

A-1: Compound represented by the following formula (A-1)

A-2: Compound represented by the following formula (A-2)

A-3: Compound represented by the following formula (A-3)

A-4: Compound represented by the following formula (A-4)

A-5: Compound represented by the following formula (A-5)

A-6: Compound represented by the following formula (A-6)

A-7: Compound represented by the following formula (A-7)

A'-1: Compound represented by the following formula (A'-1)

B1-1: Compound represented by the following formula (B1-1)

B1-2: Compound represented by the following formula (B1-2)

B2-1: Compound represented by the following formula (B2-1)

B2-2: Compound represented by the following formula (B2-2)

B3-1: Compound represented by the following formula (B3-1)

B3-2: Compound represented by the following formula (B3-2)

B3-3: Compound represented by the following formula (B3-3)

B3-4: Compound represented by the following formula (B3-4)

B4-1: Compound represented by the following formula (B4-1)

B4-2: Compound represented by the following formula (B4-2)

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

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

Heat-and-moisture resistance, heat resistance, adhesiveness, and optical properties of the 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 to 3.

<Adhesion test>

The compositions prepared in the examples and comparative examples were each applied to a TAC film (Fujitac TD80, manufactured by Fuji Film Co., Ltd.) so that the film thickness after curing was 3 μm to form a coating film. Next, a COP (cycloolefin polymer, manufactured by Nippon Zeon Co., Ltd. product: Zeonoa Film 14-060) film subjected to corona discharge treatment was laminated to the surface of the TAC film where the coating film was formed using a laminator to obtain a laminate. . Then, a test piece was produced by irradiating light equivalent to 1000 mJ/cm2 through the COP film to the laminate using an electrodeless ultraviolet light lamp and bonding it.

The obtained test piece was stored under conditions of 30°C, 50%RH, and atmospheric pressure for 12 hours from exposure. Next, a 2.0 cm wide piece was cut from the test piece to obtain a sample for evaluation. A 90 degree peeling test was performed on the obtained sample, and the adhesiveness of the evaluation sample was evaluated according to the following criteria. The 90 degree peeling test was conducted under conditions of 30°C, 50%RH, and atmospheric pressure. The larger the value of N/2cm, the better the adhesiveness.

A: More than 2.5N/2cm or destruction of substrate

B: More than 1.5N/2cm but less than 2.5N/2cm

C: More than 0.5N/2cm but less than 1.5N/2cm

D: Less than 0.5N/2cm.

<Moisture and heat resistance test>

A test piece was obtained in the same manner as in the adhesion test. The obtained test piece was kept in an environment of 85°C and 85%RH for 500 hours. After lowering the test piece to room temperature, a 90-degree peeling test was performed on the test piece in the same manner as the adhesion test, and the heat-and-moisture resistance of the evaluation sample was evaluated according to the following criteria. The larger the value of N/2cm, the better the heat and moisture resistance.

A: 1.5N/2cm or more

B: More than 1.0N/2cm but less than 1.5N/2cm

C: More than 0.5N/2cm but less than 1.0N/2cm

D: Less than 0.5N/2cm

<Optical properties test>

The polymerizable compositions prepared in the examples and comparative examples were each applied to a glass plate so that the film thickness after curing was 50 μm, and then another glass plate was attached to the surface of the glass plate on which the coating film was formed. The bonded glass plates were irradiated with energy of 1000 mJ/cm2 using a high-pressure Hg lamp, and then the glass plates were heated at 150°C for 1 hour to obtain a test piece.

b* of the obtained test piece was measured using an ultraviolet, visible, near-infrared spectrophotometer V-670 (manufactured by Nippon Bunko Corporation), and the optical properties of the test piece were evaluated based on the following criteria. The smaller the value of b*, the better the optical properties.

A: b* of the cured product is less than 5

B: b* of the cured product is 5 or more and less than 10

C: b* of the cured product is 10 or more

<Heat resistance test>

A test piece was obtained in the same manner as the optical properties test. b* of the obtained test piece was measured using an ultraviolet-visible-near-infrared spectrophotometer V-670 (manufactured by Nippon Bunko Corporation). Next, the test piece was kept in an environment of 85°C and 85%RH for 500 hours, and then b* of the test piece was measured. And the heat resistance of the test piece was evaluated based on the following criteria. The smaller △b*, the better the heat resistance.

A: Δb*<3

B: 3≤Δb*<5

C: 5≤Δb*<8

D: 8≤Δb*

As is clear from Tables 1 to 3, the cured products of the polymerizable compositions of Examples 1 to 21 had good heat and moisture resistance. These cured products also had excellent heat resistance, adhesion, 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) had poor heat and moisture resistance as well as poor heat resistance. In addition, the cured product of the polymerizable composition of Comparative Example 2 containing another component (A'-1) instead of the thioether compound (A) had poor heat-and-moisture resistance, heat resistance, and optical properties.

Claims (15)

A polymerizable composition containing a thioether compound (A), a cationic polymerizable compound (B), and a cationic polymerization initiator (C). According to paragraph 1,
A polymerizable composition in which the thioether compound (A) has an ester bond in the molecule. According to claim 1 or 2,
A polymerizable composition in which the thioether compound (A) has a group represented by the following general formula (I).

(Wherein, R ¹ is an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent, or an aliphatic group having 1 to 30 carbon atoms) A group in which at least one methylene group among the hydrocarbon groups is substituted by a divalent group selected from <Group A> below, or at least one methylene group among the aromatic hydrocarbon ring-containing groups having 6 to 30 carbon atoms described above is < Represents a group substituted by a divalent group selected from group A>,
Y ¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms, which may have a substituent, or a divalent hydrocarbon group in which at least one methylene group of the above divalent hydrocarbon groups having 1 to 30 carbon atoms is selected from <Group A> below. Represents a group substituted by a group,
* represents the number of combinations.
<Group A>: -O-, -CO-, -COO-, -OCO-, -NR ² -, -NR ³ CO- or -S-, R ² and R ³ are each independently a hydrogen atom or a carbon atom Indicates hydrocarbon groups with numbers 1 to 30.) According to paragraph 3,
A polymerizable composition in which R ¹ in general formula (I) is an aliphatic hydrocarbon group having 5 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms which may have a substituent. According to clause 3 or 4,
A polymerizable composition in which Y ¹ in general formula (I) is a divalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. According to any one of claims 3 to 5,
A polymerizable composition in which the thioether compound (A) has a plurality of groups represented by general formula (I) in the molecule. According to paragraph 1,
A polymerizable composition wherein the thioether compound (A) is a compound represented by the following general formula (IB).

(Wherein, R ¹¹ is an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent, or an aliphatic group having 1 to 30 carbon atoms. A group in which at least one methylene group among the hydrocarbon groups is substituted by a divalent group selected from <Group A1> below, or at least one methylene group among the aromatic hydrocarbon ring-containing groups having 6 to 30 carbon atoms described above is < Represents a group substituted by a divalent group selected from group A1>,
n1 represents an integer from 1 to 6,
D1 represents an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring-containing group having 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.) In clause 7,
A polymerizable composition in which D1 in the general formula (IB) has an aromatic hydrocarbon ring with a monocyclic structure. According to paragraph 7 or 8,
A polymerizable composition in which R ¹¹ in the general formula (IB) is an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. According to any one of claims 1 to 9,
A polymerizable composition containing 0.1 parts by mass or more and less than 10 parts by mass of a thioether compound (A) relative to 100 parts by mass of the cationically polymerizable compound (B). According to any one of claims 1 to 10,
A polymerizable composition in which the cationically polymerizable compound (B) contains at least one member selected from the group consisting of an alicyclic epoxy compound (B1), an aliphatic epoxy compound (B2), and an aromatic epoxy compound (B3). A photocurable adhesive containing the polymerizable composition according to any one of claims 1 to 11. A method for producing a cured product, comprising the step of irradiating the polymerizable composition according to any one of claims 1 to 11 with active energy rays, or the step of heating. A cured product of the polymerizable composition according to any one of claims 1 to 11. Use of the polymerizable composition according to any one of claims 1 to 11 as a photocurable adhesive.