CN116745337A - Polymerizable composition, photocurable adhesive, method for producing cured product, and cured product - Google Patents

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

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CN116745337A
CN116745337A CN202280012229.XA CN202280012229A CN116745337A CN 116745337 A CN116745337 A CN 116745337A CN 202280012229 A CN202280012229 A CN 202280012229A CN 116745337 A CN116745337 A CN 116745337A
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carbon atoms
polymerizable composition
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井上尭大
板野和幸
松土和彦
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Adeka Corp
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/223—Di-epoxy compounds together with monoepoxy compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds

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  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

The invention provides a polymerizable composition which can produce a cured product having excellent moist heat resistance. The present invention provides a polymerizable composition containing a thioether compound (A), a cationically polymerizable compound (B) and a cationic polymerization initiator (C). The thioether compound (A) preferably has an ester bond in the molecule. The polymerizable composition preferably contains 0.1 part by mass or more and less than 10 parts by mass of the thioether compound (a) per 100 parts by mass of the cationically polymerizable compound (B).

Description

Polymerizable composition, photocurable adhesive, method for producing cured product, and cured product
Technical Field
The present invention relates to a polymerizable composition and a cured product of the polymerizable composition.
Background
The cationically polymerizable composition is used in the fields of inks, paints, various coating agents, adhesives, optical members, and the like.
For example, patent documents 1 to 3 below disclose cationic polymerizable compositions used as various photocurable adhesives.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2011-236389
Patent document 2: japanese patent application laid-open No. 2012-149762
Patent document 3: international publication No. 2008/111584
Disclosure of Invention
Problems to be solved by the invention
However, the cured products of the polymerizable compositions described in patent documents 1 to 3 are insufficient in wet heat resistance.
Accordingly, an object of the present invention is to provide a polymerizable composition capable of producing a cured product excellent in moist heat resistance.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above-described problems, and as a result, have completed the present invention.
Specifically, the present invention provides a polymerizable composition containing a thioether compound (A), a cationically polymerizable compound (B) and a cationic polymerization initiator (C).
The present invention also provides a photocurable adhesive comprising the above-mentioned polymerizable composition.
The present invention also provides a method for producing a cured product, which comprises a step of irradiating the polymerizable composition with an active energy ray or a step of heating the polymerizable composition.
The present invention also provides a cured product of the polymerizable composition.
The present invention further provides the use of the above polymerizable composition as a photocurable adhesive.
Effects of the invention
The polymerizable composition of the present invention can produce a cured product having excellent moist heat resistance.
Detailed Description
The polymerizable composition of the present invention will be described in detail below.
The polymerizable composition of the present invention contains a thioether compound (A). By containing the thioether compound (a), the cured product of the polymerizable composition is excellent in wet heat resistance. Further, the cured product is excellent in heat resistance, adhesion and optical properties.
The thioether compound (a) is a compound having a thioether bond in the molecule. In the present invention, as the thioether compound (a), a known thioether compound may be used without particular limitation. In the present invention, it is preferable to use a thioether compound having an ester bond in the molecule, from the viewpoint that the wet heat resistance of the cured product of the polymerizable composition is further improved and the heat resistance and adhesion of the cured product are also improved.
As the thioether compound having an ester bond in the molecule, for example, a compound having a group represented by the following general formula (I) is preferable because the wet heat resistance of a cured product of the polymerizable composition becomes further good and the heat resistance and adhesion of the cured product also become good.
[ chemical formula 1]
(wherein R is 1 The aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent, and 1 or more methylene groups in the aliphatic hydrocarbon group having 1 to 30 carbon atoms are selected from the group consisting of <Group A>The group obtained by substitution of the 2-valent group, or 1 or more methylene groups in the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms are selected from the group consisting of<Group A>A group obtained by substitution of a 2-valent group in (a) is,
Y 1 represents a substituent-containing 2-valent hydrocarbon group having 1 to 30 carbon atoms or 1 or more methylene groups in the 2-valent hydrocarbon group having 1 to 30 carbon atoms, and is selected from the group consisting of<Group A>A group obtained by substitution of a 2-valent group in (a) is,
* Indicating the bonding site.
<Group A>：-O-、-CO-、-COO-、-OCO-、-NR 2 -、-NR 3 CO-or-S-
R 2 R is R 3 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. )
R as in the general formula (I) 1 Examples of the aliphatic hydrocarbon group having 1 to 30 carbon atoms include an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, and a cycloalkyl group having 3 to 30 carbon atoms.
R 1 The alkyl group having 1 to 30 carbon atoms may be linear or branched. Examples of the linear alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl groups. Examples of the branched alkyl group include those obtained by substituting 1 or 2 of the above-mentioned linear alkyl groups with an alkyl group having 1 to 9 carbon atoms, and specific examples thereof include 1, 3-dimethylbutyl, 1-isopropyl propyl, 1, 2-dimethylbutyl, 2-heptyl, 1, 4-dimethylpentyl, tert-heptyl, 2-methyl-1-isopropyl propyl, 1-ethyl-3-methylbutyl, isooctyl, tert-octyl, 2-ethylhexyl, 2-methylhexyl, 2-propylhexyl, isononyl, isodecyl, isoundecyl, and isododecyl. Examples of the alkyl group having 1 to 9 carbon atoms include R 1 The alkyl group having 1 to 9 carbon atoms out of the alkyl groups having 1 to 30 carbon atoms shown.
In the present invention, the number of carbon atoms of the alkyl group is preferably 5 to 23, more preferably 5 to 20, even more preferably 7 to 17, even more preferably 9 to 15, from the viewpoint that the wet heat resistance of the cured product of the polymerizable composition becomes further good and the heat resistance, adhesion and optical properties of the cured product become also good. From the same point of view, the alkyl group is preferably linear.
As R 1 Examples of the alkenyl group having 2 to 30 carbon atoms include vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl and triacontenyl, and the corresponding alkadienyl and trienyl groups.
As R 1 Examples of the alkynyl group having 2 to 30 carbon atoms include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-octynyl group, a 1-decynyl group, and a 1-octadecylynyl group.
As R 1 Examples of the cycloalkyl group having 3 to 30 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclooctadecyl, 2-bornyl, 2-isobornyl, and 1-adamantyl.
The aromatic hydrocarbon ring-containing group in the present invention means a group having an aromatic hydrocarbon ring.
R 1 The group containing an aromatic hydrocarbon ring having 6 to 30 carbon atoms may have a monocyclic structure or a polycyclic structure. The aromatic hydrocarbon ring-containing group having a polycyclic structure may have a condensed ring structure, or may be a group obtained by connecting 2 aromatic hydrocarbon rings.
The aromatic hydrocarbon ring-containing group obtained by linking 2 aromatic hydrocarbon rings may be a group obtained by linking 2 aromatic hydrocarbon rings having a single ring structure, a group obtained by linking an aromatic hydrocarbon ring having a single ring structure and an aromatic hydrocarbon ring having a condensed ring structure, or a group obtained by linking 2 aromatic hydrocarbon rings having a condensed ring structure.
The linking group linking 2 aromatic hydrocarbon rings may be any linking group that can be set to have an aromatic character as a whole of the group containing an aromatic hydrocarbon ring, and examples thereof include a single bond, a thio group (-S-) and a carbonyl group.
Examples of the aromatic hydrocarbon ring having a monocyclic structure include benzene, toluene, ethylbenzene, 2,4, 6-trimethylbenzene, and the like.
Examples of the aromatic hydrocarbon ring having a condensed ring structure include naphthalene, anthracene, phenanthrene, pyrene, and the like.
Examples of the aromatic hydrocarbon ring-containing group obtained by linking 2 aromatic hydrocarbon rings include a group obtained by linking aromatic hydrocarbon rings having a monocyclic structure such as diphenyl sulfide and benzoylphenyl.
The number of carbon atoms of the aromatic hydrocarbon ring in the present invention is preferably 6 to 20, from the viewpoint that the wet heat resistance of the cured product of the polymerizable composition becomes further excellent. The number of carbon atoms of the aromatic hydrocarbon ring is more preferably 6 to 15, from the viewpoint that the heat resistance, adhesion and optical properties of the cured product are also good in addition to the moist heat resistance.
As Y 1 Examples of the "2-valent hydrocarbon group having 1 to 30 carbon atoms" represented by R 1 The aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent or the group having 6 to 30 carbon atoms which may have a substituent, is a 2-valent group obtained by removing 1 hydrogen atom from the group containing an aromatic hydrocarbon ring.
As R in group A 2 R is R 3 Examples of the hydrocarbon group having 1 to 30 carbon atoms include an aliphatic hydrocarbon group having 1 to 30 carbon atoms and an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms.
As R 2 R is R 3 The aliphatic hydrocarbon group having 1 to 30 carbon atoms represented by the formula (I) may be represented by the formula (II) and R 1 The same groups as the aliphatic hydrocarbon groups having 1 to 30 carbon atoms.
As R 2 R is R 3 The group containing an aromatic hydrocarbon ring having 6 to 30 carbon atoms represented by the formula (I) and (II) may be represented by R 1 The same groups as the groups containing an aromatic hydrocarbon ring having 6 to 30 carbon atoms are represented.
As R 1 The table ofAn aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms, and Y 1 The substituent of the 2-valent hydrocarbon group having 1 to 30 carbon atoms represented by the formula (I) may be an alkyl group having 1 to 8 carbon atoms; ethylenically unsaturated groups such as vinyl, allyl, acrylic, and methacrylic groups; halogen atoms such as fluorine, chlorine, bromine, and iodine; acyl groups such as acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyl, oxalyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, and carbamoyl; acyloxy groups such as acetoxy and benzoyloxy; substituted amino groups such as amino group, ethylamino group, dimethylamino group, diethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexyl amino group, dodecylamino group, anilino group, chlorophenyl amino group, toluylamino group, anisamino group, N-methyl-anilino group, diphenylamino group, naphthylamino group, 2-pyridylamino group, methoxycarbonylamino group, phenoxycarbonylamino group, acetylamino group, benzoylamino group, formylamino group, pivaloylamino group, lauroylamino group, carbamoylamino group, N-dimethylaminocarbonylamino group, N-diethylaminocarbonylamino group, morpholinocarbonylamino group, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, N-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group, phenoxycarbonylamino group, sulfamoylamino group, N-dimethylaminosulfonylamino group, methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group and the like; sulfonamide, sulfonyl, carboxyl, cyano, sulfo, hydroxyl, nitro, mercapto, imide, carbamoyl, sulfonamide, phosphonic, or salts of carboxyl, sulfo, phosphonic, and phosphonic groups, and the like. Examples of the alkyl group having 1 to 8 carbon atoms include R 1 The alkyl group having 1 to 8 carbon atoms out of the alkyl groups having 1 to 30 carbon atoms shown.
The number of carbon atoms of the group specified in the present invention includes the number of carbon atoms of the substituent. For example, methylphenyl is a group having an aromatic hydrocarbon ring having 7 carbon atoms.
In addition, the number of carbon atoms of a group in which 1 or more methylene groups specified in the present invention are substituted with a 2-valent group selected from the group < group a > includes the number of carbon atoms of a 2-valent group. For example, the number of carbon atoms of a group in which 1 methylene group in an alkyl group having 10 carbon atoms is substituted with-COO-is set to 10. The number of carbon atoms of the group in which 1 methylene group in the alkyl group having 10 carbon atoms was replaced with-O-was set to 9. The same applies to the number of carbon atoms of a group in which 1 or more methylene groups are substituted with a 2-valent group selected from the group consisting of < group A1>, < group B >, < group C >, < group D >, < group E >, < group F > and < group G >, which will be described later.
In the present invention, R in the general formula (I) is represented by the following formula (I) from the viewpoint of improving the adhesiveness and heat resistance of a cured product of the polymerizable composition 1 The aliphatic hydrocarbon group having 5 to 20 carbon atoms which may have a substituent or the group containing an aromatic hydrocarbon ring having 6 to 20 carbon atoms which may have a substituent is preferable, the aliphatic hydrocarbon group having 5 to 20 carbon atoms is more preferable, and the alkyl group having 5 to 20 carbon atoms is still more preferable. From the same viewpoint, the alkyl group having 5 to 20 carbon atoms is preferably linear. From the standpoint of compatibility, the alkyl group having 5 to 20 carbon atoms preferably has no substituent.
In the present invention, Y in the general formula (I) is selected from the group consisting of a cured product of the polymerizable composition having good adhesion and heat resistance 1 The substituted C1-10 hydrocarbon group is preferable, and the substituted C1-10 alkylene group or the substituted C1-10 arylene group is more preferable. From the same viewpoint, the alkylene group having 1 to 10 carbon atoms and the arylene group having 1 to 10 carbon atoms preferably have no substituent. Further, from the viewpoint of both heat resistance and compatibility of a cured product of the polymerizable composition, the number of carbon atoms of the alkylene group is preferably 1 to 8, more preferably 2 to 6. The alkylene group is preferably linear.
In the present invention, when the thioether compound has a group represented by the general formula (I) in the molecule, the number of the group represented by the general formula (I) in the compound may be 1 or more. The thioether compound preferably has a plurality of groups represented by the general formula (I) in the molecule, more preferably 2 to 8, still more preferably 2 to 6, particularly preferably 2 to 4, from the viewpoint of improving the adhesiveness and heat resistance of the cured product of the polymerizable composition.
In the present invention, as the thioether compound having a group represented by the general formula (I), for example, a compound represented by the following general formula (I-A) can be used.
[ chemical formula 2]
(wherein R is 1 The aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent, and 1 or more methylene groups in the aliphatic hydrocarbon group having 1 to 30 carbon atoms are selected from the group consisting of<Group A>The group obtained by substitution of the 2-valent group, or 1 or more methylene groups in the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms are selected from the group consisting of<Group A>A group obtained by substitution of a 2-valent group in (a) is,
Y 1 more than 1 methylene group in the substituent-capable 2-valent hydrocarbon group having 1 to 30 carbon atoms or the 2-valent hydrocarbon group having 1 to 30 carbon atoms is selected from the following<Group A>A group obtained by substitution of a 2-valent group in (a) is,
n represents an integer of 1 to 6,
d represents an n-valent group.
<Group A>：-O-、-CO-、-COO-、-OCO-、-NR 2 -、-NR 3 CO-or-S-
R 2 R is R 3 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. )
R in formula (I-A) 1 、R 2 、R 3 Y and Y 1 The groups represented by the general formula (I) are the same.
When n in the formula (I-A) is 1, examples of the 1-valent group represented by D include an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent, a group obtained by substituting 1 or more methylene groups in the aliphatic hydrocarbon group having 1 to 30 carbon atoms with a 2-valent group selected from the following < group B >, or a group obtained by substituting 1 or more methylene groups in the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms with a 2-valent group selected from the following < group B >.
<Group B>：-O-、-CO-、-COO-、-OCO-、-NR 20 -、-NR 30 CO-or-S-
R 20 R is R 30 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
Examples of the C1-30 aliphatic hydrocarbon group which may have a substituent(s) and the C6-30 aromatic hydrocarbon ring-containing group which may have a substituent(s) and which may have a 1-valence are the same as those described above for R 1 The aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent and the group having 6 to 30 carbon atoms which may have a substituent are the same groups as those of the group containing an aromatic hydrocarbon ring.
As a means of<Group B>R in (a) 20 R is R 30 Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by the formula (I) include those mentioned above as R 2 R is R 3 The same hydrocarbon group as the hydrocarbon group having 1 to 30 carbon atoms is represented.
When n in the formula (I-A) is 2, the group represented by the following formula (1) is exemplified as the 2-valent group represented by D.
[ chemical formula 3]
*-Z 1 -Y 10 -Z 2 -* (1)
(wherein Y is 10 Represents a single bond, -CO-, -NR 200 -, -S-, a 2-valent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, or 1 or more methylene groups in the 2-valent hydrocarbon group having 1 to 30 carbon atoms is selected from the group consisting of<Group C>A group obtained by substitution of a 2-valent group in (a) is,
R 200 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms,
Z 1 z is as follows 2 Each independently represents a group containing an aliphatic hydrocarbon group having 1 to 30 carbon atoms and optionally having a substituent, or an aromatic hydrocarbon ring having 6 to 30 carbon atoms and optionally having a substituent, which are directly bonded to each other,
* Indicating the bonding site.
<Group C>：-O-、-CO-、-COO-、-OCO-、-NR 21 -、-NR 31 CO-or-S-
R 21 R is R 31 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. )
As Y in formula (1) 10 Examples of the "2-valent hydrocarbon group having 1 to 30 carbon atoms" which may have a substituent(s) include those mentioned above and Y 1 The same hydrocarbon group as the 2-valent hydrocarbon group having 1 to 30 carbon atoms.
R as in formula (1) 200 、R 21 R is R 31 Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by the formula (I) include those mentioned above as R 2 R is R 3 The same hydrocarbon group as the hydrocarbon group having 1 to 30 carbon atoms is represented.
As Z in the formula (1) 1 Z is as follows 2 The aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent(s) and having a valence of 2 may be represented by R 1 A 2-valent group obtained by removing 1 hydrogen atom from the aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.
As Z in the formula (1) 1 Z is as follows 2 Examples of the "C6-30" C2 aromatic hydrocarbon ring-containing group which may have a substituent "include R 1 A 2-valent group obtained by removing 1 hydrogen atom from the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent.
When n in the formula (I-A) is 3, the 3-valent group represented by D may be a group represented by the following formula (2).
[ chemical formula 4]
(wherein Y is 11 Represents a substituent-containing 3-valent hydrocarbon group having 1 to 30 carbon atoms or 1 or more methylene groups in the 3-valent hydrocarbon group having 1 to 30 carbon atoms, and is selected from the group consisting of<Group D>A group obtained by substitution of a 2-valent group in (a) is,
Z 1 、Z 2 z is as follows 3 Each independently represents a group containing an aliphatic hydrocarbon group having 1 to 30 carbon atoms and optionally having a substituent, or an aromatic hydrocarbon ring having 6 to 30 carbon atoms and optionally having a substituent, which are directly bonded to each other,
* Indicating the bonding site.
<Group D>：-O-、-CO-、-COO-、-OCO-、-NR 22 -、-NR 32 CO-or-S-
R 22 R is R 32 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. )
As Y in formula (2) 11 Examples of the "3-valent hydrocarbon group having 1 to 30 carbon atoms" which may have a substituent(s) include those represented by Y 1 A 3-valent group obtained by further removing 1 hydrogen atom from the represented 2-valent hydrocarbon group having 1 to 30 carbon atoms.
R as in formula (2) 22 R is R 32 Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by the formula (I) include those mentioned above as R 2 R is R 3 The same hydrocarbon group as the hydrocarbon group having 1 to 30 carbon atoms is represented.
As Z in the formula (2) 1 、Z 2 Z is as follows 3 The aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent(s) represented by the formula (I) may be an aliphatic hydrocarbon group having 2 valences, such as R 1 A 2-valent group obtained by removing 1 hydrogen atom from the aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.
As Z in the formula (2) 1 、Z 2 Z is as follows 3 Examples of the "C6-30" C2 aromatic hydrocarbon ring-containing group which may have a substituent "include those represented by the above-mentioned R 1 The substituent-containing aromatic hydrocarbon ring group having 6 to 30 carbon atoms is obtained by removing 1 hydrogen atomA valence 2 group.
When n in the formula (I-A) is 4, the 4-valent group represented by D may be a group represented by the following formula (3).
[ chemical formula 5]
(wherein Y is 12 Represents a substituent-containing 4-valent hydrocarbon group having 1 to 30 carbon atoms or 1 or more methylene groups in the 4-valent hydrocarbon group having 1 to 30 carbon atoms, and is selected from the group consisting of<Group E>A group obtained by substitution of a 2-valent group in (a) is,
Z 1 、Z 2 、Z 3 z is as follows 4 Each independently represents a group containing an aliphatic hydrocarbon group having 1 to 30 carbon atoms and optionally having a substituent, or an aromatic hydrocarbon ring having 6 to 30 carbon atoms and optionally having a substituent, which are directly bonded to each other,
* Indicating the bonding site.
<Group E>：-O-、-CO-、-COO-、-OCO-、-NR 23 -、-NR 33 CO-or-S-
R 23 R is R 33 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. )
As Y in formula (3) 12 Examples of the "4-valent hydrocarbon group having 1 to 30 carbon atoms" which may have a substituent(s) include those represented by Y 1 A 4-valent group obtained by further removing 2 hydrogen atoms from the represented 2-valent hydrocarbon group having 1 to 30 carbon atoms.
R as formula (3) 23 R is R 33 Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by the formula (I) include those mentioned above as R 2 R is R 3 The same hydrocarbon group as the hydrocarbon group having 1 to 30 carbon atoms is represented.
As Z in the formula (3) 1 、Z 2 、Z 3 Z is as follows 4 The aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent(s) represented by the formula (I) may be an aliphatic hydrocarbon group having 2 valences, such as R 1 Represented number of carbon atoms which may have substituent(s)1 to 30, and a 2-valent group obtained by removing 1 hydrogen atom from an aliphatic hydrocarbon group.
As Z in the formula (3) 1 、Z 2 、Z 3 Z is as follows 4 Examples of the "C6-30" C2 aromatic hydrocarbon ring-containing group which may have a substituent "include those represented by the above-mentioned R 1 A 2-valent group obtained by removing 1 hydrogen atom from the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent.
When n in the formula (I-A) is 5, the group represented by the following formula (4) is exemplified as the 5-valent group represented by D.
[ chemical formula 6]
(wherein Y is 13 Represents a substituent-containing C1-30 hydrocarbon group or 1 or more methylene groups in the C1-30 hydrocarbon group, and is selected from the group consisting of<Group F>A group obtained by substitution of a 2-valent group in (a) is,
Z 1 、Z 2 、Z 3 、Z 4 z is as follows 5 Each independently represents a group containing an aliphatic hydrocarbon group having 1 to 30 carbon atoms and optionally having a substituent, or an aromatic hydrocarbon ring having 6 to 30 carbon atoms and optionally having a substituent, which are directly bonded to each other,
* Indicating the bonding site.
<Group F>：-O-、-CO-、-COO-、-OCO-、-NR 24 -、-NR 34 CO-or-S-
R 24 R is R 34 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. )
As Y in formula (4) 13 Examples of the "5-valent hydrocarbon group having 1 to 30 carbon atoms" which may have a substituent(s) include those represented by Y 1 A 5-valent group obtained by further removing 3 hydrogen atoms from the represented 2-valent hydrocarbon group having 1 to 30 carbon atoms.
R in formula (4) 24 R is R 34 Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by the formula (I) include those mentioned above as R 2 R is R 3 The same hydrocarbon group as the hydrocarbon group having 1 to 30 carbon atoms is represented.
As Z in the formula (4) 1 、Z 2 、Z 3 、Z 4 Z is as follows 5 The aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent(s) represented by the formula (I) may be an aliphatic hydrocarbon group having 2 valences, such as R 1 A 2-valent group obtained by removing 1 hydrogen atom from the aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.
As Z in the formula (4) 1 、Z 2 、Z 3 、Z 4 Z is as follows 5 Examples of the "C6-30" C2 aromatic hydrocarbon ring-containing group which may have a substituent "include those represented by the above-mentioned R 1 A 2-valent group obtained by removing 1 hydrogen atom from the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent.
When n in the formula (I-A) is 6, the 6-valent group represented by D may be a group represented by the following formula (5).
[ chemical formula 7]
(wherein Y is 14 Represents a substituent-containing 6-valent hydrocarbon group having 1 to 30 carbon atoms or 1 or more methylene groups in the 6-valent hydrocarbon group having 1 to 30 carbon atoms, and is selected from the group consisting of<Group G>A group obtained by substitution of a 2-valent group in (a) is,
Z 1 、Z 2 、Z 3 、Z 4 、Z 5 z is as follows 6 Each independently represents a group containing an aliphatic hydrocarbon group having 1 to 30 carbon atoms and optionally having a substituent, or an aromatic hydrocarbon ring having 6 to 30 carbon atoms and optionally having a substituent, which are directly bonded to each other,
* Indicating the bonding site.
<Group G>：-O-、-CO-、-COO-、-OCO-、-NR 25 -、-NR 35 CO-or-S-
R 25 R is R 35 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. )
As Y in formula (5) 14 Examples of the "6-valent hydrocarbon group having 1 to 30 carbon atoms" which may have a substituent(s) include those represented by Y 1 A 6-valent group obtained by further removing 4 hydrogen atoms from the represented 2-valent hydrocarbon group having 1 to 30 carbon atoms.
R in formula (5) 25 R is R 35 Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by the formula (I) include those mentioned above as R 2 R is R 3 The same hydrocarbon group as the hydrocarbon group having 1 to 30 carbon atoms is represented.
As Z in the formula (5) 1 、Z 2 、Z 3 、Z 4 、Z 5 Z is as follows 6 The aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent(s) represented by the formula (I) may be an aliphatic hydrocarbon group having 2 valences, such as R 1 A 2-valent group obtained by removing 1 hydrogen atom from the aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.
As Z in the formula (5) 1 、Z 2 、Z 3 、Z 4 、Z 5 Z is as follows 6 Examples of the "C6-30" C2 aromatic hydrocarbon ring-containing group which may have a substituent "include those represented by the above-mentioned R 1 A 2-valent group obtained by removing 1 hydrogen atom from the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent.
In the present invention, n in the formula (I-A) is preferably 1 to 6, more preferably 1 to 5, and even more preferably 1 to 4, from the viewpoint that the moisture-heat resistance of the cured product of the polymerizable composition becomes further good and the heat resistance, adhesion and optical characteristics of the cured product become also good.
When n in the formula (I-A) is 1, the 1-valent group represented by D is preferably an aliphatic hydrocarbon having 1 to 30 carbon atoms which may have a substituent, from the viewpoints that the moisture-heat resistance of a cured product of the polymerizable composition becomes further good and the heat resistance, adhesion and optical properties of the cured product become also goodA group or an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent. From the same viewpoint, the aromatic hydrocarbon ring-containing group is preferably an aromatic hydrocarbon ring having a monocyclic structure, and more preferably a group in which 2 aromatic hydrocarbon rings having a monocyclic structure are linked. In addition, from the point of view of the polymerizable composition for better moist heat resistance, preferably 2 aromatic hydrocarbon ring through the-S-connection. In addition, from the standpoint of improving heat resistance of a cured product of the polymerizable composition, the aromatic hydrocarbon ring-containing group preferably has a substituent. Further, from the viewpoint of compatibility, the substituent is preferably an alkyl group having 1 to 10 carbon atoms or a hydroxyl group, and more preferably an aromatic hydrocarbon ring-containing group is substituted with an alkyl group or a hydroxyl group. The alkyl group is preferably branched. Examples of the alkyl group having 1 to 10 carbon atoms include the above-mentioned R 1 The alkyl group having 1 to 10 carbon atoms out of the alkyl groups having 1 to 30 carbon atoms shown. From the same viewpoint, the number of carbon atoms of the aliphatic hydrocarbon group represented by D is preferably 5 to 20, more preferably 8 to 19, and even more preferably 10 to 15. The aliphatic hydrocarbon group is preferably an alkyl group which may have a substituent, more preferably an alkyl group which does not have a substituent. In the case where the 1-valent group represented by D is an aliphatic hydrocarbon that may have a substituent, R 1 Preferably a group in which 1 or more methylene groups in the aliphatic hydrocarbon group having 5 to 23 carbon atoms which may have a substituent or the aliphatic hydrocarbon group having 5 to 23 carbon atoms which may have a substituent are substituted with-COO-or-OCO-, more preferably a group in which 1 or more methylene groups in an aliphatic hydrocarbon group having 5 to 23 carbon atoms which may have a substituent are substituted with-COO-or-OCO-, more preferably a group in which 1 or more methylene groups in an alkyl group having 5 to 23 carbon atoms which may have a substituent is substituted with-COO-or-OCO-, more preferably, the unsubstituted alkyl group has 9 to 23 carbon atoms and 1 methylene group is replaced with-COO-or-OCO-. By setting the number of carbon atoms of the aliphatic hydrocarbon group to the above-described range, compatibility and heat resistance become further excellent. In addition, through R 1 The heat resistance is further improved by having-COO-or-OCO-in its structure. From the viewpoint of the resistance to heat and humidity,R 1 the number of-COO-and-OCO-in the group represented is preferably 1 to 3, more preferably 1 to 2.
When n in the formula (I-A) is 2, Y in the formula (1) is selected from the group consisting of a cured product of the polymerizable composition having further improved wet heat resistance and improved heat resistance, adhesion and optical properties 10 preferably-S-. In Y 10 In the case of-S-, Z is preferred 1 Z is as follows 2 Is a C1-30 aliphatic hydrocarbon group having 2 valences, which may have a substituent, or Z 1 Z is as follows 2 A compound which is a 2-valent aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms and may have a substituent.
Z is a component of the polymerizable composition which is excellent in moisture and heat resistance of a cured product thereof and in heat resistance, adhesion and optical characteristics of the cured product 1 Z is as follows 2 The aliphatic hydrocarbon group having 2 valence and 1 to 30 carbon atoms represented is preferably an alkylene group having 1 to 30 carbon atoms. From the same point of view, the alkylene group is preferably linear. In addition, the alkylene group preferably has no substituent. Further, from the standpoint of compatibility, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 4.
Z is a component of the polymerizable composition which is excellent in moisture and heat resistance of a cured product thereof and in heat resistance, adhesion and optical characteristics of the cured product 1 Z is as follows 2 The group containing an aromatic hydrocarbon ring having 2 valences of 6 to 30 carbon atoms represented is preferably an aromatic hydrocarbon ring having a monocyclic structure, and more preferably a phenylene group. The aromatic hydrocarbon ring-containing group preferably has a substituent. The substituent is preferably an alkyl group having 1 to 10 carbon atoms. From the standpoint of compatibility, the alkyl group is preferably branched. Examples of the alkyl group having 1 to 10 carbon atoms include the above-mentioned R 1 The alkyl group having 1 to 10 carbon atoms out of the alkyl groups having 1 to 30 carbon atoms shown.
When n in the formula (I-A) is 4, the moisture and heat resistance of the cured product of the polymerizable composition are further improved, and the heat resistance, adhesion and light of the cured product are improvedY in formula (3) is from the viewpoint of improving the chemical properties 12 The aliphatic hydrocarbon group having 4 valence and 1 to 30 carbon atoms is preferable, and the alkane tetrayl group having 1 to 30 carbon atoms is more preferable. The number of carbon atoms of the alkane tetrayl group is preferably 1 to 10, more preferably 1 to 7.
Z in formula (3) 1 、Z 2 、Z 3 Z is as follows 4 Preferably a direct bond.
The thioether compound (A) of the present invention is preferably a compound represented by the following general formula (I-B) in that the wet heat resistance of a cured product of the polymerizable composition is further improved and the heat resistance and adhesion of the cured product are also improved.
[ chemical formula 7A ]
(wherein R is 11 The aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent, and 1 or more methylene groups in the aliphatic hydrocarbon group having 1 to 30 carbon atoms are selected from the group consisting of<Group A1>The group obtained by substitution of the 2-valent group, or 1 or more methylene groups in the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms are selected from the group consisting of<Group A1>A group obtained by substitution of a 2-valent group in (a) is,
n1 represents an integer of 1 to 6,
d1 represents a group in which 1 or more methylene groups in an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent or an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent are substituted with a 2-valent group selected from the following < group A1 >.
<Group A1>：-O-、-CO-、-COO-、-OCO-、-NR 2a -、-NR 3a CO-or-S-
R 2a R is R 3a Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. )
As R 11 The table ofExamples of the aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent and the group having 6 to 30 carbon atoms which may have a substituent and containing an aromatic hydrocarbon ring include those mentioned above as R 1 The aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent and the group having 6 to 30 carbon atoms which may have a substituent are the same groups as those of the group containing an aromatic hydrocarbon ring.
Examples of the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent represented by D1 include those mentioned above for R 1 The same groups as those containing an aromatic hydrocarbon ring having 6 to 30 carbon atoms and optionally having a substituent are represented.
As a means of<Group A1>R in (a) 2a R is R 3a Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by the formula (I) include those mentioned above as R 2 R is R 3 The same hydrocarbon group as the hydrocarbon group having 1 to 30 carbon atoms is represented.
R in the above general formula (I-B) is a group that provides a cured product of the polymerizable composition with further improved wet heat resistance and improved heat resistance, adhesion and optical properties 11 An aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent is preferable. From the same point of view, the aliphatic hydrocarbon group is preferably an alkyl group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 10, more preferably 4 to 8. The aliphatic hydrocarbon group is preferably unsubstituted.
In view of further improving the wet heat resistance of a cured product of the polymerizable composition and improving the heat resistance, adhesion and optical properties of the cured product, n1 in the general formula (I-B) is preferably 1 to 4, more preferably 2 to 3.
The aromatic hydrocarbon ring-containing group represented by D1 in the general formula (I-B) is preferably an aromatic hydrocarbon ring having a monocyclic structure, and more preferably a phenyl group, from the viewpoint that the moisture-heat resistance of a cured product of the polymerizable composition becomes further good and the heat resistance, adhesion and optical properties of the cured product become also good. The number of carbon atoms of the aromatic hydrocarbon ring-containing group is preferably 6 to 20, more preferably 6 to 16, and still more preferably 6 to 110. In addition, from the polymerizabilityThe aromatic hydrocarbon ring-containing group preferably has a substituent in view of improving heat resistance of a cured product of the composition. The substituent is preferably an alkyl group having 1 to 10 carbon atoms, particularly 1 to 4 carbon atoms, or a hydroxyl group, and more preferably an aromatic hydrocarbon ring-containing group is substituted with an alkyl group and a hydroxyl group, from the viewpoint of compatibility. The alkyl group having 1 to 10 carbon atoms includes the above-mentioned R 1 The alkyl group having 1 to 10 carbon atoms out of the alkyl groups having 1 to 30 carbon atoms shown.
In the present invention, as the thioether compound (a), commercially available ones can be used. Examples of the commercial products of the thioether compound (A) include ADK STAB AO-412S, ADK STAB AO-503 and ADK STAB AO-26 (manufactured by Kyowa Co., ltd., ai Dike); irganox PS800FL, irganox PS802FL (manufactured by BASF corporation), and the like.
In the present invention, 1 kind of the above-mentioned thioether compound may be used alone, or 2 or more kinds may be used in combination. When 2 or more thioether compounds are used in combination, it is preferable to use a compound represented by the formula (I-A) in combination with a compound represented by the formula (I-A) in which n is 2, in view of further improving the wet heat resistance of a cured product of the polymerizable composition and improving the heat resistance, adhesion and optical properties of the cured product.
The content of the thioether compound (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, still more preferably 0.3 part by mass or more and less than 3 parts by mass, and particularly preferably 0.4 part by mass or more and less than 2 parts by mass, based on 100 parts by mass of the cation polymerizable compound (B) described later, from the viewpoint of improving heat resistance and adhesiveness of the cured product of the polymerizable composition.
Next, the cationically polymerizable compound (B) contained in the polymerizable composition of the present invention will be described.
The cationically polymerizable compound in the present invention is a compound that causes a polymerization reaction or a crosslinking reaction by a cationic polymerization initiator activated by light irradiation or heating.
In the present invention, as the cationically polymerizable compound (B), a known cationically polymerizable compound may be used without particular limitation. Examples of the cationically polymerizable compound (B) include an epoxy compound and an oxetane compound (B4). From the viewpoint that the heat and humidity resistance of the polymerizable composition is further improved and the heat resistance and the adhesiveness are also improved, the cation polymerizable compound (B) preferably contains at least 1 selected from the group consisting of an alicyclic epoxy compound (B1), an aliphatic epoxy compound (B2), and an aromatic epoxy compound (B3).
In the present invention, the cationically polymerizable compound (B) preferably contains an alicyclic epoxy compound (B1) from the viewpoint of improving the curability of the polymerizable composition. The alicyclic epoxy compound has an oxidized cycloolefin structure and does not have an aromatic ring.
The oxidized cycloolefin structure is a structure in which an aliphatic ring and an epoxy ring share a part of a 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 1 cycloolefin oxide structure in 1 molecule, or may have 2 or more structures. The alicyclic epoxy compound (B1) preferably has 1 or 2 cycloolefin oxide structures in 1 molecule, from the viewpoint that the moisture and heat resistance of a cured product of the polymerizable composition becomes further good and the heat resistance, adhesion and optical properties of the cured product also become good.
Examples of the alicyclic epoxy compound having a 1-epoxycycloolefin 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-epoxy2-epoxyethylcyclohexane, and limonene dioxide.
Examples of the alicyclic epoxy compound having a 2-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate, 3, 4-epoxy-1-methylcyclohexyl-3, 4-epoxy-1-methylhexane carboxylate, 6-methyl-3, 4-epoxycyclohexylmethyl-6-methyl-3, 4-epoxycyclohexane carboxylate, 3, 4-epoxy-3-methylcyclohexylmethyl-3, 4-epoxy-3-methylcyclohexane carboxylate, 3, 4-epoxy-5-methylcyclohexylmethyl-3, 4-epoxy-5-methylcyclohexane carboxylate, bis (3, 4-epoxycyclohexylmethyl) adipate, propane-2, 2-diyl-bis (3, 4-epoxycyclohexane), 2-bis (3, 4-epoxycyclohexyl) propane, ethylene bis (3, 4-epoxycyclohexane carboxylate) and the like are given.
As the alicyclic epoxy compound (B1), commercially available ones can be used. Specific examples of the commercial products include CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2000, CELLOXIDE 3000 (manufactured by Daicel), LDO (manufactured by Symrise), and the like.
In the present invention, 1 kind of the alicyclic epoxy compound (B1) may be used alone, or 2 or more kinds may be used in combination.
The content of the alicyclic epoxy compound (B1) in the cationically polymerizable compound (B) is preferably 1 to 20 parts by mass, more preferably 3 to 10 parts by mass, based on 100 parts by mass of the cationically polymerizable compound (B), from the viewpoint that the heat resistance and the adhesiveness of the cured product of the polymerizable composition are improved.
In the present invention, the cationic polymerizable compound (B) preferably contains the aliphatic epoxy compound (B2) from the viewpoint that the polymerizable composition is a composition having low viscosity and excellent handleability.
The aliphatic epoxy compound (B2) is a compound having 1 or more epoxy groups and having no aromatic ring and an oxidized cycloolefin structure. Examples of the aliphatic epoxy compound include monofunctional epoxy compounds and polyfunctional epoxy compounds. Examples of the monofunctional epoxy compound include glycidyl ethers of aliphatic alcohols and glycidyl esters of alkyl carboxylic acids. Examples of the polyfunctional epoxy compound include polyglycidyl ethers of aliphatic polyols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, and the like. In the present invention, the aliphatic epoxy compound (B2) is preferably monofunctional or 2-functional, from the viewpoint that the polymerizable composition is a composition having low viscosity and excellent handleability.
Representative examples of the aliphatic epoxy compound (B2) include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and polyglycidyl ethers of a polyhydric alcohol such as polyether polyol obtained by adding 1 or 2 or more alkylene oxides to an aliphatic polyhydric alcohol such as propylene glycol, trimethylolpropane, and glycerin. Examples of the aliphatic higher alcohol include monoglycidyl ether and glycidyl ester of a higher fatty acid, epoxidized soybean oil, octyl epoxystearate, butyl epoxystearate, epoxidized soybean oil, and epoxidized polybutadiene.
As the aliphatic epoxy compound (B2), commercially available ones can be used. Examples of the commercial products of the aliphatic epoxy compound (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, DENACOL EX-512, DENACOL EX-521, DENACOL EX-611, DENACOL EX-612, DENACOL EX-614, DENACOL EX-622, DENACOL EX-810, DENACOL EX-811, DENACOL EX-850, DENACOL EX-851, DENACOL EX-830, DENACOL EX-832, DENACOL EX-841, DENACOL EX-861, DENACOL EX-941, DENACOL EX-920, and DENACOL EX-911 (NagaseEX-31, manufactured by NACche Co., ltd); epoligo M-1230, epoligo 40E, epolight 100E, epolight 200E, epolight 400 6278P, epolight 200P, epolight 400P, epolight NP, epoligo 1600, epoligo 80MF, epoligo 100MF (manufactured by Kyowa Chemie Co., ltd.), ADEKA Glycirol ED-503, ADEKAGlycirol ED-503G, ADEKA Glycirol ED-506, ADEKA Glycirol ED-523T (manufactured by Kyowa Co., ltd.), EPOGEY 2EH (manufactured by Sichuan Kabushiki Kaisha), and the like.
In the present invention, 1 kind of the above aliphatic epoxy compound (B2) may be used alone, or 2 or more kinds may be used in combination.
The content of the aliphatic epoxy compound (B2) in the cationically polymerizable compound (B) is preferably 20 to 60 parts by mass, more preferably 30 to 50 parts by mass, based on 100 parts by mass of the cationically polymerizable compound (B), from the viewpoint that the heat resistance and the adhesiveness of the cured product of the polymerizable composition are improved.
In the present invention, the cation polymerizable compound (B) preferably contains the aromatic epoxy compound (B3) from the viewpoint of improving heat resistance of a cured product of the polymerizable composition.
The aromatic epoxy compound (B3) is a compound having an aromatic ring and at least 1 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 2-functional aromatic epoxy compound, from the viewpoint that the heat resistance of the cured product of the polymerizable composition is improved.
Examples of the monofunctional aromatic epoxy compound include a monohydric phenol having 1 aromatic ring such as phenol, cresol, and butylphenol, and a glycidyl ether compound of a compound obtained by further adding an alkylene oxide thereto.
Examples of the polyfunctional aromatic epoxy compound include glycidyl ethers of bisphenol a, bisphenol F, or a compound obtained by further adding an alkylene oxide thereto; glycidyl ethers of aromatic compounds having 2 or more phenolic hydroxyl groups such as resorcinol, hydroquinone and catechol; polyglycidyl etherate of aromatic compounds having at least 2 alcoholic hydroxyl groups such as xylylene glycol, and xylylene glycol; and glycidyl esters of polybasic acid aromatic compounds having 2 or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid.
As the aromatic epoxy compound (B3), commercially available ones can be used. Specific examples of the commercial products of the aromatic epoxy compound (B3) include DENACOL EX-121, DENACOL EX-141, DENACOL EX-142, DENACOL EX-145, DENACOL EX-146, DENACOL EX-147, DENACOL EX-201, DENACOL EX-203, DENACOL EX-711, DENACOL EX-721, ONCOAT EX-1020, ONCOAT EX-1030, ONCOAT EX-1040, ONCOAT EX-1050, ONCOAT EX-1051, ONCOAT EX-1010, ONCOAT EX-1011, and ONCOAT 1012 (manufactured by Nagasechinemtex Co.). OGSOL PG-100, OGSOL EG-200, OGSOL EG-210, OGSOL EG-250 (manufactured by Osaka Gas Chemicals Co.); HP4032, HP4032D, HP4700 (manufactured by DIC Co.); ESN-475V (manufactured by Nippon Kagaku Co., ltd.); epikote YX8800 (mitsubishi chemical company); marproof G-0105SA, marproof G-0130SP (manufactured by Nipple Co., ltd.); EPICLON N-665 and EPICLON HP-7200 (manufactured by DIC Co.); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-2000-L, NC-3000, NC-7000L (manufactured by Japanese chemical Co., ltd.); ADEKAGlycirol ED-501, ADEKA Glycirol ED-502, ADEKA Glycirol ED-509, ADEKA Glycirol ED-529, ADEKA RESIN EP-4000, ADEKARESIN EP-4005, ADEKARESIN EP-4100E, ADEKA RESIN EP-4901 (manufactured by Kyowa Co., ltd.); TECHMOREVG-3101L, EPOX-MKR, EPOX-MKR151 (manufactured by Printec), YX-4000 (manufactured by Mitsubishi Chemical), and the like.
In the present invention, 1 kind of the above aromatic epoxy compound (B3) may be used alone, or 2 or more kinds may be used in combination.
The content of the aromatic epoxy compound (B3) in the cationically polymerizable compound (B) is preferably 30 to 70 parts by mass, more preferably 40 to 60 parts by mass, based on 100 parts by mass of the cationically polymerizable compound (B), from the viewpoint that the heat resistance and the adhesiveness of the cured product of the polymerizable composition are improved.
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) from the viewpoint of improving heat resistance and adhesion of a cured product of the polymerizable composition.
The cation polymerizable compound (B) preferably contains an oxetane compound (B4) from the viewpoint that the wet heat resistance of the cured product of the polymerizable composition becomes further excellent.
The oxetane compound (B4) is a compound having at least 1 oxetanyl group and having no epoxy group. In the present invention, an oxetane compound having 1 or 2 oxetanyl groups is preferably used in view of further improving the wet heat resistance of the cured product of the polymerizable composition.
Examples of oxetane compounds having 1 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-hydroxybutoxymethyl) oxetane.
Examples of oxetane compounds having 2 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, 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-oxetanylmethoxy) oxetane, and methyl bisoxetane.
As the oxetane compound (B4), commercially available ones can be used. Examples of commercial products of OXETANE compounds include ARON OXETANE OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by east Asia Synthesis), ETERNACOLL OXBP, OXTP (manufactured by Yu Xingxing) and the like.
In the present invention, 1 kind of the oxetane compound (B4) may be used alone, or 2 or more kinds may be used in combination.
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, based on 100 parts by mass of the cationically polymerizable compound (B), from the viewpoint that the moisture-heat resistance of the cured product of the polymerizable composition is further improved and the heat resistance and the adhesiveness of the cured product are improved.
The content of the cationic polymerizable compound (B) in the polymerizable composition of the present invention is preferably 50 parts by mass or more and less than 99 parts by mass, more preferably 75 parts by mass or more and less than 99 parts by mass, and still more preferably 85 parts by mass or more and less than 99 parts by mass, based on 100 parts by mass of the solid content of the polymerizable composition, in view of further improving the wet heat resistance and heat resistance of the cured product of the polymerizable composition and improving the adhesiveness and optical characteristics of the cured product. The solid component is a component obtained by removing a solvent described later from the polymerizable composition.
Next, the cationic polymerization initiator (C) contained in the polymerizable composition of the present invention will be described.
In the present invention, the cationic polymerization initiator (C) is a compound capable of releasing a substance that initiates cationic polymerization by irradiation with light or heating.
In the present invention, as the cationic polymerization initiator (C), a photo-cationic polymerization initiator or a thermal cationic polymerization initiator may be used. In the present invention, the cationic polymerization initiator (C) is preferably a cationic polymerization initiator from the viewpoint of low cure shrinkage and excellent adhesion.
The photo-cation polymerization initiator may be any compound as long as it is a compound capable of emitting a substance that initiates cation polymerization by irradiation with light, and is preferably a double salt that is an onium salt that emits a lewis acid by irradiation with light, or a derivative thereof.
Examples of the onium salt include double salts or derivatives thereof, and examples thereof include salts of cations and anions represented by the following general formula (i).
[A] m+ [B] m- (i)
Here, the cation [ A ]] m+ Onium, the structure of which can be represented by the following general formula, for example.
[(R 110 ) x Q] m+ (ii)
In the above general formula (ii), R 110 An organic group having 1 to 60 carbon atoms and containing several atoms other than carbon atoms.
x represents an integer of 1 to 5.
x R 110 Independent of each other, may be the same or different.
x R 110 At least 1 of (a) represents the above-mentioned organic group having an aromatic ring.
Q represents an atom or an atomic group selected from the group consisting of S, N, se, te, P, as, sb, bi, O, I, br, cl, F and n=n. In addition, in the case of cation [ A ]] m+ When the valence of Q in (a) is Q, the relationship of m=x-Q must be established. Where n=n is treated as valence 0.
Furthermore, anions [ B ]] m- Preferably, the structure of the halide complex is represented by the following general formula (iii).
[LX y ] m- (iii)
In the above general formula (iii), L represents a metal or a semi-metal (metal) as a 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. Furthermore, in the case of the anion [ B ]] m- When the valence of L in (a) is p, the relationship of m=y-p must be established.
As the anion [ LX ] of the above general formula (iii) y ] m- Specific examples of (C) include tetrakis (pentafluorophenyl) borate 6 F 5 ) 4 B] - Tetrafluoroborate (BF) 4 ) - Hexafluorophosphate (PF) 6 ) - Hexafluoroantimonate (SbF) 6 ) - Hexafluoroarsenate (AsF) 6 ) - Hexachloroantimonate (SbCl) 6 ) - Tris (pentafluoromethyl) trifluorophosphate ion (FAP anion), and the like.
Furthermore, anions [ B ]] m- The structure represented by the following general formula (iv) may be used.
[LX y-1 (OH)] m- (iv)
L, X and b are the same as described above.
Examples of other anions include perchlorate ion (ClO 4 ) - Trifluoromethyl sulfite ion (CF) 3 SO 3 ) - Fluorosulfonate ion (FSO) 3 ) - Toluene sulfonate anion, trinitrobenzene sulfonate anion, camphor sulfonate, nonafluorobutane sulfonate, hexadecane sulfonate, tetraaryl borate, tetra (pentafluorophenyl) borate, and the like.
Among such onium salts, sulfonium salts of the group I or group II, which are described below, and sulfonium salts of anions such as hexafluorophosphate, hexafluoroantimonate, tetrakis (pentafluorophenyl) borate, are preferred in terms of good curability of the polymerizable composition and good adhesion of the cured product of the polymerizable composition.
[ chemical formula 8]
< group I >
[ chemical formula 9]
< group II >
As the photo cation polymerization initiator, commercially available ones can be used. Examples of the commercial products of the photo-cation polymerization initiator include "KAYARAD (registered trademark) PCI-220" and "KAYARAD (registered trademark) PCI-620" manufactured by Nippon chemical Co., ltd; "UVI-6990" manufactured by Dow Chemical company; "ADEKA ARKLS (registered trademark) SP-150", "ADEKA OPTOMER (registered trademark) SP-170", and "ADEKA OPTOMER (registered trademark) SP-500", manufactured by Kyowa Corp. Ai Dike; "CI-5102", "CIT-1370", "CIT-1682", "CIP-1866S", "CIP-2048S", "CIP-2064S" manufactured by Cao Corp; "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 Kagaku; "PI-2074" manufactured by Rhodia Co., ltd; and CPI-100P manufactured by San-Apro.
The content of the photo-cationic polymerization 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, based on 100 parts by mass of the cationic polymerizable compound, from the viewpoint that the adhesiveness of the cured product of the polymerizable composition is good and the curability of the polymerizable composition is good.
In the present invention, as the thermal cationic polymerization initiator, a compound that generates a cationic species or a lewis acid by heating may be used without particular limitation. Specifically, salts such as sulfonium salts, thiophenium salts (Japanese text: frame material), benzyl ammonium, pyridinium salts, and hydrazine 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; a polyepoxide addition modified product produced by reacting the above polyamine with various epoxy resins such as phenyl glycidyl ether, butyl glycidyl ether, glycidyl ethers such as bisphenol a-diglycidyl ether and bisphenol F-diglycidyl ether, or glycidyl esters of carboxylic acids by a conventional method; amidated modified products produced by reacting the organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid, dimer acid, etc. by a conventional method; a mannich modified product produced by reacting the polyamine with an aldehyde such as formaldehyde, and a phenol having at least 1 hydroformylation-reactive site in a core such as phenol, cresol, xylenol, t-butylphenol, resorcinol, etc., by a conventional method; anhydrides of polycarboxylic acids (aliphatic dicarboxylic acids such as 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-methylglutaric acid, 2-methylsuberic acid, 3, 8-dimethylsebacic acid, 3, 7-dimethylsebacic acid, hydrodimer acid, dimer acid, and other aromatic dicarboxylic acids, phthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and other alicyclic dicarboxylic acids, such as cyclohexane dicarboxylic acid, tricarboxylic acids, trimers of trimellitic acid, trimesic acid, castor oil fatty acid, and other tetracarboxylic acids, such as pyromellitic acid); dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, amine imides, and the like.
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, more preferably 0.1 to 8 parts by mass, based on 100 parts by mass of the cationic polymerizable compound (B), from the viewpoint that the curability of the polymerizable composition is improved.
As the thermal cationic polymerization initiator, commercially available ones can be used. Examples of the commercially available thermal cationic polymerization initiator include Adeka Opton CP-77, adeka Opton CP-66 (manufactured by Kabushiki Kaisha Ai Dike), CI-2639, CI-2624 (Japan Cauda), san-Aid SI-60, san-Aid SI-80 and San-Aid SI-100 (manufactured by Sanxinafol chemical industry).
The polymerizable composition of the present invention may contain a solvent in which the thioether compound (a), the cationically polymerizable compound (B) and the cationic polymerization initiator (C) are soluble or dispersible. The solvent is a compound which is not classified into the above components and is liquid at 25 ℃ under 1 atmosphere. 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, dipropylene glycol dimethyl ether, and the like; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (Texanol); cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, isopropanol or n-propanol, isobutanol or n-butanol, and pentanol; ether ester solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), 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, D-limonene, pinene, etc.; paraffin solvents such as mineral spirits, SWASOL #310 (COSMO pine oil (co)), solvoso #100 (Exxon chemical (co)), and the like; halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1, 2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; propylene carbonate, carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, and the like, and these solvents may be used as a mixed solvent of 2 or more.
The polymerizable composition of the present invention may be optionally added with various resin additives such as other monomers, other polymerization initiators, inorganic fillers, organic fillers, pigments, colorants such as dyes, photosensitizers, defoamers, thickeners, surfactants, leveling agents, flame retardants, thixotropic agents, diluents, plasticizers, stabilizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flow regulators, adhesion promoters, and the like.
The total amount of any components other than the thioether compound (a), the cation polymerizable compound (B) and the cation polymerization initiator (C) in the polymerizable composition of the present invention also varies depending on the use of the present invention, but is preferably set to 20 parts by mass or less, particularly 10 parts by mass or less, per 100 parts by mass of the cation polymerizable compound (a) from the viewpoint of further improving the effect of the present invention.
The polymerizable composition of the present invention is obtained by combining a thioether compound (A), a cationically polymerizable compound (B) and a cationic polymerization initiator (C). Even if the thioether compound (a) is combined with the radical polymerizable composition and the radical polymerization initiator, the effect of the present invention that a cured product having good wet heat resistance can be obtained is not exhibited. Further, the cured product of the polymerizable composition containing the radical polymerizable composition and the radical polymerization initiator has poor adhesion. Therefore, the polymerizable composition of the present invention preferably does not contain a radical polymerizable composition or a radical polymerization initiator.
The radical polymerizable composition is a compound capable of undergoing radical polymerization. Examples of the radical polymerizable compound include compounds having an ethylenically unsaturated group such as an acrylic group, a methacrylic group, and a vinyl group. Specifically, examples thereof include radical polymerizable compounds described in Japanese patent application laid-open No. 2018/012383 and radical polymerizable organic substances described in Japanese patent application laid-open No. 2014/021023.
The radical polymerization initiator is a compound which generates a radical capable of initiating polymerization by exposure to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron rays, X rays, or the like or by heating. Specifically, examples thereof include acetophenone-based compounds, benzil-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and oxime ester-based compounds described in Japanese patent application laid-open No. 2018/012383, thermal radical polymerization initiators such as azo-based compounds, peroxides, and persulfates, and photo radical polymerization initiators described in Japanese patent application laid-open No. 2016-210849.
As a specific use of the polymerizable composition of the present invention, examples thereof include optical materials such as spectacles and imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, adhesives, printing plates, insulating varnishes, insulating sheets, laminated plates, printed boards, sealing agents such as sealants for semiconductor devices, LED encapsulation, liquid crystal injection ports, organic EL, optical elements, electrical insulation, electronic components and separation films, molding materials, putties, glass fiber impregnating agents, and the like a passivation film such as a filling agent, a semiconductor or solar cell, an interlayer insulating film, a protective film, a prism sheet used for a backlight of a liquid crystal display device, a lens portion of a lens sheet such as a fresnel lens sheet or a lenticular lens sheet used for a screen of a projection television or the like, an optical lens such as a microlens, an optical element, an optical connector, an optical waveguide, a molding casting agent for optical molding or the like, examples of the substrate that can be used as the coating agent include metal, wood, rubber, plastic, glass, and ceramic products.
The polymerizable composition of the present invention is excellent in moist heat resistance of a cured product by using the thioether compound (a), the cationic polymerizable compound (B) and the cationic polymerization initiator (C) in combination. In addition, the polymerizable composition of the present invention is excellent in heat resistance, adhesiveness and optical properties by using these components in combination. Therefore, the polymerizable composition of the present invention is particularly useful as an adhesive, particularly a photocurable adhesive.
Next, the photocurable adhesive of the present invention will be described.
The photocurable adhesive of the present invention contains the polymerizable composition of the present invention. The photocurable adhesive of the present invention contains the polymerizable composition of the present invention, and therefore is excellent in moist heat resistance. In addition, the photocurable adhesive of the present invention is excellent in 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 an active energy ray or heating the polymerizable composition. The irradiation conditions and heating conditions of the active energy rays are not limited, and known conditions may be employed.
Next, the use of the polymerizable composition of the present invention as a photocurable adhesive will be described.
In the present invention, the polymerizable composition is used as a photocurable adhesive for bonding 2 members by irradiation with light. The amount of the polymerizable composition to be used, the method to be applied to the member, the wavelength of the light to be irradiated, the amount of the light to be irradiated, and the like are not particularly limited, and known methods and conditions can be appropriately employed. Further, according to the present invention, there is also provided a method of bonding 2 members by the above-mentioned polymerizable composition. Specifically, the polymerizable composition is placed between 2 members, and then the polymerizable composition is irradiated with light to cure the polymerizable composition, thereby bonding the 2 members.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
Examples and comparative examples
The polymerizable compositions 1 to 21 of examples 1 to 21 and the polymerizable compositions of comparative examples 1 and 2 were prepared by thoroughly mixing the respective components in the following formulation shown in tables 1 to 3. The symbols in the table refer to the following components. In addition, the numerical values in the table represent parts by mass.
A-1: a compound represented by the following formula (A-1)
A-2: a compound represented by the following formula (A-2)
A-3: a compound represented by the following formula (A-3)
A-4: a compound represented by the following formula (A-4)
A-5: a compound represented by the following formula (A-5)
A-6: a compound represented by the following formula (A-6)
A-7: a compound represented by the following formula (A-7)
A' -1: a compound represented by the following formula (A' -1)
[ chemical formula 10]
[ chemical formula 11]
[ chemical formula 12]
[ chemical formula 13]
/>
[ chemical formula 13A ]
[ chemical formula 13B ]
[ chemical formula 13C ]
[ chemical formula 14]
B1-1: a compound represented by the following formula (B1-1)
B1-2: a compound represented by the following formula (B1-2)
B2-1: a compound represented by the following formula (B2-1)
B2-2: a compound represented by the following formula (B2-2)
B3-1: a compound represented by the following formula (B3-1)
B3-2: a compound represented by the following formula (B3-2)
B3-3: a compound represented by the following formula (B3-3)
B3-4: a compound represented by the following formula (B3-4)
B4-1: a compound represented by the following formula (B4-1)
B4-2: a compound represented by the following formula (B4-2)
[ chemical formula 15]
[ chemical formula 16]
[ chemical formula 17]
[ chemical formula 18]
[ chemical formula 19]
[ chemical formula 20]
[ chemical formula 21]
[ chemical formula 22]
/>
[ chemical formula 23]
[ chemical formula 24]
C-1: a50% by mass solution of propylene carbonate of a compound represented by the following formula (C1-2)
C-2: a50% by mass solution of propylene carbonate of a compound represented by the following formula (C2)
[ chemical formula 25]
[ chemical formula 26]
The wet heat resistance, adhesiveness and optical properties of the cured products of the polymerizable compositions prepared in examples and comparative examples were evaluated by the following methods. The results are shown in tables 1 to 3.
< adhesion test >
The compositions prepared in examples and comparative examples were applied to TAC films (Fujitac TD80, fuji photo Co., ltd.) so that the film thickness after curing became 3. Mu.m, respectively, to form coating films. Then, a COP (cycloolefin polymer, model No. ZeonorFilm 14-060 manufactured by Japanese Zeon Co., ltd.) film subjected to corona discharge treatment was bonded to the surface of the TAC film on which the coating film was formed using a laminator to obtain a laminate. Then, the laminate was irradiated with a light corresponding to 1000mJ/cm through a COP film using an electrodeless ultraviolet lamp 2 And bonding them together to produce a test piece.
The test piece obtained was stored at 30℃under 50% RH and atmospheric pressure for a period of 12 hours after exposure. Next, a sample for evaluation was obtained by cutting out a test piece to a width of 2.0 cm. The obtained samples were subjected to a 90-degree peel test, and the adhesiveness of the samples for evaluation was evaluated according to the following criteria. The 90 degree peel test was performed at 30℃under 50% RH and atmospheric pressure. The larger the value of N/2cm, the more excellent the adhesion.
A:2.5N/2cm or more or substrate breakage
B:1.5N/2cm or more and less than 2.5N/2cm
C:0.5N/2cm or more and less than 1.5N/2cm
D: below 0.5N/2cm.
< test of moist Heat >
Test pieces were obtained in the same manner as in the adhesion test. The test piece obtained was kept at 85℃and 85% RH for 500 hours. After the test piece was cooled to room temperature, a 90-degree peel test was performed on the test piece in the same manner as in the adhesion test, and the wet heat resistance of the evaluation sample was evaluated according to the following criteria. The larger the value of N/2cm, the more excellent the wet heat resistance.
A:1.5N/2cm or more
B:1.0N/2cm or more and less than 1.5N/2cm
C:0.5N/2cm or more and less than 1.0N/2cm
D: below 0.5N/2cm
< test of optical Properties >
The polymerizable compositions prepared in examples and comparative examples were applied to glass plates so that the film thickness after curing became 50. Mu.m, and then, the other glass plates were bonded to the surfaces of the glass plates on which the coating films were formed. Irradiation of the laminated glass plate with a high-pressure Hg lamp of 1000mJ/cm 2 The glass plate was then heated at 150℃for 1 hour to obtain a test piece.
The optical properties of the obtained test pieces were evaluated according to the following criteria by measuring b x of the obtained test pieces using an ultraviolet-visible near infrared spectrophotometer V-670 (manufactured by japan spectroscopic corporation). The smaller the value of b, 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 and less than 10
C: b of the cured product is 10 or more
< test for Heat resistance >
Test pieces were obtained in the same manner as in the optical property test. The resulting test piece b was measured using an ultraviolet-visible near infrared spectrophotometer V-670 (manufactured by japan spectroscopy). Next, the test piece was kept at 85 ℃ and 85% rh for 500 hours, and then b was measured. The heat resistance of the test piece was then evaluated according to the following criteria. The smaller Δb is, the more excellent the heat resistance is.
A：Δb*＜3
B：3≤Δb*＜5
C：5≤Δb*＜8
D：8≤Δb*
/>
TABLE 3 Table 3
As shown in tables 1 to 3, the cured products of the polymerizable compositions of examples 1 to 21 were excellent in wet heat resistance. These cured products are also excellent in heat resistance, adhesion and optical properties. In contrast, the cured product of the polymerizable composition of comparative example 1 containing no thioether compound (a) was poor in heat resistance in addition to poor in moist heat resistance. In addition, the cured product of the polymerizable composition of comparative example 2 containing the other component (a' -1) in addition to the thioether compound (a) was poor in heat resistance and optical properties in addition to poor in wet heat resistance.

Claims (15)

1. A polymerizable composition comprising a thioether compound (A), a cationically polymerizable compound (B) and a cationic polymerization initiator (C).
2. The polymerizable composition according to claim 1, wherein the thioether compound (A) has an ester bond in a molecule.
3. The polymerizable composition according to claim 1 or 2, wherein the thioether compound (A) has a group represented by the following general formula (I),
wherein R is 1 The aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent, and 1 or more methylene groups in the aliphatic hydrocarbon group having 1 to 30 carbon atoms are selected from the group consisting of<Group A>The group obtained by substitution of the 2-valent group in (a) or 1 or more methylene groups in the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms are selected from the group consisting of<Group A>A group obtained by substitution of a 2-valent group in (a) is,
Y 1 represents a substituent-containing 2-valent hydrocarbon group having 1 to 30 carbon atoms or 1 or more methylene groups in the 2-valent hydrocarbon group having 1 to 30 carbon atoms, and is selected from the group consisting of<Group A>A group obtained by substitution of a 2-valent group in (a) is,
* The bonding site is indicated as being the bonding site,
<group A>：-O-、-CO-、-COO-、-OCO-、-NR 2 -、-NR 3 CO-, or-S-, R 2 R is R 3 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
4. The polymerizable composition according to claim 3, wherein R in the general formula (I) 1 Is an aliphatic hydrocarbon group having 5 to 20 carbon atoms which may have a substituent or an aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms which may have a substituent.
5. The polymerizable composition according to claim 3 or 4, wherein Y in the general formula (I) 1 Is a 2-valent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.
6. The polymerizable composition according to any one of claims 3 to 5, wherein the thioether compound (A) has a plurality of groups represented by the general formula (I) in the molecule.
7. The polymerizable composition according to claim 1, wherein the thioether compound (A) is a compound represented by the following general formula (I-B),
wherein R is 11 The aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent, and 1 or more methylene groups in the aliphatic hydrocarbon group having 1 to 30 carbon atoms are selected from the group consisting of<Group A1>The group obtained by substitution of the 2-valent group in (a) or 1 or more methylene groups in the aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms are selected from the group consisting of<Group A1>A group obtained by substitution of a 2-valent group in (a) is,
n1 represents an integer of 1 to 6,
d1 represents an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent or an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms which may have a substituent,
<Group A1>：-O-、-CO-、-COO-、-OCO-、-NR 2a -、-NR 3a CO-or-S-
R 2a R is R 3a Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
8. The polymerizable composition according to claim 7, wherein D1 in the general formula (I-B) has an aromatic hydrocarbon ring having a monocyclic structure.
9. The polymerizable composition according to claim 7 or 8, wherein R in the general formula (I-B) 11 Is an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.
10. The polymerizable composition according to any one of claims 1 to 9, wherein the sulfide compound (a) is contained in an amount of 0.1 parts by mass or more and less than 10 parts by mass based on 100 parts by mass of the cationically polymerizable compound (B).
11. The polymerizable composition according to any one of claims 1 to 10, wherein the cationically polymerizable compound (B) contains at least 1 selected from the group consisting of an alicyclic epoxy compound (B1), an aliphatic epoxy compound (B2) and an aromatic epoxy compound (B3).
12. A photocurable adhesive comprising the polymerizable composition according to any one of claims 1 to 11.
13. A method for producing a cured product, comprising the step of irradiating the polymerizable composition according to any one of claims 1 to 11 with active energy rays or the step of heating the composition.
14. A cured product of the polymerizable composition according to any one of claims 1 to 11.
15. The use of the polymerizable composition according to any one of claims 1 to 11 as a photocurable adhesive.
CN202280012229.XA 2021-03-31 2022-03-28 Polymerizable composition, photocurable adhesive, method for producing cured product, and cured product Pending CN116745337A (en)

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