JP2022157564A - Polymerizable composition, photocurable adhesive, method for producing cured product, and cured product - Google Patents

Abstract

To provide a polymerizable composition which has low viscosity and gives a cured product excellent in moist heat resistance and adhesive force.SOLUTION: The polymerizable composition contains a cationically polymerizable compound (A) and a photocationic polymerization initiator (B). The cationically polymerizable compound (A) contains an epoxy polymer (A1) and a monofunctional epoxy compound (A2). The cationically polymerizable compound (A) preferably contains an aliphatic epoxy compound (A3), preferably contains an oxetane compound (A4), and preferably contains an alicyclic epoxy compound (A6).SELECTED DRAWING: None

Description

The present invention relates to a polymerizable composition containing a cationically polymerizable compound.

Cationic polymerizable compositions are used in fields such as inks, paints, various coating agents, adhesives, and optical members.
For example, Patent Documents 1 to 3 below disclose various photocurable adhesives.

JP 2011-236389 A JP 2012-149262 A WO2008/111584

An object of the present invention is to provide a polymerizable composition from which a cured product having low viscosity and excellent wet heat resistance and adhesive strength can be obtained.

As a result of intensive studies, the present inventors have obtained a polymerizable composition that provides a cured product with excellent wet heat resistance and adhesive strength by using an epoxy polymer and a monofunctional epoxy compound in combination as cationic polymerizable compounds. The present inventors have found that it is possible to achieve the present invention.

The present invention provides a polymerizable composition containing a cationic polymerizable compound (A) and a photocationic polymerization initiator (B), wherein the cationic polymerizable compound (A) comprises an epoxy polymer (A1) and a monofunctional epoxy compound. A polymerizable composition containing (A2).

INDUSTRIAL APPLICABILITY The polymerizable composition of the present invention is particularly useful as an adhesive because it has a low viscosity and the cured product thereof has excellent moist heat resistance and adhesive strength.

The polymerizable composition of the present invention is described below.
The polymerizable composition of the present invention contains an epoxy polymer (A1) and a monofunctional epoxy compound (A2) as cationically polymerizable compounds (A).

The epoxy polymer (A1) is preferably a polyfunctional epoxy compound having a specific novolak structure, such as a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a phenol-naphthol novolak type epoxy resin, and a bisphenol novolak type epoxy resin. , and aralkyl-type epoxy resins in which an aralkyl group is introduced into the main chain of a novolac structure.

In the present invention, a polymerizable composition in which the epoxy polymer (A1) has a structural unit represented by the following general formula (I) is preferable because a cured product having excellent moist heat resistance and adhesive strength can be obtained.

式中、Ａｒは、ベンゼン環又はナフタレン環を表し、
Ｒ^１は、ハロゲン原子、水酸基、ニトロ基、シアノ基、置換基を有していてもよい炭素原子数１～２０の炭化水素基、置換基を有していてもよい炭素原子数２～１０の複素環基、置換基を有していてもよい炭素原子数３～３０の複素環含有基、又は前記炭素原子数１～２０の炭化水素基中のメチレン基の１つ以上が下記＜群Ａ＞より選ばれる２価の基により置換された基、若しくは前記炭素原子数３～３０の複素環含有基中のメチレン基の１つ以上が下記＜群Ａ＞より選ばれる２価の基により置換された基を表し、
Ｙ^１、Ｙ^２及びＹ^３は、それぞれ独立に、置換基を有してもよい炭素原子数１～２０の炭化水素基又は該炭素原子数１～２０の炭化水素基中のメチレン基の１つ以上が下記＜群Ａ＞より選ばれる２価の基により置換された基であり、
ａは、０～４の整数を表し、
ｂは、０～４の整数を表し、
ｃは、０～４の整数を表し、
ａ＋ｂは１～４であり、ａ＋ｂ＋ｃは１～４である。
＜群Ａ＞：－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ^１１－、－ＮＲ^１２ＣＯ－、－Ｓ－
Ｒ^１１及びＲ^１２は、それぞれ独立に、水素原子、又は炭素原子数１～２０の炭化水素基を表す。

In the formula, Ar represents a benzene ring or a naphthalene ring,
R ¹ is a halogen atom, a hydroxyl group, a nitro group, a cyano group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted carbon atom number of 2 to 10 heterocyclic group, an optionally substituted heterocyclic ring-containing group having 3 to 30 carbon atoms, or one or more of the methylene groups in the hydrocarbon group having 1 to 20 carbon atoms is the following <group A>, or one or more of the methylene groups in the heterocyclic ring-containing group having 3 to 30 carbon atoms is substituted by a divalent group selected from the following <Group A> represents a substituted group,
Y ¹ , Y ² and Y ³ are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or one methylene group in the hydrocarbon group having 1 to 20 carbon atoms one or more is a group substituted with a divalent group selected from the following <group A>,
a represents an integer from 0 to 4,
b represents an integer from 0 to 4,
c represents an integer from 0 to 4,
a+b is 1-4 and a+b+c is 1-4.
<Group A>: -O-, -CO-, -COO-, -OCO-, -NR ¹¹ -, -NR ¹² CO-, -S-
R ¹¹ and R ¹² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

Halogen atoms in general formula (I) include fluorine, chlorine, bromine and iodine atoms.

The hydrocarbon group having 1 to 20 carbon atoms in the general formula (I) is a group having 1 to 20 carbon atoms consisting of a carbon atom and a hydrogen atom. Examples of hydrocarbon groups having 1 to 20 carbon atoms include aliphatic hydrocarbon groups having 1 to 20 carbon atoms and aromatic hydrocarbon ring-containing groups having 6 to 20 carbon atoms.

The aliphatic hydrocarbon groups having 1 to 20 carbon atoms in the general formula (I) include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms and cycloalkyl groups having 4 to 20 carbon atoms. A cycloalkylalkyl group and the like can be mentioned.

The alkyl group having 1 to 20 carbon atoms may be linear or branched. Straight chain alkyl groups include methyl, ethyl, propyl, butyl, iso-amyl, tert-amyl, hexyl, heptyl and octyl. Branched alkyl groups include iso-propyl, sec-butyl, tert-butyl, iso-butyl, iso-pentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl and iso-heptyl. , tert-heptyl, iso-octyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hebrotadecyl, octadecyl and the like.

Cycloalkyl groups having 3 to 20 carbon atoms include saturated monocyclic alkyl groups having 3 to 20 carbon atoms, saturated polycyclic alkyl groups having 3 to 20 carbon atoms, and hydrogen atoms in the rings of these groups. Examples include groups having 4 to 20 carbon atoms in which one or more atoms are substituted with an alkyl group. Examples of the saturated monocyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. Examples of the saturated polycyclic alkyl groups include adamantyl, decahydronaphthyl, octahydropentalene and bicyclo[1.1.1]pentanyl. Examples of the alkyl group substituting the hydrogen atom in the ring of the saturated monocyclic or saturated polycyclic alkyl group include the groups exemplified as the alkyl group having 1 to 20 carbon atoms. Examples of a group in which one or more hydrogen atoms in the ring of a saturated polycyclic alkyl group are substituted with an alkyl group include bornyl and the like.

A cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of an alkyl group is substituted with a cycloalkyl group. A cycloalkyl group in a cycloalkylalkyl group may be monocyclic or polycyclic. The monocyclic cycloalkylalkyl groups having 4 to 20 carbon atoms include, for example, cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl and cyclooctyl. methyl, 2-cyclononylethyl, 2-cyclodecylethyl and the like. The polycyclic cycloalkylalkyl groups having 4 to 20 carbon atoms include 3-3-adamantylpropyl and decahydronaphthylpropyl.

The aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms in general formula (I) is a hydrocarbon group containing an aromatic hydrocarbon ring and not containing a heterocyclic ring, and having an aliphatic hydrocarbon group. may be Examples of aromatic hydrocarbon ring-containing groups include aryl groups having 6 to 20 carbon atoms and arylalkyl groups having 7 to 20 carbon atoms.

The aryl group having 6 to 20 carbon atoms may have a monocyclic structure, a condensed ring structure, or two aromatic hydrocarbon rings linked together. Examples of the aryl group having a condensed ring structure having 6 to 20 carbon atoms include a hydrocarbon-type aromatic condensed ring group having a structure in which two or more aromatic hydrocarbon rings are condensed and having 7 to 20 carbon atoms. .

Examples of monocyclic aryl groups having 6 to 20 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, 2,4,6-trimethylphenyl and the like. Examples of hydrocarbon type aromatic condensed ring groups having 7 to 20 carbon atoms include naphthyl, anthracenyl, phenanthryl, pyrenyl, fluorenyl and indenofluorenyl.

The aryl group in which two aromatic hydrocarbon rings are linked may be one in which two monocyclic aromatic hydrocarbon rings are linked. It may be one in which an aromatic hydrocarbon ring having a condensed ring structure and an aromatic hydrocarbon ring having a condensed ring structure are connected to each other.
A linking group that links two aromatic hydrocarbon rings includes a single bond, a sulfide group (--S--), a carbonyl group, and the like.
Examples of the aryl group in which two monocyclic aromatic hydrocarbon rings are linked include biphenyl, diphenylsulfide, and benzoylphenyl.

An arylalkyl group having 7 to 20 carbon atoms is a group in which one or more hydrogen atoms in an alkyl group are substituted with an aryl group. Examples of arylalkyl groups having 7 to 20 carbon atoms include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl and naphthylpropyl groups. .

As a substituent that may be possessed by a hydrocarbon group having 1 to 20 carbon atoms, a reactive group that can form a carbon-carbon covalent bond by reacting with each other, since the curability is improved. A group having a group is preferred. Examples of reactive groups include epoxy groups such as glycidyl ether groups and cycloalkene oxide groups; ethylenically unsaturated groups such as acrylic groups, methacrylic groups, vinyl groups and vinyl ether groups; halogen atoms; cyano groups; nitro groups; , amino group, carboxyl group, mercapto group and isocyanate group. Among the reactive groups, a glycidyl ether group and a cycloalkene oxide group are preferable because of good adhesiveness, and a glycidyl ether group is particularly preferable because of good heat resistance. For the portion other than the reactive group of the group having a reactive group, one or more of the hydrocarbon group having 1 to 15 carbon atoms or the methylene group in the hydrocarbon group having 1 to 15 carbon atoms is > is a group substituted with a divalent group selected from >, and the hydrocarbon group having 1 to 15 carbon atoms is selected from those exemplified as the hydrocarbon groups having 1 to 20 carbon atoms. is 1 to 15.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include groups obtained by removing one hydrogen atom from the above hydrocarbon groups having 1 to 20 carbon atoms, such as an alkylene group and an arylene group. These groups may have the same substituents as the hydrocarbon groups having 1 to 20 carbon atoms.

The heterocyclic group having 2 to 10 carbon atoms in general formula (I) is a group obtained by removing one hydrogen atom from a heterocyclic compound. The heterocyclic group may have a monocyclic structure or a condensed ring structure. Examples of the heterocyclic group having a condensed ring structure having 2 to 10 carbon atoms include a heterocyclic ring-containing condensed ring group having a structure in which a heterocyclic ring and a heterocyclic ring or a hydrocarbon ring are condensed and having 3 to 10 carbon atoms. be done. Specific heterocyclic groups include, for example, pyridyl, quinolyl, thiazolyl, tetrahydrofuranyl, dioxolanyl, tetrahydropyranyl, methylthiophenyl, hexylthiophenyl, benzothiophenyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolidinyl. , piperidinyl, piperazinyl, pyrimidinyl, furyl, thienyl, benzoxazol-2-yl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, morphonyl and the like.
The heterocyclic group may have a substituent, and the substituent includes a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, --COOH, _--SO.sub.2H , and the like.

The heterocyclic ring-containing group having 3 to 30 carbon atoms in the general formula (I) is a group having 3 to 30 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group is replaced with a heterocyclic group. Examples of the heterocyclic group include the groups exemplified as the heterocyclic group having 2 to 10 carbon atoms. Examples of the hydrocarbon group include the aforementioned hydrocarbon groups having 1 to 20 carbon atoms.
The heterocyclic ring-containing group may have an aromatic hydrocarbon ring-containing group, may have an aliphatic hydrocarbon group, or may have a substituent. Examples of such substituents include halogen atoms, cyano groups, nitro groups, hydroxyl groups, thiol groups, —COOH, —SO ₂ H, and the like.
In addition, "3 to 30 carbon atoms" of a heterocyclic ring-containing group having 3 to 30 carbon atoms means the total number of carbon atoms in the heterocyclic ring-containing group.

A group in which two or more methylene groups in a hydrocarbon group having 1 to 20 carbon atoms and a heterocyclic ring-containing group having 3 to 30 carbon atoms are substituted with a divalent group selected from the above <group A>, The divalent groups do not have adjacent structures.

In the present invention, the number of carbon atoms in a group defines the number of carbon atoms in the group after the substitution when hydrogen atoms in the group are substituted with a substituent. For example, when the hydrogen atom of the alkyl group having 1 to 20 carbon atoms is substituted, the 1 to 20 carbon atoms refers to the number of carbon atoms after the hydrogen atom is substituted, and the hydrogen atom is substituted. It does not refer to the number of carbon atoms before
In the present invention, the number of carbon atoms in a group in which a methylene group in a group having a predetermined number of carbon atoms is replaced with a divalent group defines the number of carbon atoms in the group before the substitution. For example, in the case of a group in which the methylene group in the alkyl group having 1 to 20 carbon atoms is replaced with a divalent group, the 1 to 20 carbon atoms means that the methylene group in the alkyl group is replaced with a divalent group. It refers to the number of carbon atoms before it is replaced, not the number of carbon atoms after it is replaced.

In the general formula (I), Y ¹ is preferably a group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, and among them, it has a substituent A polymerizable composition having an arylene group having 6 to 20 carbon atoms, which may be substituted, is preferable because a cured product having excellent wet heat resistance and adhesive strength can be obtained. Arylene groups include phenylene, biphenylene and naphthylene groups. A phenylene group is preferable because a polymerizable composition having low viscosity and excellent handling can be obtained. Therefore, it is preferable.

Y ² and Y ³ in the general formula (I) preferably represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms, especially an alkylene group having 1 to 20 carbon atoms. An alkylene group having 1 to 10 carbon atoms is particularly preferable, and an alkylene group having 1 to 5 carbon atoms is particularly preferable because a cured product having excellent moisture and heat resistance can be obtained.

It is preferable that a in the general formula (I) is an integer of 1 to 4, b is 0 to 3, and C is an integer of 0 to 3. Among them, a is an integer of 1 to 2, and c is an integer of 0 to 2. A polymerizable composition having an integer is preferable because a cured product excellent in moist heat resistance and adhesive strength can be obtained, and a polymerizable composition in which a is 1 and c is 0 is particularly preferable.

In the present invention, the polymerizable composition in which the structural unit represented by the general formula (I) is a structural unit represented by the following general formula (Ia) is a cured product having excellent wet heat resistance and adhesive strength. It is preferable because it can be obtained.

式中、Ｒ^２は、炭素原子数１～１０の脂肪族炭化水素基を表し、
Ｙ^４は、置換基を有していてもよい炭素原子数６～２０のアリーレン基を表し、
Ｙ^５は、２価の炭素原子数１～１０のアルキレン基を表し、
ｄは、１～４の整数を表し、
ｅは、０～３の整数を表し、
ｄ＋ｅは１～４である。

In the formula, R ² represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms,
Y ⁴ represents an optionally substituted arylene group having 6 to 20 carbon atoms,
Y ⁵ represents a divalent alkylene group having 1 to 10 carbon atoms,
d represents an integer of 1 to 4,
e represents an integer from 0 to 3,
d+e is 1-4.

Specific examples of the structural units of the epoxy polymer (A1) include the following structural units.

In the present invention, the epoxy equivalent of the epoxy polymer (A1) is 180 g/eq. 350 g/eq. A polymerizable composition having a molecular weight of less than is preferable because it can be cured at a low exposure dose and a cured product having excellent heat resistance can be obtained. The epoxy equivalent is 200 g/eq. above 325 g/eq. More preferably less than 220 g/eq. 300 g/eq. is particularly preferred.

Commercial products can be used as the epoxy polymer (A1). Pharmaceutical) and the like.

The monofunctional epoxy compound (A2) is a compound having only one epoxy group and no alicyclic epoxy group. An alicyclic epoxy group refers to a cycloalkene oxide structure.
Monofunctional epoxy compounds (A2) include monofunctional aromatic epoxy compounds and monofunctional aliphatic epoxy compounds.

A monofunctional aromatic epoxy compound is an epoxy compound having only one epoxy group and an aromatic ring. Monoglycidyl ethers of phenols or alkylene oxide adducts thereof, glycidyl esters of benzoic acids such as benzoic acid, toluic acid and naphthoic acid, and epoxidized styrene oxides can be mentioned.

A monofunctional aliphatic epoxy compound is an epoxy compound that has only one epoxy group and does not have an aromatic ring or an alicyclic epoxy group. Ester etc. are mentioned. Representative compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ethers, monoglycidyl ethers of higher aliphatic alcohols, and glycidyl esters of higher fatty acids.

In the present invention, the epoxy equivalent of the monofunctional epoxy compound (A2) is 150 g/eq. 500 g/eq. A polymerizable composition having a viscosity of less than 10% is preferable because a cured product having low viscosity, excellent handleability, and excellent moist heat resistance can be obtained. The epoxy equivalent is 160 g/eq. above 475 g/eq. More preferably less than 170 g/eq. 450 g/eq. It is particularly preferred that it is less than.

Commercially available monofunctional epoxy compounds (A2) can also be used. EX-171 (manufactured by Nagase ChemteX), ADEKA GLYCIROL ED-501, ADEKA GLYCIROL ED-502, ADEKA GLYCIROL ED-509S, ADEKA GLYCIROL ED-529 (ADEKA), EPOLITE M-1230 (KYOEISHA CHEMICAL) ), Epogose 2EH (manufactured by Yokkaichi Gosei), Cardolite LITE513E (manufactured by Cardolite), and the like.

A polymerizable composition containing 50 parts by mass or more and less than 99 parts by mass of the cationic polymerizable compound (A) in 100 parts by mass of the solid content of the polymerizable composition is preferable because a cured product having excellent moist heat resistance is obtained. It is more preferably from 85 parts by mass to less than 95 parts by mass, and particularly preferably from 85 parts by mass to less than 95 parts by mass. The term "solid content" as used herein refers to parts by mass obtained by removing the parts by mass of the solvent described below from the parts by mass of the entire polymerizable composition.

In the present invention, the polymerizable composition containing 5 parts by mass or more and less than 50 parts by mass of the epoxy polymer (A1) in 100 parts by mass of the cationic polymerizable compound (A) provides a cured product having excellent resistance to moist heat. preferable. The content of the epoxy polymer (A1) is particularly preferably 10 parts by mass or more and less than 40 parts by mass in order to achieve both low viscosity and heat resistance.

In the present invention, the polymerizable composition containing 0.5 parts by mass or more and 50 parts by mass or less of the monofunctional epoxy compound (A2) in 100 parts by mass of the cationically polymerizable compound (A) has a low viscosity and excellent handling. It is preferable because a cured product having excellent moist heat resistance can be obtained. The content of the monofunctional epoxy compound (A2) is more preferably 1.0 parts by mass or more and 40 parts by mass or less, and is 5 parts by mass or more and 30 parts by mass or less in order to achieve both low viscosity and heat resistance. is particularly preferred.

The cationically polymerizable compound (A) preferably contains an aliphatic epoxy compound (A3), since a polymerizable composition having a low viscosity and excellent handleability can be obtained.

The aliphatic epoxy compound (A3) is a compound having at least two epoxy groups and not having an aromatic ring and an alicyclic epoxy group. Polyfunctional epoxy compounds such as ether compounds and polyglycidyl esters of aliphatic long-chain polybasic acids are included. Representative compounds include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, and dipentaerythritol. hexaglycidyl ether, diglycidyl ether of polyethylene glycol, glycidyl ether of polyhydric alcohol such as diglycidyl ether of polypropylene glycol; aliphatic polyhydric alcohol such as propylene glycol, trimethylolpropane, glycerin; Polyglycidyl ethers of polyether polyols obtained by addition of oxides, diglycidyl esters of aliphatic long-chain dibasic acids, epoxidized soybean oil, epoxidized polybutadiene and the like can be mentioned.

Aliphatic epoxy compounds (A3) can also be used commercially available products, for example, Denacol EX-810, Denacol EX-861, Denacol EX-211, Denacol EX-252, Denacol EX-614, Denacol EX-313, Denacol EX-512, Denacol EX-321 (manufactured by Nagase ChemteX), Adeka Resin EP-4088S, Adeka Glycirolle ED-503G, Adeka Glycirol ED-506, Adeka Glycirol ED-523T, Adeka Glycirol ED-505, (ADEKA ), Epolite 40E, Epolite 70P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF, Epolite 4000 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

In the present invention, the polymerizable composition containing 10 parts by mass or more and less than 50 parts by mass of the aliphatic epoxy compound (A3) in 100 parts by mass of the cationically polymerizable compound (A) has a low viscosity and excellent handling properties. preferable. The content of the aliphatic epoxy compound (A3) is more preferably 15 parts by mass or more and 30 parts by mass or less in order to achieve both low viscosity and heat resistance.

The cationically polymerizable compound (A) preferably contains an oxetane compound (A4) since a polymerizable composition having good curability can be obtained.

The oxetane compound (A4) is a compound having at least one oxetanyl group and no epoxy group. Examples of compounds having one oxetanyl group include 3-ethyl-3-(hydroxymethyl)oxetane, 3 -ethyl-3-(methoxymethyl)oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(cyclohexyloxymethyl) ) oxetane, 3-ethyl-3-(4-hydroxybutyroxymethyl)oxetane and the like, and compounds having two oxetanyl groups include, 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-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, 3-ethyl-3-( 3-ethyl-3-oxetanylmethyloxymethyl)oxetane, xylylenebisoxetane and the like.

As the oxetane compound (A4), a commercially available product can also be used. Ethanacol OXBP, OXTP (manufactured by Ube Industries, Ltd.) and the like can be mentioned.

In the present invention, a polymerizable composition containing 1 part by mass or more and 30 parts by mass or less of the oxetane compound (A4) in 100 parts by mass of the cationically polymerizable compound (A) is preferable because of good curability. The content of the oxetane compound (A4) is more preferably 15 parts by mass or more and 25 parts by mass or less for compatibility of curability, adhesiveness and heat resistance.

The cationic polymerizable compound (A) may contain an aromatic epoxy compound (A5).
The aromatic epoxy compound (A5) is a compound other than the epoxy polymer (A1) having an aromatic ring and at least two epoxy groups, such as bisphenol A, bisphenol F, or a compound obtained by further adding an alkylene oxide thereto. Glycidyl etherified products; Glycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, and catechol; Aromatic compounds having two or more alcoholic hydroxyl groups, such as benzenedimethanol, benzenediethanol, and benzenedibutanol polyglycidyl etherified compounds; glycidyl esters of polybasic aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid, and trimellitic acid;

Commercially available aromatic epoxy compounds (A5) can also be used, such as Denacol EX-201 (manufactured by Nagase ChemteX Corporation), Ogusol PG-100, Ogusol EG-200, Ogsol EG-280, and Ogsol CG-500 ( Osaka Gas Chemicals), Epiclon 830, Epiclon 840 (manufactured by DIC), ADEKA RESIN EP-4100, ADEKA RESIN EP-4900 (manufactured by ADEKA), YX-4000 (manufactured by Mitsubishi Chemical), and the like.

The cationically polymerizable compound (A) preferably contains an alicyclic epoxy compound (A6) because it has a low viscosity, is easy to handle, and provides a polymerizable composition with good curability.

The alicyclic epoxy compound (A6) is a compound having a cycloalkene oxide structure and no aromatic ring.
A cycloalkene oxide structure is a cyclic structure in which an aliphatic ring and an epoxy ring are combined, such as a cyclohexene oxide structure or a cyclopentene oxide structure obtained by epoxidizing a cyclohexene ring-containing compound or a cyclopentene ring-containing compound with an oxidizing agent. It is a structure that shares parts.

Among alicyclic epoxy compounds, compounds having one cycloalkene oxide structure include, for example, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentadiene diepoxide, and epoxyhexahydrophthalate. dioctyl acid, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane and the like.

A commercially available product can be used as the alicyclic epoxy compound (A6), and examples thereof include Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxide 3000 (manufactured by Daicel) and LDO (manufactured by Symrise).

In the present invention, the polymerizable composition containing 0.5 parts by mass or more and 15 parts by mass or less of the alicyclic epoxy compound (A6) in 100 parts by mass of the cationically polymerizable compound (A) has a low viscosity and is easy to handle. and is preferred because of good curability. The content of the alicyclic epoxy compound (A6) is preferably 1 part by mass or more and 10 parts by mass or less for compatibility of curability, adhesiveness and heat resistance.

The polymerizable composition of the present invention contains a photocationic polymerization initiator (B).
The photocationic polymerization initiator (B) may be any compound as long as it can release a substance that initiates cationic polymerization upon irradiation with light. A double salt, which is a salt, or a derivative thereof is preferable because a polymerizable composition having excellent curability can be obtained.

Examples of double salts that are onium salts or derivatives thereof include salts of cations and anions 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, for example, by the following general formula.
[(R ²¹ ) _x Q] ^m+ (ii)
In general formula (ii) above, R ²¹ represents an organic group having 1 to 60 carbon atoms and optionally containing any number of atoms other than carbon atoms.
x represents an integer of 1 to 5;
Each of x R ²¹ is independent and may be the same or different.
At least one of x R ²¹ represents the above organic group having an aromatic ring.
Q represents an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F and N=N. Further, when the valence of Q in the cation [A] ^m+ is q, it is necessary that the relationship m=x−q holds true. However, N=N is treated as valence 0.

Further, 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 above general formula (iii), L represents a metal or metalloid that is the central atom of the halide complex, 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 to 7; Further, when the valence of L in the anion [B] ^m− is p, it is necessary that the relationship m=y−p holds true.

Specific examples of the anion [LX _y ] ^m- of the general formula (iii) include tetrakis(pentafluorophenyl)borate [(C ₆ F ₅ ) ₄ B] ⁻ , tetrafluoroborate (BF ₄ ) ⁻ , hexa fluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , hexafluoroarsenate (AsF ₆ ) ⁻ , hexachloroantimonate (SbCl ₆ ) ⁻ , tris(pentafluoromethyl)trifluorophosphate ion (FAP anion ) and the like.

Also, 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.
Other anions include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethylsulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , toluenesulfonate anion, trinitrobenzene sulfonic acid anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis(pentafluorophenyl)borate and the like.

In the present invention, among such onium salts, in order to obtain a polymerizable composition with more excellent curability, a sulfonium cation such as a triphenylsulfonium cation represented by Group I or Group II below, and hexafluorophosphate , hexafluoroantimonate, tetrakis(pentafluorophenyl)borate and other anions are preferred.

In the present invention, a composition containing 1 part by mass or more and 20 parts by mass or less of the photocationic polymerization initiator (B) with respect to 100 parts by mass of the cationic polymerizable compound (A) is preferable because of its good curability. The content of the photo cationic polymerization initiator (B) is more preferably 2 parts by mass or more and 10 parts by mass or less for both curability and heat resistance.

Photocationic polymerization initiator (B) can be a commercially available product, for example, Kayarad PCI-220, Kayarad PCI-620 (manufactured by Nippon Kayaku), UVI-6990 (manufactured by Dow Chemical), Adeka Adeka Arcles SP-150, Adeka Optomer SP-170 (manufactured by ADEKA), CI-5102, CIT-1370, CIT-1682, CIP-1866S, CIP-2048S, CIP-2064S (manufactured by Nippon Soda), 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 (manufactured by Midori Chemical), PI-2074 (manufactured by Rhodia), CPI-100P (manufactured by Sun-Apro) and the like.

A solvent capable of dissolving or dispersing each component can be used in the polymerizable composition of the present invention. A solvent is a compound that is liquid at 25° C. and 1 atm without being classified into the components described above. 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; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1 , 2-diethoxyethane, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether and other ether solvents; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, succinic acid Ester solvents such as dimethyl and texanol; Cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol and amyl alcohol ; Ether esters such as 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 Solvents; BTX solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; Paraffinic solvents such as 310 (Cosmo Matsuyama Oil Co., Ltd.) and Solvesso #100 (Exxon Chemical Co., Ltd.); halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, trichlorethylene, methylene chloride, and 1,2-dichloroethane solvent; halogenated aromatic hydrocarbon solvent such as chlorobenzene; propylene carbonate, carbitol solvent, 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 as a mixed solvent of two or more.

The polymerizable composition of the present invention may optionally contain other monomers, other polymerization initiators, inorganic fillers, organic fillers, pigments, colorants such as dyes, photosensitizers, antifoaming agents, thickeners, Various resins such as surfactants, leveling agents, flame retardants, thixotropic agents, diluents, plasticizers, stabilizers, polymerization inhibitors, UV absorbers, antioxidants, antistatic agents, flow control agents, adhesion promoters, etc. Additives and the like can be added.
However, it is preferable that the polymerizable composition of the present invention does not contain a radically polymerizable compound and a radical polymerization initiator because the adhesiveness becomes poor.

The content of the solvent in the polymerizable composition of the present invention is preferably 50 parts by mass or less, preferably 30 parts by mass or less, and particularly preferably 10 parts by mass or less with respect to 100 parts by mass of the polymerizable composition. When the content of the solvent is within the above range, it is preferable because damage to the substrate is small.

In the polymerizable composition of the present invention, the total amount of optional components other than the cationic polymerizable compound (A) and the photocationic polymerization initiator (B) depends on the application of the present invention, etc., but the effect of the present invention is further enhanced. From the viewpoint of enhancement, it is preferably 20 parts by mass or less with respect to 100 parts by mass of the cationically polymerizable compound (A), and in order to achieve both performance improvement by adding optional components and the characteristics of the present invention, it is 10 parts by mass or less. is particularly preferred.

Specific uses of the polymerizable composition of the present invention include optical materials such as spectacles and imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, adhesives, printing plates, and insulating varnishes. , insulating sheets, laminates, printed circuit boards, sealants and molding materials for semiconductor devices, LED packages, liquid crystal inlets, organic EL, optical elements, electrical insulation, electronic parts, separation films, etc. , Putty, Glass fiber impregnating agent, Sealing agent, Passivation film for semiconductors and solar cells, Interlayer insulating film, Protective film, Prism lens sheet used for backlight of liquid crystal display device, Screen for projection TV, etc. Lens parts of lens sheets such as Fresnel lens sheets and lenticular lens sheets, or backlights using such sheets, optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, and optical molding Casting agents and the like can be mentioned, and examples of substrates that can be applied as coating agents include metals, wood, rubber, plastics, glass, ceramic products, and the like.
In particular, the polymerizable composition of the present invention is useful as an adhesive because it has a low viscosity and gives a cured product with excellent moist heat resistance and adhesive strength.

EXAMPLES The present invention will be described in more detail below with reference to Examples, etc., but the present invention is not limited to these Examples.

[Examples 1 to 18, Comparative Examples 1 to 7]
A polymerizable composition was prepared by mixing each component according to the formulation shown in Tables 1 to 3, and evaluated for viscosity, optical properties, initial adhesiveness, adhesiveness, resistance to moist heat and heat resistance. The evaluation results are shown in Tables 1-3.
Each component in the table is as follows.

<Evaluation method>
(viscosity)
The viscosity μ immediately after production of the polymerizable compositions obtained in Examples and Comparative Examples was measured using a viscometer (cone-plate viscometer (TVE-22L manufactured by Toki Sangyo Co., Ltd.)) under an atmosphere of 25°C. , was evaluated according to the following criteria. The lower the viscosity, the better the handleability, so it is preferable.
S: μ≦35 mPa·s
A: 35 mPa s < μ ≤ 60 mPa s
B: 60 mPa s < μ ≤ 150 mPa s
C: 150mPa s<μ

(optical properties)
Each of the polymerizable compositions obtained in Examples and Comparative ^Examples was applied to a glass plate to a thickness of 50 μm, and another glass plate was attached. C. for 1 hour to obtain a test piece. The b* of the obtained test piece was measured using an ultraviolet-visible-near-infrared spectrophotometer V-670 (manufactured by JASCO Corporation) and evaluated according to the following criteria. The smaller the b* value, the better the optical properties, so it is preferable.
A: b*≤5
B: 5<b*≦10 or less C: 10<b*

(initial adhesiveness)
A test piece obtained in the same manner as the test piece used for evaluating optical properties was allowed to stand for 3 minutes under conditions of 30°C, 50% RH, and atmospheric pressure, and then cut into a width of 2.0 cm. A sample for evaluation was obtained. A 90° peel test was performed using this evaluation sample, and evaluation was made according to the following criteria. The higher the initial adhesiveness, the better the curability, so it is preferable.
S: 2.5 N/2 cm or more or substrate breakage A: 1.5 N/2 cm or more and less than 2.5 N/2 cm B: 0.5 N/2 cm or more and less than 1.5 N/2 cm C: less than 0.5 N/2 cm

(Adhesiveness)
A test piece obtained in the same manner as the test piece used for evaluating optical properties was allowed to stand for 12 hours under conditions of 30°C, 50% RH, and atmospheric pressure, and then cut into a width of 2.0 cm for evaluation. samples were obtained. A 90° peel test was performed using this evaluation sample, and evaluation was made according to the following criteria. The higher the adhesiveness, the better it is as an adhesive, so it is preferable.
S: 2.5 N/2 cm or more or substrate breakage A: 1.5 N/2 cm or more and less than 2.5 N/2 cm B: 0.5 N/2 cm or more and less than 1.5 N/2 cm C: less than 0.5 N/2 cm

(Damp heat resistance)
A test piece obtained in the same manner as the test piece used to evaluate the optical properties was allowed to stand for 500 hours under conditions of 85°C, 85% Rh, and atmospheric pressure, and then the test piece was cut into a width of 2.0 cm for evaluation. samples were obtained. A 90° peel test was performed using this evaluation sample, and evaluation was made according to the following criteria. The higher the adhesiveness, the better the moist heat resistance, so it is preferable, and it can be judged that the wet heat resistance is particularly excellent if it is S to A.
S: 1.5 N/2 cm or more A: 1.0 N/2 cm or more and less than 1.5 N/2 cm B: 0.5 N/2 cm or more and less than 1.0 N/2 cm C: less than 0.5 N/2 cm

(Heat-resistant)
For the test piece obtained in the same manner as the test piece used for evaluating optical properties, b* was measured using an ultraviolet-visible-near-infrared spectrophotometer V-670 (manufactured by JASCO Corporation). After leaving for 500 hours under the conditions of 200° C., 85% Rh and atmospheric pressure, b* was measured again to calculate the difference Δb* from the initial b*, and evaluated according to the following criteria. The smaller Δb* is, the better the heat resistance is, so it is preferable.
S: Δb*<3
A: 3 ≤ Δb * < 5
B: 5≤Δb*<8
C: 8≤Δb*

As shown in Tables 1 to 3, the polymerizable composition of the present invention has low viscosity, excellent handleability, and excellent curability. Moreover, the cured product of the polymerizable composition of the present invention is particularly useful as an adhesive because it has excellent adhesive strength, moist heat resistance and heat resistance.

Claims (13)

A polymerizable composition containing a cationic polymerizable compound (A) and a photocationic polymerization initiator (B),
A polymerizable composition in which the cationic polymerizable compound (A) contains an epoxy polymer (A1) and a monofunctional epoxy compound (A2). 2. The polymerizable composition according to claim 1, wherein the epoxy polymer (A1) is a polymer having a structural unit represented by general formula (I) below.

In the formula, Ar represents a benzene ring or a naphthalene ring,
R ¹ is a halogen atom, a hydroxyl group, a nitro group, a cyano group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted carbon atom number of 2 to 10 a heterocyclic group, an optionally substituted heterocyclic ring-containing group having 3 to 30 carbon atoms, or one or more of the methylene groups in the hydrocarbon group having 1 to 20 carbon atoms is the following <group A>, or one or more of the methylene groups in the heterocyclic ring-containing group having 3 to 30 carbon atoms is substituted by a divalent group selected from the following <Group A> represents a substituted group,
Y ¹ , Y ² and Y ³ are each independently a divalent optionally substituted hydrocarbon group having 1 to 20 carbon atoms or methylene in the hydrocarbon group having 1 to 20 carbon atoms one or more of the groups is a group substituted with a divalent group selected from the following <group A>,
a represents an integer from 0 to 4,
b represents an integer from 0 to 4,
c represents an integer from 0 to 4,
a+b is 1-4 and a+b+c is 1-4.
<Group A>: -O-, -CO-, -COO-, -OCO-, -NR ¹¹ -, -NR ¹² CO-, -S-
R ¹¹ and R ¹² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 3. The polymerizable composition according to claim 2, wherein Y ¹ is an optionally substituted arylene group having 6 to 20 carbon atoms. The polymerizable composition according to any one of claims 1 to 3, wherein the cationic polymerizable compound (A) contains an aliphatic epoxy compound (A3). The polymerizable composition according to any one of claims 1 to 4, wherein the cationic polymerizable compound (A) contains an oxetane compound (A4). The polymerizable composition according to any one of claims 1 to 5, wherein the cationic polymerizable compound (A) contains an alicyclic epoxy compound (A6). The epoxy equivalent of the epoxy polymer (A1) is 180 g/eq. 350 g/eq. The polymerizable composition according to any one of claims 1 to 6, which is less than The epoxy equivalent of the monofunctional epoxy compound (A2) is 150 g/eq. 500 g/eq. The polymerizable composition according to any one of claims 1 to 7, which is less than The polymerizable composition according to any one of claims 1 to 8, wherein the content of the epoxy polymer (A1) is 5 parts by mass or more and less than 50 parts by mass in 100 parts by mass of the cationically polymerizable compound (A). The polymerization according to any one of claims 1 to 9, wherein the content of the monofunctional epoxy compound (A2) is 0.5 parts by mass or more and less than 50 parts by mass in 100 parts by mass of the cationically polymerizable compound (A). sex composition. A photocurable adhesive containing the polymerizable composition according to any one of claims 1 to 10. A method for producing a cured product, comprising a step of irradiating the polymerizable composition according to any one of claims 1 to 10 with an active energy ray or a step of heating. A cured product of the polymerizable composition according to any one of claims 1 to 10.