JP7755938B2 - polymerizable composition - Google Patents

Description

The present invention relates to a polymerizable composition, a cured product of the polymerizable composition, a method for producing the cured product, and a curable adhesive.

Cationically polymerizable compositions are used in fields such as inks, paints, various coatings, adhesives, and optical components.

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

JP 2011-236389 A Japanese Patent Application Laid-Open No. 2012-149262 International Publication No. 2008/111584

However, the cured products of the polymerizable compositions described in Patent Documents 1 to 3 did not have sufficient moist heat resistance.

Therefore, an object of the present invention is to provide a polymerizable composition that can produce a cured product with excellent moist heat resistance.

The inventors of the present invention have conducted extensive research to solve the above problems and have completed the present invention.
That is, the present invention provides a polymerizable composition containing a phosphorus-based antioxidant (A), a cationically polymerizable compound (B), and a cationic polymerization initiator (C).

The present invention also provides a photocurable adhesive containing the polymerizable composition.
The present invention also provides a method for producing a cured product, which comprises a step of irradiating the polymerizable composition with active energy rays or a step of heating the polymerizable composition.
The present invention further provides a cured product of the polymerizable composition.

The polymerizable composition of the present invention makes it possible to produce a cured product with excellent resistance to moist heat.

The polymerizable composition of the present invention will be described in detail below.
The polymerizable composition of the present invention contains a phosphorus-based antioxidant (A), a cationic polymerizable compound (B), and a cationic polymerization initiator (C). By combining the phosphorus-based antioxidant (A), the cationic polymerizable compound (B), and the cationic polymerization initiator (C), the cured product of the polymerizable composition exhibits excellent moist heat resistance. Furthermore, the cured product also exhibits excellent heat resistance, adhesiveness, and optical properties.
An antioxidant is a compound that prevents components contained in a polymerizable composition from being oxidized in the presence of oxygen. A phosphorus-based antioxidant is an antioxidant that contains a phosphorus atom in the molecule.

In the present invention, any known phosphorus-based antioxidant can be used without any particular restrictions as the phosphorus-based antioxidant (A). The phosphorus-based antioxidant (A) preferably has 1 to 4 phosphorus atoms in the molecule, and more preferably has 1 or 2 phosphorus atoms, because this further improves the moist heat resistance of the cured product of the polymerizable composition, and also improves the heat resistance, adhesiveness, and optical properties of the cured product.
From the same viewpoint, the phosphorus-based antioxidant (A) preferably has at least one oxygen atom in the molecule, more preferably 2 to 10 oxygen atoms, and even more preferably 3 to 6 oxygen atoms, so that the cured product of the polymerizable composition has better moist heat resistance and also has better heat resistance, adhesiveness, and optical properties.

In the present invention, it is preferable that the phosphorus-based antioxidant (A) contains a group represented by the following general formula (I), as this will further improve the moist heat resistance of the cured product of the polymerizable composition, and will also improve the heat resistance, adhesiveness, and optical properties of the cured product.

(In the formula, * represents a bond.)

In the present invention, the phosphorus-based antioxidant (A) preferably has a group represented by the following general formula (II), since this further improves the moist heat resistance of the cured product of the polymerizable composition, and also improves the heat resistance, adhesiveness, and optical properties of the cured product.

(In the formula, R ¹ and R ² each independently represent a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent,
a represents an integer of 0 to 5;
* represents a bond,
When a is an integer of 2 or more, the groups bonded to the multiple bonds * may be the same or different.
Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by ^R1 and ^R2 (also referred to as ^R1 , etc.) in general formula (II) include an aliphatic hydrocarbon group having 1 to 30 carbon atoms and an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms. In the present invention, the hydrocarbon group preferably has 1 to 20 carbon atoms, since this further improves the moist heat resistance of the cured product of the polymerizable composition and also improves the heat resistance, adhesiveness, and optical properties of the cured product.

Examples of the aliphatic hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ and R ² include an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms.

The alkyl group having 1 to 30 carbon atoms, represented by ^R1 or the like, may be linear or branched. Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl groups. Examples of the branched alkyl group include groups in which one or more of the linear alkyl groups mentioned above have been substituted with alkyl groups having 1 to 4 carbon atoms, and specific examples thereof include 1,3-dimethylbutyl, 1-isopropylpropyl, 1,2-dimethylbutyl, 2-heptyl, 1,4-dimethylpentyl, tert-heptyl, 2-methyl-1-isopropylpropyl, 1-ethyl-3-methylbutyl, isooctyl, tert-octyl, 2-ethylhexyl, 2-methylhexyl, 2-propylhexyl, isononyl, isodecyl, isoundecyl, and isododecyl groups. Examples of the alkyl group having 1 to 4 carbon atoms include alkyl groups having 1 to 30 carbon atoms represented by ^R1 , and having 1 to 4 carbon atoms.
In the present invention, since the cured product of the polymerizable composition has better moist heat resistance and also has good heat resistance, adhesiveness, and optical properties, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 4 to 20, even more preferably 7 to 17, and still more preferably 9 to 15. From the same viewpoint, the alkyl group is preferably linear.

Examples of the cycloalkyl group having 3 to 30 carbon atoms, represented by ^R1 or the like, include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclooctadecyl group, a 2-bornyl group, a 2-isobornyl group, a 1-adamantyl group, etc. In the present invention, the number of carbon atoms in the alkyl group is preferably 3 to 20, since this further improves the moist heat resistance of the cured product of the polymerizable composition and also improves the heat resistance, adhesiveness, and optical properties of the cured product.

In the present invention, the term "aromatic hydrocarbon ring-containing group" refers to a group having an aromatic hydrocarbon ring. In the present invention, aromatic hydrocarbon ring-containing groups substituted with an alkyl group having 1 to 20 carbon atoms, preferably 5 to 14 carbon atoms, are also encompassed in the aromatic hydrocarbon ring-containing group. Examples of the alkyl group having 1 to 20 carbon atoms that substitutes the aromatic hydrocarbon ring-containing group include alkyl groups having 1 to 30 carbon atoms, represented by ^R1 , that have 1 to 20 carbon atoms.
The aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms, represented by ^R1 or the like, may have a monocyclic structure or a polycyclic structure. The aromatic hydrocarbon ring-containing group having a polycyclic structure may have a fused ring structure or may have two aromatic hydrocarbon rings linked together.
The aromatic hydrocarbon ring-containing group in which two aromatic hydrocarbon rings are linked may be one in which two aromatic hydrocarbon rings of a monocyclic structure are linked, one in which an aromatic hydrocarbon ring of a monocyclic structure and an aromatic hydrocarbon ring of a fused ring structure are linked, or one in which an aromatic hydrocarbon ring of a fused ring structure and an aromatic hydrocarbon ring of a fused ring structure are linked.
The linking group linking two aromatic hydrocarbon rings may be any group that can impart aromaticity to the aromatic hydrocarbon ring-containing group as a whole, and examples thereof include a single bond, a sulfide group (—S—), and a carbonyl group.
Examples of the aromatic hydrocarbon ring having a monocyclic structure include benzene, toluene, ethylbenzene, and 2,4,6-trimethylbenzene.
Examples of the aromatic hydrocarbon ring having a fused 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 aromatic hydrocarbon rings with a monocyclic structure are linked, such as diphenyl sulfide and benzoylphenyl.
In the present invention, the aromatic hydrocarbon ring preferably has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, because this leads to better moist heat resistance of the cured product of the polymerizable composition, and also leads to better heat resistance, adhesiveness, and optical properties of the cured product.

Substituents of the aliphatic hydrocarbon group having 1 to 30 carbon atoms and the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms represented by ^R1 and the like include ethylenically unsaturated groups such as vinyl, allyl, acryl, 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, oxaloyl, stearoyl, and the like. acyl groups such as acetyloxy and benzoyloxy; acyl groups such as amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino, 2- Examples of substituted amino groups include 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, and phenylsulfonylamino; 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, phosphate group, and salts of a carboxyl group, sulfo group, phosphonic acid group, or phosphate group.

In the present invention, it is preferable that R 1 and R ² in general formula (II) are aromatic hydrocarbon ring-containing groups having 6 to 30 carbon atoms which may have a substituent, because this leads to further improved moist heat resistance of the ^cured product of the polymerizable composition, and also leads to improved heat resistance, adhesiveness, and optical properties of the cured product.
When R ¹ and R ² are aromatic hydrocarbon ring-containing groups of 6 to 30 carbon atoms which may have a substituent, the moist heat resistance of the cured product of the polymerizable composition will be even better, and the heat resistance, adhesiveness, and optical properties of the cured product will also be good. Therefore, the hydrocarbon group is preferably an aromatic hydrocarbon ring-containing group of 6 to 30 carbon atoms which has a substituent, more preferably an aromatic hydrocarbon ring-containing group of a monocyclic structure having 7 to 30 carbon atoms and substituted with at least one alkyl group having 1 to 20 carbon atoms, and even more preferably an aromatic hydrocarbon ring-containing group of a monocyclic structure having 7 to 30 carbon atoms and substituted with an alkyl group having 1 to 20 carbon atoms at least at the para-position relative to the bonding position of -O-.
Furthermore, when ^R1 and ^R2 are aromatic hydrocarbon ring-containing groups of 6 to 30 carbon atoms which may have a substituent, the cured product of the polymerizable composition will have better moist heat resistance, and the cured product will also have good heat resistance, adhesion, and optical properties, so a is preferably 1. When a is 1, the cured product of the polymerizable composition will have better moist heat resistance, and the cured product will also have good heat resistance, adhesion, and optical properties, so the group bonded to the bond is preferably an aromatic hydrocarbon ring-containing group of 6 to 30 carbon atoms which may have a substituent, more preferably an aromatic hydrocarbon ring-containing group of 6 to 30 carbon atoms which has a substituent, even more preferably an aromatic hydrocarbon ring-containing group of 7 to 20 carbon atoms and having a monocyclic structure substituted with at least one alkyl group of 1 to 20 carbon atoms, and most preferably an aromatic hydrocarbon ring-containing group of 7 to 20 carbon atoms and having a monocyclic structure substituted with an alkyl group of 1 to 20 carbon atoms at least at the para-position relative to the bonding position of the bond. From the same viewpoint, it is preferable that the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms is directly bonded to the benzene ring in general formula (II). Examples of the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms bonded to the bond and the alkyl group having 1 to 20 carbon atoms substituting the aromatic hydrocarbon ring-containing group include the same as those described for the group represented by ^R1 etc.

In the present invention, it is preferred that R 1 and R ² in general formula (II) are optionally substituted aliphatic hydrocarbon groups having 1 to 30 carbon atoms, and a is ^1, because this will result in a cured product of the polymerizable composition having better moist heat resistance and also having better heat resistance, adhesiveness, and optical properties.
When ^R1 and ^R2 are an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, the cured product of the polymerizable composition will have better moist heat resistance, and the cured product will also have better heat resistance, adhesiveness, and optical properties. Therefore, the aliphatic hydrocarbon group is preferably an alkyl group having 7 to 17 carbon atoms which may have a substituent, and more preferably an alkyl group having 9 to 15 carbon atoms which has no substituent.
When a is 1, the moist heat resistance of the cured product of the polymerizable composition is further improved, and the heat resistance, adhesiveness, and optical properties of the cured product are also improved, so it is preferable that the group bonded to the benzene ring in general formula (II) is also represented by general formula (II). From the same viewpoint, it is preferable that the groups represented by general formula (II) are directly bonded to each other.

The number of carbon atoms in a group defined in this invention includes the number of carbon atoms in the substituent. For example, a methylphenyl group is an aromatic hydrocarbon ring-containing group having 7 carbon atoms.

In the present invention, the phosphorus-based antioxidant (A) preferably has a plurality of groups represented by general formula (I) or general formula (II) in its molecule, more preferably 2 to 6 groups, even more preferably 2 to 4 groups, and most preferably 2 groups, in order to further improve the moist heat resistance of the cured product of the polymerizable composition, and also to improve the heat resistance, adhesiveness, and optical properties of the cured product.

In the present invention, the molecular weight of the phosphorus-based antioxidant (A) is preferably 200 to 2,000, more preferably 400 to 1,800, and particularly preferably 600 to 1,500, because this further improves the moist heat resistance of the cured product of the polymerizable composition, and also improves the heat resistance, adhesiveness, and optical properties of the cured product.

In the present invention, it is preferable that the phosphorus-based antioxidant (A) be liquid at 25°C and 1 atmosphere, as this improves the handleability of the polymerizable composition.

In the present invention, the P equivalent of the phosphorus-based antioxidant (A) is preferably 250 to 1000 g/eq., more preferably 300 to 900 g/eq., and particularly preferably 400 to 900 g/eq., because this further improves the moist heat resistance of the cured product of the polymerizable composition and also improves the heat resistance, adhesiveness, and optical properties of the cured product.
The P equivalent of the phosphorus-based antioxidant (A) can be calculated by the following formula.

<P equivalent> = {molecular weight of phosphorus-based antioxidant (A)} / {number of phosphorus atoms contained in phosphorus-based antioxidant (A)}

Specific examples of compounds having a group represented by general formula (I) or a group represented by general formula (II) include the following. These compounds may be used alone or in combination of two or more.

In the present invention, commercially available products may be used as the phosphorus-based antioxidant (A). Examples of commercially available phosphorus-based antioxidants (A) include Irgafos 168 and Irgafos 168FF manufactured by BASF Japan Ltd.; and Adekastab 2112, Adekastab 1178, Adekastab 1500, Adekastab 3010, Adekastab TPP, Adekastab PEP-36, Adekastab HP-10, Adekastab PEP-8, Adekastab C, and Adekastab 135A manufactured by ADEKA Corporation.

In the present invention, the above phosphorus-based antioxidants may be used alone or in combination of two or more.
The content of the phosphorus-based antioxidant (A) in the polymerizable composition of the present invention is preferably 0.1 part by mass or more and less than 10 parts by mass, more preferably 0.2 part by mass or more and less than 5 parts by mass, and even more preferably more than 0.2 part by mass and less than 3 parts by mass, relative to 100 parts by mass of the cationically polymerizable compound (B) described below, in order to further improve the moist heat resistance of a cured product of the polymerizable composition and to improve the heat resistance, adhesiveness, and optical properties of the cured product.

Next, the cationically polymerizable compound (B) contained in the polymerizable composition of the present invention will be described.
In the present invention, the cationically polymerizable compound (B) means a compound that undergoes a polymerizing or crosslinking reaction in the presence of a cationic polymerization initiator activated by light irradiation or heat.

In the present invention, any known cationically polymerizable compound can be used as the cationically polymerizable compound (B) without any particular restrictions. Examples of the cationically polymerizable compound (B) include epoxy compounds and oxetane compounds (B4). The cationically polymerizable compound (B) preferably contains at least one selected from the group consisting of alicyclic epoxy compounds (B1), aliphatic epoxy compounds (B2), and aromatic epoxy compounds (B3), as this further improves the moist heat resistance of the polymerizable composition and also improves the heat resistance and adhesiveness of the cured product.

In the present invention, the cationically polymerizable compound (B) preferably contains an alicyclic epoxy compound (B1) because the cationically polymerizable compound (B) provides good curability of the polymerizable composition. The alicyclic epoxy compound is a compound having a cycloalkene oxide structure and no aromatic ring.
The cycloalkene oxide structure is a structure in which an aliphatic ring and an epoxy ring share a part of the ring structure, such as a cyclohexene oxide structure or a cyclopentene oxide structure, which is 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 cycloalkene oxide structure per molecule, or two or more cycloalkene oxide structures. It is preferable that the alicyclic epoxy compound (B1) have one or two cycloalkene oxide structures per molecule, as this will further improve the moist heat resistance of the cured product of the polymerizable composition, and will also improve the heat resistance, adhesiveness, and optical properties of the cured product.

Examples of alicyclic epoxy compounds having one cycloalkene oxide structure include 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentadiene diepoxide, dioctyl epoxyhexahydrophthalate, 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, and ethylene bis(3,4-epoxycyclohexanecarboxylate).

Commercially available products can be used as the alicyclic epoxy compound (B1). Specific examples of commercially available products include Celloxide 2021P, Celloxide 2081, Celloxide 2000, and Celloxide 3000 (manufactured by Daicel Corporation), and LDO (manufactured by Symrise Co., Ltd.).

In the present invention, the above-mentioned alicyclic epoxy compounds (B1) may be used alone or in combination of two or more.
The content of the alicyclic epoxy compound (B1) in the cationically polymerizable compound (B) is preferably 1 to 20 parts by mass, and more preferably 2 to 10 parts by mass, of the alicyclic epoxy compound (B1) per 100 parts by mass of the cationically polymerizable compound (B), because this further improves the moist heat resistance of a cured product of the polymerizable composition and also improves the heat resistance and adhesiveness of the cured product.

In the present invention, the cationically polymerizable compound (B) preferably contains an aliphatic epoxy compound (B2), since this results in a polymerizable composition with low viscosity and excellent handleability.

The aliphatic epoxy compound (B2) is a compound having one or more epoxy groups and not having an aromatic ring or a 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 alkylcarboxylic 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 bifunctional, since this results in a polymerizable composition with low viscosity and excellent handleability.

Representative examples of aliphatic epoxy compounds (B2) include glycidyl ethers of polyhydric alcohols such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, and diglycidyl ether of polypropylene glycol; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, and glycerin; and diglycidyl esters of aliphatic long-chain dibasic acids. Further examples include monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized soybean oil, and epoxidized polybutadiene.

Commercially available aliphatic epoxy compounds (B2) can be used. Examples of commercially available aliphatic epoxy compounds (B2) include Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, and Denacol EX-5. 12, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Examples of suitable glycerols include Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, and Denacol EX-931 (manufactured by Nagase ChemteX Corporation); Epolight M-1230, Epolight 40E, Epolight 100E, Epolight 200E, Epolight 400E, Epolight 70P, Epolight 200P, Epolight 400P, Epolight 1500NP, Epolight 1600, Epolight 80MF, and Epolight 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Adekaglycirol ED-503, Adekaglycirol ED-503G, Adekaglycirol ED-506, and Adekaglycirol ED-523T (manufactured by ADEKA Corporation), and Epogose 2EH (manufactured by Yokkaichi Chemical Co., Ltd.).

In the present invention, the above-mentioned aliphatic epoxy compounds (B2) may be used alone or in combination of two or more.
The content of the aliphatic epoxy compound (B2) in the cationically polymerizable compound (B) is preferably 5 to 50 parts by mass, more preferably 10 to 45 parts by mass, and even more preferably 20 to 40 parts by mass of the aliphatic epoxy compound (B2) per 100 parts by mass of the cationically polymerizable compound (B), because this further improves the moist heat resistance of a cured product of the polymerizable composition and also improves the heat resistance and adhesiveness of the cured product.

In the present invention, the cationically polymerizable compound (B) preferably contains an aromatic epoxy compound (B3) because the cured product of the polymerizable composition has good heat resistance.
The aromatic epoxy compound (B3) is a compound having an aromatic ring and at least one epoxy group. The aromatic epoxy compound (B3) may be monofunctional or polyfunctional. In the present invention, the aromatic epoxy compound (B3) preferably contains at least a monofunctional aromatic epoxy compound or a bifunctional aromatic epoxy compound, since this further improves the compatibility and adhesiveness of the polymerizable composition.

Examples of monofunctional aromatic epoxy compounds include glycidyl ethers of monohydric phenols having one aromatic ring, such as phenol, cresol, and butylphenol, or compounds obtained by further adding alkylene oxide to these phenols.
Examples of polyfunctional aromatic epoxy compounds include glycidyl ethers of bisphenol A, bisphenol F, or compounds obtained by further 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 ethers of aromatic compounds having two or more alcoholic hydroxyl groups, such as benzenedimethanol, benzenediethanol, and benzenedibutanol; and 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 (B3) can be used. Specific examples of commercially available aromatic epoxy compounds (B3) include Denacol EX-121, Denacol EX-141, Denacol EX-142, Denacol EX-145, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, Oncoat EX-1020, Oncoat EX-1030, and Oncoat EX-10. 40, Oncoat EX-1050, Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, Oncoat 1012 (manufactured by Nagase ChemteX Corporation); Oxol PG-100, Oxol EG-200, Oxol EG-210, Oxol EG-250 (manufactured by Osaka Gas Chemicals Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC Corporation); ESN-475V (manufactured by Nippon Steel Corporation) Sumikin Chemical & Material Co., Ltd.); Epicoat YX8800 (Mitsubishi Chemical Corporation); Marproof G-0105SA, Marproof G-0130SP (NOF Corporation); Epicron N-665, Epicron HP-7200 (DIC Corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, EPPN-501H, EPPN-501HY, EP Examples include PN-502H, NC-2000-L, NC-3000, and NC-7000L (manufactured by Nippon Kayaku Co., Ltd.); ADEKA GLYCIROL ED-501, ADEKA GLYCIROL ED-502, ADEKA GLYCIROL ED-509, ADEKA GLYCIROL ED-529, ADEKA RESIN EP-4000, ADEKA RESIN EP-4005, ADEKA RESIN EP-4100E, and ADEKA RESIN EP-4901 (manufactured by ADEKA Corporation); TECHMORE VG-3101L, EPOX-MKR710, and EPOX-MKR151 (manufactured by Printec Co., Ltd.), and YX-4000 (manufactured by Mitsubishi Chemical Corporation).

In the present invention, the above-mentioned aromatic epoxy compounds (B3) may be used alone or in combination of two or more.
The content of the aromatic epoxy compound (B3) in the cationically polymerizable compound (B) is preferably 20 to 60 parts by mass, and more preferably 30 to 50 parts by mass, of the aromatic epoxy compound (B3) per 100 parts by mass of the cationically polymerizable compound (B), because this further improves the moist heat resistance of a cured product of the polymerizable composition and also improves the heat resistance and adhesiveness of the cured product.

In the present invention, the cationically polymerizable compound (B) preferably contains an alicyclic epoxy compound (B1), an aliphatic epoxy compound (B2), and an aromatic epoxy compound (B3), because this leads to further improved moist heat resistance of a cured product of the polymerizable composition and improved heat resistance and adhesiveness of the cured product.
The total amount of the alicyclic epoxy compound (B1), the aliphatic epoxy compound (B2), and the aromatic epoxy compound (B3) per 100 parts by mass of the cationically polymerizable compound (B) is preferably from 50 parts by mass to 100 parts by mass, more preferably from 60 parts by mass to 95 parts by mass, and particularly preferably from 80 parts by mass to 90 parts by mass, because this further improves the moist heat resistance of the cured product of the polymerizable composition and also improves the heat resistance and adhesiveness of the cured product.

The cationically polymerizable compound (B) preferably contains an oxetane compound (B4) because this improves the moist heat resistance of the cured product of the polymerizable composition.
The oxetane compound (B4) is a compound having 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, since this further improves the moist heat resistance of the cured product of the polymerizable composition.

Examples of oxetane 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, and 3-ethyl-3-(4-hydroxybutyloxymethyl)oxetane.

Examples of oxetane compounds having two oxetanyl groups include 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, and ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether. Examples include 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, and xylylene bisoxetane.

Commercially available oxetane compounds (B4) can also be used. Examples of commercially available oxetane compounds include Aron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, and OXT-212 (manufactured by Toagosei Co., Ltd.), and Ethanacol OXBP and OXTP (manufactured by Ube Industries, Ltd.).

In the present invention, the above-mentioned oxetane compounds (B4) may be used singly or in combination of two or more.
The content of the oxetane compound (B4) in the cationically polymerizable compound (B) is preferably 1 to 30 parts by mass, more preferably 5 to 25 parts by mass, of the oxetane compound (B4) per 100 parts by mass of the cationically polymerizable compound (B), because this further improves the moist heat resistance of a cured product of the polymerizable composition and also improves the heat resistance and adhesiveness of the cured product.

The content of the cationically polymerizable compound (B) in the polymerizable composition of the present invention is preferably 50 parts by mass or more but less than 99 parts by mass, more preferably 75 parts by mass or more but less than 99 parts by mass, and even more preferably 85 parts by mass or more but less than 99 parts by mass, per 100 parts by mass of the solids content of the polymerizable composition, in order to further improve the moist heat resistance of the cured product of the polymerizable composition and to improve the heat resistance, adhesiveness, and optical properties of the cured product. The above solids content refers to the polymerizable composition excluding the solvent, which will be described later.

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 capable of releasing a substance that initiates cationic polymerization when irradiated with light or heated.
In the present invention, a photocationic polymerization initiator or a thermal cationic polymerization initiator can be used as the cationic polymerization initiator (C). In the present invention, it is preferable to use a photocationic polymerization initiator as the cationic polymerization initiator (C) because it has little cure shrinkage and excellent adhesiveness.

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

Examples of double salts that are onium salts or derivatives thereof include salts of a cation and anion represented by the following general formula (i).
[A] ^m+ [B] ^m- (i)

Here, the cation [A] ^m+ is an onium, and its structure can be represented, for example, by the following general formula:
[(R ¹¹⁰ ) _x Q] ^m+ (ii)
In the general formula (ii), R ¹¹⁰ represents an organic group having 1 to 60 carbon atoms and may contain any number of atoms other than carbon atoms.
x represents an integer of 1 to 5;
x R ^110s are each independently the same or different;
At least one of the x R ¹¹⁰ represents the 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. In addition, when the valence of Q in the cation [A] ^m+ is q, the relationship m=x-q must be established. However, N=N is treated as having a valence of 0.

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

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 ) ⁻ , hexafluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ^{− , hexafluoroarsenate (AsF 6 ) −} _{, hexachloroantimonate (SbCl 6} ⁾ ₋ ^, and tris(pentafluoromethyl)trifluorophosphate ion (FAP anion).

The anion [B] ^m− may also 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, trinitrobenzenesulfonate anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctane sulfonate, tetraarylborate, and tetrakis(pentafluorophenyl)borate.

Among these onium salts, sulfonium salts of a sulfonium cation such as the triphenylsulfonium cation represented by Group I or Group II below and an anion such as hexafluorophosphate, hexafluoroantimonate, or tetrakis(pentafluorophenyl)borate are preferred in the present invention, as they provide good curability for the polymerizable composition and good adhesion for the cured product of the polymerizable composition.

Commercially available cationic photopolymerization initiators can also be used. Examples of commercially available cationic photopolymerization initiators include "Kayarad (registered trademark) PCI-220" and "Kayarad (registered trademark) PCI-620" manufactured by Nippon Kayaku Co., Ltd.; "UVI-6990" manufactured by The Dow Chemical Company; "ADEKA ARCLES (registered trademark) SP-150," "ADEKA OPTOMER (registered trademark) SP-170," and "ADEKA OPTOMER (registered trademark) SP-500" manufactured by ADEKA Corporation; and "CI-5102," "CIT-1370," "CIT-1682," "CIP-1866S," "CIP-2048S," and "CIP-2" manufactured by Nippon Soda Co., Ltd. 064S"; "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 Co., Ltd.; "PI-2074" manufactured by Solvay Japan Co., Ltd.; and CPI-100P manufactured by San-Apro Ltd.

The content of the cationic photopolymerization initiator in the polymerizable composition of the present invention is preferably 0.1 to 15 parts by mass, more preferably 1 to 13 parts by mass, and even more preferably 3 to 13 parts by mass of the cationic photopolymerization initiator (C) per 100 parts by mass of the cationic polymerizable compound, since this improves the adhesiveness of the cured product of the polymerizable composition and the curability of the polymerizable composition.

In the present invention, any compound that generates a cationic species or a Lewis acid upon heating can be used as the thermal cationic polymerization initiator, without particular limitation. Specific examples include salts such as sulfonium salts, thiophenium salts, thioranium salts, benzylammonium salts, pyridinium salts, and hydrazinium salts; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, and isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; polyepoxy addition-modified products produced by reacting the above-mentioned polyamines with various epoxy resins such as glycidyl ethers (e.g., phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, and bisphenol F-diglycidyl ether) or glycidyl esters of carboxylic acids in a conventional manner; amidation-modified products produced by reacting the above-mentioned organic polyamines with carboxylic acids (e.g., phthalic acid, isophthalic acid, and dimer acid) in a conventional manner; and aldehydes such as formaldehyde. Mannich modified products produced by reacting phenols having at least one aldehyde reactive site on the nucleus, such as phenol, cresol, xylenol, tertiary butylphenol, and resorcinol, in a conventional manner; polycarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dicarboxylic acid, 2-methyloctanedioic ... Examples of acid anhydrides that can be used include aliphatic dicarboxylic acids such as methyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, and dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; tricarboxylic acids such as trimellitic acid, trimesic acid, and trimer of castor oil fatty acid; and tetracarboxylic acids such as pyromellitic acid; dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, and amine imides.

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 more preferably 0.1 to 8 parts by mass, per 100 parts by mass of the cationically polymerizable compound (B), since this improves the curability of the polymerizable composition.

Commercially available thermal cationic polymerization initiators can also be used. Examples of commercially available thermal cationic polymerization initiators include Adekaopton CP-77 and Adekaopton CP-66 (manufactured by ADEKA Corporation), CI-2639 and CI-2624 (Nippon Soda Co., Ltd.), and San-Aid SI-60, San-Aid SI-80, and San-Aid SI-100 (manufactured by Sanshin Chemical Industry Co., Ltd.).

The polymerizable composition of the present invention preferably contains a phenolic antioxidant, as this improves the heat resistance of the cured product of the polymerizable composition. A phenolic antioxidant is an antioxidant having at least one phenol structure.

In the present invention, any known phenolic antioxidant can be used without particular limitation. It is preferable to use a hindered phenolic antioxidant as the phenolic antioxidant, as this improves the heat resistance of the cured product of the polymerizable composition.

Hindered phenol antioxidants are antioxidants that contain at least one phenol structure, and have a structure in which at least one of the 2- and 6-positions of the hydroxyl group of the phenol structure is substituted with a substituent having 4 or more carbon atoms. Specific examples of hindered phenol antioxidants include dibutylhydroxytoluene (BHT), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 2,4,6-tris(4-hydroxy-3,5-di-tert-butylbenzyl)mesitylene, 6-(4-hydroxy-3,5-di-tert-butylanilino)-2,4-bis(octylthio)-1,3,5-tris ... riazine, 2,2'-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,2-bis[3-(4-hydroxy-3,5-di-tert-butylphenyl)propionyl]hydrazine, octyl 3-(4-hydroxy-3,5-diisopropylphenyl)propionate, 4,6-bis(octylthiomethyl)-o-cresol, N,N'-hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide], 1,6-hexanediol bis[3-(3 ,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1-dimethyl-2-[(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl-2,4,8,10-tetraoxaspiro[5.5]undecane, bis(3-tert-butyl-4-hydroxy-5-methylbenzenepropanoic acid)ethylenebis(oxyethylene), 1,3,5-tris[[4-(1,1-dimethylethyl)-3-hydroxy-2,6-dimethylphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H ,5H)-trione, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 6,6'-thiobis(2-tert-butyl-4-methylphenol), 3,5-di-tert-butyl-4-hydroxybenzyl diethyl phosphonate, 2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl acrylate, 4,4'-thiobis(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol, etc. In addition, oligomeric or polymeric compounds having a hindered phenol structure may also be used as hindered phenol antioxidants.

Commercially available phenolic antioxidants can also be used. Commercially available phenolic antioxidants include, for example, Irganox 1010, Irganox 1076, Irganox 3114, Irganox 1330, Irganox 565, Irganox 1035, Irganox MD1024, Irganox 1135, Irganox 1520L, Irganox 1098, Irganox 259, Irganox 245, Irganox 1790, Irganox 1081, and Irgamod 195, all manufactured by BASF Japan Ltd.; Sumilizer MDP-S, Sumilizer GM, and Sumilizer WX-R, all manufactured by Sumitomo Chemical Co., Ltd.; and Adekastab AO-60, Adekastab AO-50, Adekastab AO-80, and Adekastab AO-40, all manufactured by ADEKA Corporation.

In the present invention, the above-mentioned phenolic antioxidants may be used alone or in combination of two or more.
The content of the phenolic antioxidant in the polymerizable composition of the present invention is preferably 0.01 part by mass or more and 10 parts by mass or less, more preferably 0.1 part by mass or more but less than 5 parts by mass, and even more preferably 0.5 parts by mass or more and 3 parts by mass or less, relative to 100 parts by mass of the cationically polymerizable compound (B), in order to improve the heat resistance of a cured product of the polymerizable composition.

The polymerizable composition of the present invention may contain a solvent capable of dissolving or dispersing the phosphorus-based antioxidant (A), the cationic polymerizable compound (B), and the cationic polymerization initiator (C). The solvent is a compound that is liquid at 25°C and 1 atmosphere and is not classified as one of the above-mentioned components. Examples of the solvent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether 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 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; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, and propylene glycol-1-monomethyl ether-2-acetate (PGMEA). ether ester solvents such as dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethoxyethyl propionate; 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; paraffin solvents such as mineral spirits, Swazol #310 (Cosmo Matsuyama Oil Co., Ltd.), and Solvesso #100 (Exxon Chemical Co., Ltd.); carbon tetrachloride halogenated aliphatic hydrocarbon solvents such as chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; propylene carbonate, carbitol-based solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and water; and these solvents can also be used as a mixed solvent of two or more of them.

The polymerizable composition of the present invention combines a phosphorus-based antioxidant (A) with a cationic polymerizable compound (B) and a cationic polymerization initiator (C). Combining a phosphorus-based antioxidant (A) with a radically polymerizable composition and a radical polymerization initiator does not achieve the effect of the present invention of producing a cured product with good moist heat resistance. Furthermore, a cured product of a polymerizable composition containing a radically polymerizable composition and a radical polymerization initiator will have poor adhesion. Therefore, it is preferable that the polymerizable composition of the present invention does not contain a radically polymerizable composition or a radical polymerization initiator.

Radically polymerizable compositions are compounds capable of radical polymerization. Examples of radically polymerizable compounds include compounds having an ethylenically unsaturated group such as an acrylic group, a methacrylic group, or a vinyl group. Specific examples include the radically polymerizable compounds described in WO 2018/012383 and the radically polymerizable organic substances described in WO 2014/021023.

A radical polymerization initiator is a compound that generates radicals that can initiate polymerization when exposed to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams, or X-rays, or when heated. Specific examples include photoradical polymerization initiators such as acetophenone-based compounds, benzyl-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and oxime ester-based compounds, as described in International Publication No. 2018/012383, thermal radical polymerization initiators such as azo-based compounds, peroxides, and persulfates, and the photoradical polymerization initiators described in Japanese Patent Application Laid-Open No. 2016-210849.

The polymerizable composition of the present invention can optionally contain various resin additives, such as other monomers, other polymerization initiators, inorganic fillers, organic fillers, colorants such as pigments and dyes, photosensitizers, antifoaming agents, thickeners, surfactants, leveling agents, flame retardants, thixotropic agents, diluents, plasticizers, stabilizers, polymerization inhibitors, UV absorbers, antioxidants, antistatic agents, flow control agents, and adhesion promoters.

The total amount of optional components other than the phosphorus-based antioxidant (A), the cationically polymerizable compound (B), and the cationic polymerization initiator (C) in the polymerizable composition of the present invention will vary depending on the application of the present invention, but from the perspective of further enhancing the effects of the present invention, it is preferably 20 parts by mass or less, and particularly 10 parts by mass or less, per 100 parts by mass of the cationically polymerizable compound (A).

Specific applications of the polymerizable composition of the present invention include optical materials such as eyeglasses and imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, adhesives, printing plates, insulating varnishes, insulating sheets, laminates, printed circuit boards, sealants for semiconductor devices, LED packages, liquid crystal injection ports, organic EL devices, optical elements, electrical insulation, electronic components, and separation membranes, etc., molding materials, putties, glass fiber impregnating agents, fillers, passivation films for semiconductors, solar ponds, etc., interlayer insulating films, protective films, lens portions of lens sheets such as prism lens sheets used in the backlights of liquid crystal display devices, Fresnel lens sheets used in screens of projection televisions, etc., and lenticular lens sheets, or backlights using such sheets, optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, and casting agents for optical shaping. For example, substrates to which the polymerizable composition of the present invention can be applied as a coating agent include metal, wood, rubber, plastic, glass, and ceramic products.
The polymerizable composition of the present invention uses a combination of a phosphorus-based antioxidant (A), a cationic polymerizable compound (B), and a cationic polymerization initiator (C), thereby providing a cured product with excellent moist heat resistance and adhesive properties. Furthermore, the polymerizable composition of the present invention also has excellent adhesive properties and optical properties due to the use of these components in combination. Therefore, the polymerizable composition of the present invention is particularly useful as an adhesive.

The photocurable adhesive of the present invention contains the polymerizable composition of the present invention. Because the photocurable adhesive of the present invention contains the polymerizable composition of the present invention, it has excellent moist heat resistance. In addition, the photocurable adhesive of the present invention also has excellent heat resistance, adhesion, 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 by heating the polymerizable composition. The conditions for irradiating the active energy rays and the heating conditions are not limited, and known conditions can be used.

Next, a method for producing the cured product of the present invention will be described.
The method for producing a cured product of the present invention includes a step of irradiating the polymerizable composition of the present invention with active energy rays or a step of heating the composition. The conditions for irradiation with active energy rays and heating are not limited, and known conditions can be used.

The present invention will be further explained in detail below based on examples, but the present invention is not limited to these examples.

[Examples and Comparative Examples]
Polymerizable compositions 1 to 18 of Examples 1 to 18 and polymerizable compositions of Comparative Examples 1 and 2 were prepared by thoroughly mixing the components according to the formulations shown in Tables 1 and 2 below. The symbols in the tables represent the following components. The numerical values in the tables represent parts by mass.

Component A: Phosphorus-based antioxidant A-1: Compound represented by the following formula (A-1) A-2: Compound represented by the following formula (A-2)

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

Component B: Cationic polymerizable compound 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): B4-1: Compound represented by the following formula (B4-1): B4-2: Compound represented by the following formula (B4-2):

B': Radical polymerizable compound B'-1: Compound represented by the following formula (B'-1) B'-2: Compound represented by the following formula (B'-2) B'-3: Compound represented by the following formula (B'-3)

Component C: Cationic polymerization initiator C-1: 50% by mass solution of a compound represented by the following formula (C1-2) in propylene carbonate C-2: 50% by mass solution of a compound represented by the following formula (C2) in propylene carbonate

Component C': Radical polymerization initiator C'-1: Compound represented by the following formula (C'-1)

The moist heat resistance, heat resistance, adhesiveness, and optical properties of the cured products of the polymerizable compositions prepared in the Examples and Comparative Examples were evaluated using the methods described below. The results are shown in Tables 1 and 2.

<Adhesion test>
The compositions prepared in the Examples and Comparative Examples were each applied to a TAC film (FUJITAC TD80 manufactured by FUJIFILM Corporation) so that the film thickness after curing was 3 μm, forming a coating film. Next, a corona discharge-treated COP (cycloolefin polymer, manufactured by ZEON Corporation: Zeonorfilm 14-060) film was bonded to the surface of the TAC film on which the coating film had been formed using a laminator to obtain a laminate. Then, using an electrodeless ultraviolet lamp, light equivalent to 1000 mJ/ ^cm2 was irradiated through the COP film to the laminate, and a test specimen was produced by bonding.
The obtained test piece was stored under conditions of 30°C, 50% RH, and atmospheric pressure for 12 hours after exposure. Next, a 2.0 cm wide piece was cut out from the test piece to obtain an evaluation sample. The obtained sample was subjected to a 90° peel test, and the adhesiveness of the evaluation sample was evaluated according to the following criteria. The 90° peel test was performed under conditions of 30°C, 50% RH, and atmospheric pressure. The larger the value of N/2cm, the better the adhesiveness.

A: 2.5 N/2 cm or more or substrate destruction B: 1.5 N/2 cm or more but less than 2.5 N/2 cm C: 0.5 N/2 cm or more but less than 1.5 N/2 cm D: Less than 0.5 N/2 cm.

<Moisture and heat resistance test>
Test pieces were obtained in the same manner as in the adhesiveness test. The obtained test pieces were kept in an environment of 85°C and 85% RH for 500 hours. After that, the test pieces were cooled to room temperature, and then a 90° peel test was performed on the test pieces in the same manner as in the adhesiveness test, and the moist heat resistance of the evaluation sample was evaluated according to the following criteria. The larger the value of N/2cm, the better the moist heat resistance.

A: 1.5N/2cm or more B: 1.0N/2cm or more but less than 1.5N/2cm C: 0.5N/2cm or more but less than 1.0N/2cm D: Less than 0.5N/2cm

<Optical property test>
Each of the polymerizable compositions prepared in Examples and Comparative Examples was applied to a glass plate so that the film thickness after curing was 50 μm. Then, another glass plate was laminated to the surface of the glass plate on which the coating film had been formed. The laminated glass plate was irradiated with energy of 1000 mJ/ ^cm2 using a high-pressure Hg lamp, and then the glass plate was heated at 150°C for 1 hour to obtain a test piece.
The b* of the obtained test piece was measured using an ultraviolet-visible-near-infrared spectrophotometer V-670 (manufactured by JASCO Corporation), and the optical properties of the test piece were evaluated according to the following criteria. The smaller the b* value, the more excellent the optical properties.

A: b* of the cured product is less than 5. B: b* of the cured product is 5 or more but less than 10. C: b* of the cured product is 10 or more.

<Heat resistance test>
Test pieces were obtained in the same manner as in the optical property test. The b* of the obtained test pieces was measured using an ultraviolet-visible-near-infrared spectrophotometer V-670 (manufactured by JASCO Corporation). Next, the test pieces were kept in an environment of 85°C and 85% RH for 500 hours, and then the b* of the test pieces was measured. The heat resistance of the test pieces was then evaluated according to the following criteria. The smaller the Δb*, the more excellent the heat resistance.

A: Δb*<3
B: 3≦Δb*<5
C: 5≦Δb*<8
D: 8≦Δb*

As is clear from Tables 1 and 2, the cured products of the polymerizable compositions of Examples 1 to 17 exhibited excellent moist heat resistance. These cured products also exhibited excellent heat resistance, adhesion, and optical properties. In contrast, the cured product of the polymerizable composition of Comparative Example 1, which did not contain the phosphorus-based antioxidant (A), exhibited poor moist heat resistance and heat resistance. Furthermore, the cured product of the polymerizable composition of Comparative Example 2, which contained another component (A'-1) instead of the phosphorus-based antioxidant (A), exhibited poor adhesion and optical properties in addition to poor moist heat resistance and heat resistance. Furthermore, the cured products of the polymerizable compositions of Comparative Examples 3 and 4, which used a radically polymerizable compound and a radical initiator instead of the cationic polymerizable compound (B) and cationic polymerization initiator (C), exhibited poor adhesion as well as poor moist heat resistance.

Claims (8)

The composition contains a phosphorus-based antioxidant (A), a cationic polymerizable compound (B), and a cationic polymerization initiator (C),
The phosphorus-based antioxidant (A) has a plurality of groups represented by the following general formula (II):
A polymerizable composition comprising 1 to 13 parts by mass of a cationic polymerization initiator (C) relative to 100 parts by mass of a cationic polymerizable compound (B) .
(In the formula, R ¹ and R ² each independently represent a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent,
a represents an integer of 0 to 5;
* represents a bond,
When a is an integer of 2 or more, the groups bonded to the multiple bonds * may be the same or different. The polymerizable composition according to claim 1, wherein the phosphorus-based antioxidant (A) has 2 to 6 groups represented by general formula (II) in the molecule. The polymerizable composition according to claim 1 or 2, comprising 0.1 parts by mass or more and less than 10 parts by mass of a phosphorus-based antioxidant (A) per 100 parts by mass of the cationically polymerizable compound (B). The polymerizable composition according to any one of claims 1 to 3, wherein the cationically polymerizable compound (B) contains at least one selected from the group consisting of an alicyclic epoxy compound (B1), an aliphatic epoxy compound (B2), and an aromatic epoxy compound (B3). The polymerizable composition according to any one of claims 1 to 4, wherein the cationically polymerizable compound (B) contains an oxetane compound (B4). A photocurable adhesive containing the polymerizable composition described in any one of claims 1 to 5. A method for producing a cured product, comprising the steps of irradiating the polymerizable composition according to any one of claims 1 to 5 with active energy rays or heating the composition. A cured product of the polymerizable composition described in any one of claims 1 to 5.